MODERN ASPECTS OF ELECTROCHEMISTRY No. 16 - B. E. CONWAY PDF

MODERN ASPECTS OF
ELECTROCHEMISTRY
No. 16
Edited by
B . E . C O N W A Y
Department of Chemistry
University of Ottawa
Ottawa, Ontario, Canada
R A L P H E . W H I T E
Department of Chemical Engineering
Texas A&M University
College Station, Texas
and
J . O 'M . B O C K R I S
Department of Chemistry
Texas A&M University
College Station, Texas
PLENUM PRESS NEW YORK AND LONDON
The Library of Congress cataloged the first volume of this title as follows:
Modern aspects of electro chemistry, no . [1]
Washingto n, Butterwo rths, 1954-
v. illus. , 23 cm.
No . 1-2 issued as Modern aspects series of chemistry.
Edito rs: no . 1- J. Bockris (with B. E. Conway, No . 3- )
Imprint varies: no . 1, New Yo rk, Academic Press.No . 2, Lo ndo n , Butterwo rths.
1. Electro chemistry-Co llected wo rks. I. Bo ckris, Jo hn O'M. ed. II. Conway, B. E.
ed. (Series: Mo dern aspects series of chemistry)
QD552.M6 54-12732 rev
ISBN 0-306-42024-4^
1985 Plenum Press, New York
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L I S T O F C O N T R I B UT O R S
B R I A N E . C O N W A Y
Department of C hemistry
University of O ttawa
O ttawa, O ntario K I N 9B 4, C anada
S . E FR I M A
B en-Gurion University of T he N egev
B eer-S heva, Israel 84105
Y U. Y A . GUR E VI C H
A . N . Frumkin I nstitute of E lectrochemistry
A cademy of S ciences of the US S R
M oscow, US S R
A . H A M E L I N
L aboratoire d' E lectrochimie I nterfaciale du C N R S
92195 M eudon C edex, France
Y U. V. P L E S K O V
A . N . Frumkin I nstitute of E lectrochemistry
A cademy of S ciences of the US S R
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P reface
This vo lume of the Modern Aspects of Electrochemistry series co n-
tains six chapters: four are o n to pics of current fundamental interest
in the subject and two deal with mo re techno lo gical aspects of
electro chemistry.
In Chapter 1, Anto inette Hamelin deals with the to pic of
characterizatio n of the do uble layer at well-defined single-crystal
faces of so lid metals. She also gives valuable instructio ns for the
preparatio n and characterizatio n of single-crystal faces of kno wn
o rientatio n and index which will be very useful to many wo rkers
in this field, especially tho se who are just entering it as novices o r
to tho se who se crystals are no t always to o accurately characterized!
Most of the work repo rted is co ncerned with crystal faces of go ld
and silver which this autho r has specialized in studying. It is her
work in recent years that has taken experimental studies of do uble-
layer behavio r well beyo nd the co nventio nal area of research at
liquid mercury.
Chapter 2, by B. E. Co nway, deals with a curio us fundamental
but hitherto little-examined pro blem in electro de kinetics: the real
form of the Tafel equatio n with regard to the temperature depen-
dence of the Tafel-slo pe parameter b, co nventio nally written as
'b = RT/ aF\ where a is a transfer coefficient. He sho ws, extending
his 1970 paper and earlier wo rks of o thers, that this form of the
relatio n for b rarely represents the experimental behavio r for a
variety of reactio ns over any appreciable temperature range. Rather,
b is of the form RT/(a
H
+ a
s
T)F o r RT/ a'F + K, where a
H
and
a
s
are enthalpy and entro py co mpo nents of the transfer coefficient
(o r symmetry facto r for a o ne-step electro n transfer reactio n), and
K is a temperature-independent parameter, the apparent limiting
vi P reface
value of b for some systems at T = 0. These forms for b, required
by the o bserved experimental behavio r, imply that fundamental
aspects of the charge transfer and activatio n pro cess in electro de
reactio ns are no t at all fully understo o d yet. This chapter deals with
vario us po ssible interpretatio ns of the o bserved T dependence of
b
9
including the to pic of po tential dependence of the entropy of
activatio n of electro de pro cesses.
The electro chemistry of semico nducto rs has played a major
part in the develo pment of mo dern electro chemistry, especially in
recent years with regard to pho to electro chemical energy co nversio n
using illuminated semico nducto r electro des. Drs. Pleskov and
Gurevich of the Institute of Electro chemistry, Mo sco w, co ntribute
an impo rtant chapter (3) on "New Pro blems and Pro spects" in this
field. Readers will find that their chapter gives a tho ro ugh acco unt
of the current directio ns of develo pment in this field, as well as
some of the difficulties and new areas of research in this subject.
Surface-enhanced Raman scattering has been regarded, in
some ways, as the spectro sco pic "Go dsend" to electro chemists
trying to characterize submo no layer quantities of adso rbates at
electro de interfaces. Pro fesso r S. Efrima presents, in Chapter 4, a
mo numental and tho ro ughly referenced survey of the vast literature
o n this to pic that has grown in the past 14 years o r so . He presents
a "perso nal view" of this intriguing and often co ntro versial subject,
and attempts to distil o ut for the electro chemist what is of
quantitative significance in the many co ntributio ns that have been
made o n this to pic. He co ncludes by critically reviewing the vario us,
no t always mutually exclusive, theo ries of the o rigin of the SERS
effect.
Dr. Halina S. Wro blo wa, in Chapter 5, gives a valuable com-
parative acco unt of the current state of the art in develo pment of
batteries for vehicular transpo rtatio n. The Labo rato ry at Fo rd,
thro ugh Kummer, has been the "prime mo ver" in high-energy and
po wer-density battery develo pment, especially in the field of
so dium-sulfur battery systems. Dr. Wro blo wa herself has, for some
years, been* an active researcher in this field at Fo rd, so she brings
to bear o n this to pic substantial experience and an authentic critical
judgment of the viability of vario us systems that have been
engineered over the past 10-15 years, including the latest develo p-
ments.
P reface vii
The vo lume ends with a chapter o n "Structural and Transpo rt
Pro perties of Perfluo rinated Io n-Exchange Membranes" by Dr.
Richard S. Yeo and Pro fesso r Ho ward L. Yeager. The develo pment
of such membranes has revo lutio nized the electro chemical tech-
nology of the chlo rine-caustic industry and also has been of great
value in the engineering of water electro lyzers, o rganic preparatio n
cells and some designs of fuel cells. This chapter is no t only of
techno lo gical interest in the abo ve areas but deals in some detail
with fundamental pro blems of io n asso ciatio n, aggregatio n, mem-
brane structure and io n transpo rt in the so lutio n-invaded, lo cally
hydro pho bic medium which these po lymers pro vide in membranes.
University of Ottawa B. E. Co nway
Texas A&M University Ralph E. White
Texas A&M University J. O'M. Bockris
C ontents
Chapter 1
DO UB L E -L A Y E R P R O P E R T I E S A T sp A N D sd
M E T A L S I N GL E -C R Y S T A L E L E C T R O DE S
A . H amelin
I. Intro ductio n 1
II. Histo rical 3
III. Structure of Metals 4
1. Basis of Crystallo graphy 4
2. The Stereo graphic Pro jectio n 6
3. Determinatio n of Crystallo graphic Orientatio n 10
4. Mo dels o f Crystal Surfaces 15
5. Structure of Metal Surfaces 23
IV. Preparatio n of Single-Crystal-Face Electro des 28
1. Gro wing Single Crystals 28
2. Cutting the Crystal 32
3. Po lishing and Iso lating the Face of Interest 33
4. Final Surface Preparatio n 36
5. Ex Situ Check of State of Electro de Surface 37
6. In Situ Check o f State of Electro de Surface 38
V. Electro chemical Results 43
1. The pzc's 45
2. The So lutio n Side o f the o Hp 50
3. The Metal Side of the o Hp 58
4. The Ro ughness Facto r 94
5. Co nclusio ns 96
References 98
ix
x C ontents
Chapter 2
THE TEMPERATURE AND
POTENTIAL DEPENDENCE OF
ELECTROCHEMICAL REACTION RATES, AND
THE REAL FORM OF THE TAFEL EQUATION
Brian E. Co nway
I. Intro ductio n 103
1. Sco pe and Significance of this Article 103
2. Preliminary Definitio ns 104
3. The Tafel-Slo pe Parameter b 106
II. Origin o f Po tential Dependence o f Electro chemical
Reactio n Rates and the Co nventio nal Ro le of Tem-
perature 107
1. Theo retical Representatio ns of Rates of Electro de
Pro cesses 107
2. Relatio n of j3 to a 115
III. The Experimental Situatio n Regarding the Temperature
Dependence of Tafel Slo pes 116
1. General Remarks 116
2. Do cumentatio n and Examples of the Experimentally
Observed Dependence of b o n T and the Behavio r
of a with T 117
IV. Theo retical Discussio n 132
1. Interpretatio n o f the Case Where a is Pro po rtio nal
to T 132
2. General Case 134
3. A Questio n Abo ut the Electrical Energy Term /3VF
in the Rate Equatio n 135
4. Temperature-Dependent Orientatio n of So lvent
Dipo les in the Inner Regio n of the Do uble Layer and
the Entro py of Activatio n 138
5. Tafel Slo pes and Pro to n Tunneling 143
6. Behavio r of a with Temperature o n the Basis o f
Electro n and Particle Transfer Treatment of Ulstrup 147
7. No nlinear Po tential Dependence o f Electro chemical
Reactio n Rates 148
C ontents xi
8. Expansio n o f the Helmho ltz Layer with Temperature 155
9. Effects o f Specific Adso rptio n o f Anio ns 156
10. Tafel Slo pes fo r Reactio ns Pro ceeding in Multistep
Pathways 160
11. Tafel Slo pes in Relatio n to Exchange Current
Densities i
0
164
12. Electro de Area and Tafel Slo pes 167
V. Pro blems with Evaluatio n o f Heats o f Activatio n When
a is Temperature Dependent 168
1. Derivatio n o f the Apparent Heat o f Activatio n at the
Reversible Po tential 168
2. a and the Relatio n between Real and Apparent Heats
o f Activatio n 175
3. Experimental Evidence fo r the Po tential Dependence
o f the Entro py o f Activatio n, AS* 178
VI. Co nclusio ns and Final Remarks 182
References 185
Chapter 3
ELECTROCHEMISTRY OF SEMICONDUCTORS:
NEW PROBLEMS AND PROSPECTS
Yu. V. Plesko v and Yu. Ya. Gurevich
II. Characteristic Energy Levels in the Electro de/Elec-
tro lyte So lutio n System 190
1. The Electro chemical Po tential o f Electro ns in the
So lutio n Co ntaining a Redo x Co uple 191
2. Relatio nship between the Energy Scale and the Scale
o f Electro de Po tentials 196
3. Determinatio n o f the Reo rganizatio n Energy o f a
So lvent 199
III. Specific Features o f the Structure o f the Semico nduc-
to r/Electro lyte Interface 201
1. The Electrical Do uble-Layer Mo del 201
xii C ontents
2. Po tential Distributio n: "Pinning" o f Band Edges
and/o r the Fermi Level at the Surface 206
3. Determinatio n of the Flat-Band Po tential 210
IV. Quasithermo dynamic Appro ach to the Descriptio n of
Pho to electro chemical Pro cesses 216
1. Quasi-Fermi Levels 216
2. Descriptio n of the Mo st Impo rtant Types of Pho to -
electro chemical Reactio ns 218
3. Pho to co rro sio n and Stability 228
4. The Limits of Applicability of the Quasi-Fermi Level
Co ncept in Pho to electro chemical Kinetics: Alterna-
tive Appro aches 232
V. New Applicatio ns 236
1. Pho to electro chemical Co nversio n o f So lar Energy 236
2. Laser Etching o f Semico nducto rs 239
3. The Io n-Selective Field-Effect Transisto r 243
4. Characterizatio n of Semico nducting Materials 245
VI. Co ncluding Remarks 245
References 247
Chapter 4
SURFACE-ENHANCED
RAMAN SCATTERING (SERS)
S. Efrima
II. SERS Experimental Studies 255
1. Estimate of the Enhancement Facto r 256
2. Surface Preparatio n 271
3. So me Mo lecules and SERS Behavio r 291
4. Metals (o r So lids) which Exhibit SERS 307
5. Excitatio n Profiles 312
C ontents xiii
III. Theo retical Mo dels of SERS 322
1. General 322
2. Reso nance Mo dels (RE) 325
3. Electric Field and Emissio n Enhancement Mechan-
isms (LFE) 336
4. Dyes in SERSTheory 344
IV. What is "the" SERS Mechanism? 348
1. General 348
2. "The" SERS Mechanism 349
V. SERSA Useful To o l 350
References 357
Chapter 5
BATTERIES FOR VEHICULAR PROPULSION
Halina S. Wro blo wa
1. General Remarks 371
2. Battery Classificatio n 372
II. EV Battery Requirements 373
1. Perfo rmance-Related Requirements 375
2. Co st-Related Requirements 384
3. Safety and Enviro nmental Impact 389
III. Characteristics of Individual Systems 391
1. The Lead/Acid Battery 391
2. The Nickel-Iro n Battery 396
3. Zinc Batteries 399
4. High-Temperature Batteries 409
5. Rechargeable Lithium Batteries 417
6. Co nducting Po lymer Systems 418
7. Metal-Air Batteries 420
IV. Co mparative EV Battery Characteristics 423
References 427
xiv C ontents
Chapter 6
STRUCTURAL AND TRANSPORT PROPERTIES OF
PERFLUORINATED ION-EXCHANGE MEMBRANES
Richard S. Yeo and Ho ward L. Yeager
1. Histo rical Backgro und of Io n-Exchange Membrane
Cells 437
2. Requirements of High-Perfo rmance Membranes . . . 438
3. Develo pment of Perfluo rinated Io no mer Membranes 439
4. Types of Applicatio ns 440
5. The Sco pe of this Review 441
II. Micro structure 441
1. Structural Studies of Io no mers 441
2. Eisenberg's Theo ry 443
3. Io ns in Perfluo rinated Io no mers 445
4. Structural Mo dels of Nafio n 447
5. So lvatio n Pheno mena 450
III. Io n and Water Diffusion 459
1. Diffusio nal Pro perties in Dilute So lutio n Enviro n-
ments 460
2. Diffusio n Pro perties in Co ncentrated So lutio n
Enviro nments 465
IV. Transpo rt Pro perties under Industrial Electro lysis Co n-
ditio ns 470
1. Characteristics of Perfluo rinated Chlo r-Alkali Mem-
branes 471
2. Membrane Permselectivity in a Chlo r-Alkali Cell 472
3. Interpretatio n of Permselectivity as a Functio n of
Membrane Pro perties and Cell Parameters 475
V. Co nductivity and Permeability in Membranes 479
1. Co nductivity in Pure WaterSo lid Po lymer Elec-
tro lyte Systems 480
2. Co nductivity in Acidic Electro lytes 482
3. Co nductivity in Alkaline Electro lytes 485
4. Co nductivity of Nafio n in Pro tic So lvents 489
C ontents xv
5. Permeatio n of Mo lecular Species 490
VI. Co nclusio n 496
References 497
Index 505
Double-L ayer P roperties at sp and sd M etal
S ingle-C rystal E lectrodes
A. Hamelin
Laboratoire d'Electrochimie Interfaciale du CNRS,
92195 Meudon Cedex, France
I. INTRODUCTION
Writing such a chapter o n so lid metal electro des is a challenge
when, at every mo ment, the latest develo pments of surface science
give rise to new po ssibilities and new results in this area of elec-
tro chemistry. Ho wever, an attempt will be made to give an "up-to -
date snapsho t" of the state of affairs for the do uble layer at single-
crystal electro des of metals which are no t of the transitio n series.
Already in this Modern Aspects of Electrochemistry series the
theo ry and status of data for electro chemical do uble layers (dl)
were detailed,
1
"
3
but the sectio ns devo ted to results o btained with
so lid electro des and their discussio n were brief. Some aspects of
the dl on po lycrystalline metals, such as the po tential of zero charge
(pzc), were described.
4
In this series a chapter was also devo ted to
the metal-gas interface
5
; certainly the co mpariso n of this interface
with that at an electro de is fruitful, altho ugh the lo cal electric field
in the latter case can be varied far mo re easily.
Other basic bo o ks have dealt with dl pro perties witho ut giving
extensive discussio n of the dl at so lid electro des.
6
"
9
Altho ugh at
the end of the 1960s and beginning of the 1970s some reliable
results had been o btained o n po lycrystalline metals, their analysis
suffered from the unco ntro lled co mplexity of the surface structure.
2 A. Hamelin
This can be easily understo o d: When a po tential is applied to an
electro de the surface is an equipo tential but the different grains (of
different structures) at the surface have different densities of charge;
e.g., for a given po tential the density of charge can be zero for
certain patches of the electro de, po sitive for o thers, and negative
for o ther o nes (as lo ng as the patches are large eno ugh to create
their own lo cal electro chemical dl).
It will be useful to emphasize the practical aspects of the
pro blem which are two fo ld: the so lutio n side and the metal side.
On the so lutio n side at the interphase, a level of impurities which
do es no t interfere with dl measurements over the time scale of a
mercury-dro p lifetime, which is 4 s, co uld co mpletely hinder
o bservatio ns of significant current-po tential curves [*()] o r mean-
ingful differential capacity-po tential curves [C(E)] at a so lid metal
electro de which will stay 2, 3, o r 4 h in the same so lutio n. No t o nly
must the water, salts, and glassware be kept clean, but also the gas
used to remo ve oxygen and the tubing for the gas. Of co urse,
co nditio ns are less drastic for studies of stro ng adso rptio n than in
the case of no adso rptio n; also bacteria develo p less in acid so lutio ns
than in neutral o nes (which canno t be kept "unco ntaminated" mo re
than o ne o r two days). This aspect will no t be discussed in this
chapter.
The metal side of the electro chemical interphase must also be
rigo ro usly co ntro lled. Fo r crystal faces, this includes no t only the
chemical state but also the physical state of the to p layers of ato ms
at the surface (layers: 0,1,2 at least). Each metal brings specific
difficultiese.g., o ne o xidizes in air, ano ther do es no t; o ne has a
low melting po int, ano ther a high melting po int; o ne is hard, ano ther
is soft, etc. Practical requirements which are satisfacto ry for o ne
metal are no t necessarily valid for ano ther o ne. This aspect of the
pro blem is the subject of this chapter.
Both sides of the interface must be rigo ro usly clean for o bserva-
tio ns of the dl. The beginner will ask, "Ho w can I know that my
interphase is clean?" He o r she will be able to answer this questio n
by: o bservatio n of the i(E) curve in the dl range of po tential;
o bservatio n of the co ntributio n of the diffuse part of the dl o n the
C(E) curves in dilute so lutio ns (in the case of no specific adso rp-
tio n); co mpariso n of the i(E) and C(E) curves; o bserving the
stability of these two curves; etc. Co mpariso n with the results
Double-L ayer P roperties at M etal E lectrodes 3
published for po lycrystalline electro des of o ne metal gives indica-
tio ns of what sho uld be o bserved at faces of this metal (as lo ng as
they were o btained with great care). Furthermo re, as ex situ and
no nelectro chemical in situ metho ds beco me increasingly available
in labo rato ries, they will co ntribute to the co ntro l and understanding
of the electro chemical interphase.
I I . H I S T O R I C A L
A review paper
10
published in 1983 gives all references for dl work
at sp and sd metal faces up to July 1982, since then, numero us
o ther papers were published.
As in any rapidly develo ping field, many publicatio ns can claim
little mo re than being the first to examine such faces of a particular
metal in given co nditio ns. All publicatio ns except o ne (Ref. 11)
deal with results o btained in the aqueo us so lvent; all publicatio ns
except two (Refs. 12 and 13) deal with results o btained at ro o m
temperature. Faces of o nly seven no ntransitio n metals were studied
(Ag, Au, Cu, Zn, Pb, Sn, and Bi). Only for go ld has a large number
of high-index faces been studied in o rder to give a general view of
the influence of the crystallo graphic o rientatio n (co ) of the electro de
surface; these faces are distributed o nly o n the three main zo nes
of the unit pro jected stereo graphic triangle (see Sectio n III. 2), so
it wo uld be interesting to make faces having co 's which are inside
this triangle.
Fro m 1956 to the end of the 1960s dl pro perties were studied
by co nventio nal electro chemical metho ds, but during the last
decade a number of results o btained by o ptical measurements o r
o ther physical metho ds were published. It is so metimes difficult to
determine whether a paper pertains to the study of dl pro perties
o r to the study of the metal surface pro perties in the presence of
the electro chemical dl. All are of interest to electro chemists who
work with metal faces.
Anyway, experimental results on well-defined faces of no n-
transitio n metals are mo re and mo re numero us every year; their
understanding is related to the theo ries develo ped no t o nly from
results o btained o n mercury but also from kno wledge of so lid
surfaces.
4 A . H amelin
I I I . S T R UC T UR E O F M E T A L S
1. B asis of C rystallography
The essential characteristic of a single crystal is the perio dic nature
of its structure. Its ato mic structural arrangement can be related to
a netwo rk of po ints in space called the lattice. The co o rdinates of
a given po int in a lattice (o r ato m in a structure) are referred to as
the crystal axes, for instance, for the cubic system, axes at right
angles to each o ther. Seven different systems of axes are used in
crystallo graphy and there are seven crystal systems. The axes form
the edges of a parallelo piped called the unit cell which is the
fundamental building blo ck of the crystal. The unit cell has a definite
ato mic arrangement with lattice po ints at each co rner and, in some
cases, lattice po ints at the center of the face o r at the center of the
vo lume.
Most of the metals crystallize in the cubic system (face cen-
tered, bo dy centered). Zn and Cd crystallize in the hexago nal sys-
tem, Bi in the rho mbo hedral system, and Sn in the tetrago nal
system. In this chapter emphasis will be placed on the cubic sys-
tem, for Au, Ag, Cu, Pb, and so fo rth, are face-centered-cubic
metals (fee).
Miller indices are universally used as a system of no tatio n for
faces of a crystal. The o rientatio n of the plane of a face is given
relative to the crystal axes and its no tatio n is determined as fo llo ws:
1. Find the intercepts on the axes.
2. Take their recipro cals.
3. Reduce to the three (o r four for the hexago nal clo se-
packed (hep) systemt) smallest integers having the same
ratio .
4. Enclo se in parentheses, e.g., (hkl).
All parallel planes have the same indices. Negative intercepts
result in indices indicated with a bar abo ve. Curly brackets signify
a family of planes that are equivalent in the crystalthe six different
t A system of rectangular axes could also be used for hep structure; a four-axes
system is preferred where three axes are drawn on the basal hexagon and the
fourth axis perpendicularly. Therefo re, four Miller jndices are necessary to give
the po sitio n of a plane: {0001} is the basal plane, {1100} the prism plane, andthe
third apex of the unit projected stereo graphic triangle (see Section III.2) is {1120}.
Double-L ayer P roperties at M etal E lectrodes
faces of a cube, for instance, o r the family of planes {110} which is
{110} = (110) + (Oil) + (101) + (TiO) + (llO) + (Oil)
+(o i l )+(IOT)+(To i )+(Ti O)+(To T)+(o i l )
All these planes have the same ato mic co nfiguratio n. Fo r pure
metals the high level of symmetry allows us to write indifferently
parentheses o r curly brackets. The Miller indices of some impo rtant
planes of the cubic and the hexago nal clo se-packed systems are
given in Fig. 1.
(100) (110) (111)
(a) (102) (113)
--(0001)
(1100) -
(1120)
(1010)
1
(b)
Figure 1. (a) The three rectangular axes and the (111) plane for the
cubic system. Some impo rtant planes and their Miller indices for
the cubic system are shown, (b) The four axes and some impo rtant
planes for the hexago nal clo se-packed system.
6 A . H amelin
Any two no nparallel planes intersect alo ng a line; they are
planes of a zone and the directio n of their intersectio n is the zo ne
axis. A set of crystal planes which meet alo ng parallel lines is kno wn
as planes of a zo ne. The impo rtant zo nes in a crystal are tho se to
which many different sets of planes belo ng. On a crystal the faces
of a zo ne form a belt aro und the crystal. Zo nes are useful in
interpreting X-ray diffraction patterns (see Sectio n III. 3). Zo nes
are deno ted [hkl].
Fo r a detailed study of Section III, the reader can refer to a
universally accepted textbo o kReference 14.
2. T he S tereographic P rojection
The angular relatio nships amo ng crystal faces (o r ato mic planes)
canno t be accurately displayed by perspective drawings; but if they
are pro jected in a stereo graphic way they can be precisely reco rded
and then clearly understo o d.
Let us assume a very small crystal is lo cated at the center of
a reference sphere (ato mic planes are assumed to pass thro ugh the
center of the sphere). Each crystal plane within the crystal can be
represented by erecting its no rmal, at the center of the sphere, which
pierces the spherical surface at a po int kno wn as the pole of the
Figure 2. Angle <f> between two po les measured
o n a great circle.
Double-Layer Properties at Metal Electrodes
plane. The angle between any two planes is equal to the angle
between their po les measured o n a great circle of the sphere (in
degrees) as in Fig. 2.
As it is inco nvenient to use a spherical pro jectio n to determine
angles amo ng crystal faces o r angular distances of planes on a zo ne,
a map of the sphere is made, so that all work can be do ne on flat
sheets of paper.
The simple relatio n between the reference sphere and its stereo -
graphic pro jectio n (its map) is easily understo o d, by co nsidering
the sphere to be transparent and a light so urce lo cated at a po int
o n its surface (see Fig. 3). The pattern made by the shado ws of the
po les which are on the hemisphere o ppo site to the light so urce,
falls within the basic circle sho wn on the figure. The o ther hemi-
sphere will pro ject o utside the basic circle and extend to infinity.
To represent the who le within the same basic circle the light so urce
is put o n the left and the screen tangent to the sphere on the right
side; the po ints of this latter hemisphere are distinguished from
tho se of the first by a no tatio n such as plus and minus. All plo tting
can be do ne by trigo no metric relatio nships directly on graph paper.
; Projection plane
Light
'source
Figure 3. S tereographic projection. P ole
P of the crystallographic plane projects to
P' on the projection plane (R ef. 14).
Reference
sphere
Basic c.rcle
8 A . H amelin
The pro jectio n of the net of latitude and lo ngitude lines of the
reference sphere upo n a plane forms a stereo graphic netthe Wulff
net (Fig. 4). The angles between any two po ints can be measured
with this net by bringing the po ints on the same great circle and
co unting their difference in latitude keeping the center of the
pro jectio n at the central po int of the Wulff net.
Stereographic projections of lo w-index planes in a cubic crystal
and in a hep crystal are given in Fig. 5. Only o ne side of the
pro jectio n is visible; thus it must no t be fo rgo tten that "belo w"
(001) there is (OOl), "belo w" the planes of the {111} family represen-
ted on Fig. 5a there are the (ITT), (111), (111), and (III) planes,
and so o n for o ther families of planes. This fact must be kept in
Figure 4. Stereo graphic net, Wulff o r meridio nal type, with 2 graduatio n (Ref. 14).
mind when assessing the faces to simulate an "ideal" po lycrystalline
surface from three o r mo re families of faces.
15
Fo r electro chemists using single-crystal electro des, the high
level of symmetry of the crystal of pure metals allows all types of
planes to be represented o n a single trianglethe unit projected
stereographic triangle. The co of a face is represented by a single
po int; therefo re the azimuthal o rientatio n is no t specified. When
impo rtant, the azimuth is added; it is deno ted [Me/]. Any co can
be represented on the unit pro jected triangle; this is do ne for faces
of high indices on a figure presented in Sectio n III. 4.
Some of the most impo rtant angles between the faces are given
in Table 1.
r
113
013
113
u
213
102
\
213
X
) 103
/
/
- V o u i "
)103
213
\
013
1113
) 130
) 150
) 150
') 130
Figure 5 (a) Standard (001) stereo graphic pro jectio n of poles and zones circles
for cubic crystals (after E A. Wo o d, Crystal Orientation Manual, Co lumbia Univ.
Press, New York, 1963).
10 A . H amelin
2310
Figure 5. (b) Standard (0001) pro jectio n for zinc (hexago nal, c/a = 1.86) (Ref. 14).
3. Determination of C rystallographic O rientation
The diffraction of X-rays by a crystal, i.e., by a three-dimensio nal
grating, is analo go us to the diffraction of light by a o ne-dimensio nal
grating. When the incident and scattered rays make equal angles
with the ato mic plane there is reinfo rcementthe ato mic plane
behaves like a mirro r that is reflecting a po rtio n of the X-rays. The
geometry of the lattice determines entirely the directio n of the
reflected beams, i.e., the reflected beams are go verned by the distri-
butio n of ato ms within the unit cell following Bragg's law and the
Laiie equatio ns.
14
By using these principles the electro chemist has only to find
o ut the co of a piece of metal which was reco gnized as being an
T able 1
S ymmetries and A ngular S pecifications of P rincipal Index Faces of S ingle C rystals
i
Face o f reference
Symmetry o f the
spo ts aro und
this face
Angles between the
zo nes intersecting
at this face
Angles between the
face o f reference
and the lo w-index
faces o r the
lo w-index zo nes
[010][011] =
[010][031] =
[010][021] =
[OlO]
601 9.46
501 11.31
401 14.03
301 18.43
502 21.80
201 26.56
503 30.85
302 33.41
705 35.51
403 36.86
605 39.81
101 45.00
(100)
Fo urfo ld
45.00
[001][013]
[001][012]
[Oil]
711 11.41
611 13.26
511 15.78
411 19.46
31125. 26
733 31.21
21135. 26
533 41.08
322 43.31
755 45.28
433 46.66
11154. 73
= 18.30
= 26.56
[031]
913 19.36
813 21.58
713 24.30
613 27.80
513 32.30
413 38.50
[10l][0lI] =
[101][213] =
[101][112] =
[io l]
545 5.76
323 10.03
535 12.27
212 15.80
737 18.41
525 19.46
313 22.00
515 27.21
101 35.26
( HI )
Threefo ld
60.00
[011][123]
30.00
[Oil]
655 5.03
433 7.96
755 9.45
322 11.41
533 14.41
955 16.58
211 19.46
733 23.51
31129. 50
= 19.10
[112]
534 11.53
957 13.13
423 15.23
735 18.08
312 22.20
[010][101] =
[010][141] =
[101][323] =
[101][lll] =
[101][313] =
[101]
717 5.76
515 8.05
414 10.13
727 11.41
313 13.26
525 15.80
737 16.86
212 19.46
535 22.98
323 25.23
(101)
Two fo ld
90.00
19.46
[010][131]
[010][121]
13.26
[010]
605 5.18
403 8.13
302 11.31
503 14.05
201 18.43
703 21.80
502 23.20
301 26.40
401 30.96
501 33.68
601 35.53
100 45.00
= 25.23
= 35.26
[111]
817 6.41
615 8.95
514 10.90
413 13.95
312 19.10
523 23.41
734 25.28
21130. 00
; } .
M
|
12 A . H amelin
individual crystal (see Sectio n IV.2); the metal crystal system and
the crystal parameters can then be found in handbo o ks.
The mo st co nvenient metho d for determining the co of an
individual crystal is the back-reflection Laiie method. This metho d
requires o nly simple equipment: the crystal is po sitio ned in a
go nio meter head (o r any instrument which pro vides adjustable
o rientatio n) and a flat X-ray film in a lightpro o f ho lder is mo unted
no rmal to the X-ray beam. The film must be at a precise distance
R from the crystal (3, 6, o r 12 cm) (Fig. 6). t
The interpretatio n of the pho to graph o btained after abo ut
20 min, is carried o utt by making use of a chart develo ped by
Greninger
16
(Fig. 7), a standard pro jectio n of the crystal system
(Fig. 5 for the cubic system), and a table of the angles between the
different faces (Table 1 for the cubic system).
Fo r planes in a given zo ne, which form a belt aro und the
crystal, a co ne of reflected X-rays cuts the film alo ng a hyperbo la.
The clo sest appro ach of the hyperbo la to the center of the film is
equal to #tan2</>, where <j> is the angle of inclinatio n of the zo ne
axis (to the plane of the film). When the zo ne axis is parallel to
the film the hyperbo la degenerates into a straight line passing
thro ugh the center of the film. A back-reflectio n pattern of a fee
crystal (go ld) is shown in Fig. 8. The circle at the center is due to
the punched ho le necessary for the pinho le co llimato r of the
incident X-ray beam. The spo ts on o ne row (a hyperbo la) are
reflections from vario us planes of o ne zo ne.
First, attentio n is directed only to hyperbo las densely packed
with spo ts and to spo ts which lie at the intersectio ns of these
hyperbo las. These spo ts co rrespo nd to lo w-index planes: (100),
(110), and (111) (for the fee system). Their symmetryeasily
o bservedallo ws indices to be tentatively assigned to them. The
assigned indices are checked by reading the angles between the
planes (the spo ts) on a zo ne (a hyperbo la) using Table 1. A Grenin-
t Tungsten target X-ray tubes are co nvenient fo r this wo rk. Place a small piece o f
metal o n the lo wer right-hand side o f the black paper which co vers the film, so
as to have a guidemark o n the film.
X The film must be read fro m the side o n which the reflected rays were incident.
When, after develo ping, the film is dry, it is advisable to repro duce it o n tracing
paper using ink. Then the suppo sed zo nes and angles are drawn with pencil so
that they can be easily erased if mistaken.
13
film holder
x-ray
generator
black paper
on film
pin-hole
collimator
Figure 6. An X-ray go nio meter for the Laiie back-reflection
method (CNRS, France).
ger chart is used for reading angular relatio ns on back-reflectio n
films (for a crystal at a 3-cm distance from the film; see Fig. 7).
Keeping the center of the traced pattern (repro ducing the spo ts
and axes of the film) carefully to the center of the chart, any row
of spo ts can be made to co incide with o ne of the hyperbo las
extending ho rizo ntally acro ss the chart by turning it thro ugh an
angle a, where a is the azimuthal angle. cj> is determined directly
from the chart (Fig. 8).
By tilting the po sitio n of the crystal by the angles a and </>,
any plane (any cho sen co) can be set parallel to the film (perpen-
dicular to the X-ray beam). Then ano ther pho to graph gives a pattern
A . H amelin
figure 7. Chart for back-reflection pho to graphs printed in the size for a 3-cm
listance from specimen to film and graduated in 2 intervals (Ref. 14).
vith the cho sen co at its center; the pro minent zo nes and the sets
)f indices assigned to the spo ts must co incide with a standard
;tereo graphic pro jectio n having the cho sen co at its center. Then
he crystal must be cut parallel to the film to have the desired face
>f a precise co .
The technique described abo ve for crystal o rientatio n is
me of the simplest; o thers are used in crystallo graphy labo rato ries.
Figure 8. Back-reflection pattern of a gold crystal drawn on tracing paper
superimpo sed o n a Greninger chart.
4. M odels of C rystal S urfaces
An atomically flat surface is the surface of an ideal crystal when
cut by a plane. The ideal-half-crystal is made of semiinfinite regular
arrays of ato ms. The o rientatio n of the dividing plane can be
specified by a set of Miller indices (see Sectio n III. 2). Assuming
that the metal ato ms are hard spheres, any ato mically flat surface
can be represented by ball models.
16
A . H amelin
-M-
+
f-f-
--

o
>-
o
o
^ ; % %
?
Yf[120]
(a)
Yf[233]
(b)
(210) (311]
(c)
Figure 9. B all models for five faces of the fee system (R ef. 17). (a) P hotographs, (b) Drawings looking normally at
the model. T he center of each surface atom which lies on, or inside, the unit-cell boundary is marked with a dot; in
some cases this is all that can be shown of that atom. 0, 1, 2 are the number of the layer of atoms (0, 2 implies that
one atom lies directly behind the other), (c) M iller indices.
I S A . H amelin
Fo r the fee and hep systems, the bulk of the crystal has a
clo se-packed structure. By inserting (theo retically) a dividing plane
and remo ving the unwanted balls from o ne side of this, a surface
mo del is pro duced. Fo r o ur metals the mo del is made of balls of
o ne size, the diameter being a measure of the spacing between
nearest-neighbo r ato ms. Figure 9 shows the ball mo dels of the five
faces of Fig. 1, for the fee system. These mo dels give an o verall
picture of the crystal surfaces, but for detailed work the precise
dispo sitio n of the ato ms is necessary; it is also given o n Fig. 9. The
shape and dimensio ns of the unit cell of surface is drawn by means
of do tted lines on the drawings.
The unit cell of the surface can be defined either by co nsidering
only the o utermo st plane of surface ato ms, o r by co nsidering, in a
mo re realistic interpretatio n, all ato ms which have less than their
full co mplement of neighbo ring ato ms. Fo r the fee system, an ato m
in the bulk metal has 12 nearest-neighbo r ato ms (its co o rdinatio n
is 12); the number of surface ato ms of given co o rdinatio n for the
five faces of Fig. 9 is given in Table 2. It can be easily understo o d
that, in the fee system, a surface ato m of co o rdinatio n n has 12 - n
"bro ken bo nds". This is just a descriptio n based on the geo metrical
co ncept of "bo nds"; no physical reality can be ascribed to it.
A surface (hkl) can be represented by its o utward no rmal h
(having h, /c, / co mpo nents); a bo nd can be specified by a vecto r
u (having w, V, W co mpo nents). Fo r the fee structure, an ato m may
have 12 nearest-neighbo r bo nds, but o nly six of these can give
po sitive scalar pro ducts h u for h within the unit triangle. Fo r a
T able 2
N umbers of S urface A toms of Given
C oordination in Unit C ells of Various
S ingle-C rystal Faces for the fee S ystem
^"""^Co o rdinatio n
Face ^~" \ ^^
(100)
(110)
(111)
(210)
(311)
6
0
0
0
1
0
7
0
1
0
0
1
8
1
0
0
0
0
9
0
0
1
1
0
10
0
0
0
0
1
11
0
1
0
1
0
particular h,
h u
a
> h u
b
> h u
c
> h u
d
> h u
e
> h u
f
> 0
The o rdered subset of bo nds u
a
, . . . , u
f
is termed the bond order
appro priate to the particular h. If h is visualized as moving over
the unit pro jected stereo graphic triangle, then the bo nd o rder
changes at certain po ints thus dividing the unit triangle into regions
(such that the bo nd o rder is fixed within a regio n but changes o n
passing to an adjacent regio n). Fo r the fee structure five regio ns
may be co nsidered o n the triangle (Fig. 10a). Fo r the elec-
tro chemists, up to no w, it is no t necessary to go into further details
of bo nd o rders; they are given in An Atlas of Models of Crystal
Surfaces.
17
Fo r the fee system for each of the three families of planes
{111}, {100}, and {110} there is only o ne type of site where an ato m
co uld be added in the nearest-neighbo r po sitio n; they are called
singular faces (Fig. 9). Ato mically flat surfaces nearly parallel to a
singular face are called vicinal faces. The vicinal faces can be
described by the co mpo sitio n of terraces of singular faces and by
monoatomic steps (Fig. 11). The mo no ato mic steps are either densely
packed in ato ms o r kinked. This mo del is called the TLK model
(terrace, ledge, kink) and it can be easily extended to all faces o n
the three main zo nes of the unit triangle.
These faces are called stepped faces. Fo r instance, the (221)
face which is 15.79 from the (111) face o n the zo ne from (111) to
(110) is made of terraces (111) o riented and mo no ato mic steps
deno ted (111) [(111) steps] because they have threefo ld symmetry
like the (111) face (Fig. 9). Fo r the (211) face, which is 19.46 from
the (111) face on the (lll)-(100) zo ne, there are also (111) terraces
and densely packed steps but deno ted (100) because they have
fourfold symmetry like the (100) face (Fig. 9). Fo r the (310) face,
which is 18.43 from the (100) face o n the (100)-(110)
ZO
ne the
terraces are (100) o riented and the mo no ato mic steps which are
made of kinks are deno ted (110) (Fig. 11).
Accepting this TLK mo del, a very co nvenient notation was
pro po sed for stepped surfaces (see Appendix of Ref. 18). Thus a
stepped surface is called n(h
t
k
t
l
t
) - (h
s
k
s
l
s
), where (h
t
k
t
l
t
) represents
the co of the terraces, (h
s
k
s
l
s
) represents the step face, and n deno tes
the width of the terraces in number of ato ms. Fo r instance, (221)
4 ( 1 1 1 )
(100)
(111)
(210)
(a)
(10 1 0)= (310)= (210)= (320) =
) 3(100H110)2(110)-(100)3(110)-(100)
(b)
Figure 10. Unit stereographic triangle for the fee structure with the (100) face at the center of the projection, (a) R egions which
correspond to different bond orders (R ef. 17):
region 1 2 3 4 5
bond order abcdef abcedf abcefd abecdf abecfd
(b) A ccepting the notation of L ang et a/. ,
18
namely n(h
t
k
t
l
t
) - (/i
5
fc
5
/J , where (h
t
k
t
l
t
) represents the terrace, (h
s
k
s
l
s
) represents the step
face, and n measures the width of the terrace in number of atoms.
[011]
(211)
Yf[114]
( 221)
Yf[130]
(a)
(310) (c)
Figure 11. M odels for the (221), (211), and (310) faces of the fee system. C omments are the same
as for Figure 9.
I
I
22 A . H amelin
is 4(111)-(111) because the terraces for an ideal (221) face are four
ato ms wide and the terraces and steps are bo th (111) o riented. Most
of the faces which have been used by electro chemists are represen-
ted on the unit pro jected stereo graphic triangle of Fig. 10b with
their Miller indices and their no tatio n as stepped faces. Each of
the three sides of the triangle seems to be made of two sectio ns
where there are systematic changes of the co mpo sitio n of the
surface. The (311) and (210) faces appear as "turning po ints" o n
the (lll)-(lOO) and (100)-(110) zo nes, respectively. But the (331)
face on the (lll)-(HO) zo ne canno t be co nsidered a turning po int
because the (110) face itself is made up of small terraces which are
(111) o riented and steps which are (111) o riented; in fact, (110) is
2(111)-(111). Therefo re, for the fee system, o n the three main zo nes
five sectio ns are o bserved for the bo nd-o rder no tatio n. But when
T able 3
T ypes of S tepped S urfaces in C ubic S ystem
Stepped-surface designatio n
/ i n\ /-i-i-t\
Example: 9(111)-(111)
n(lll)-(100)
Example: 10(lll)-(100)
n(lUU)-(lll)
Example: 10(100)-(l 11)
n(lOOMHO)
Example: 9(100)-(110)
Example: 5(110)-(lll)
fH ilU)-(lUU)
Example: 9(110)-(100)
Miller indices
(n, n, n -2)
(997)
(n + l , n - l , i , - l )
(11,9,9)
(2/1-1,1,1)
(19,1,1)
(",1,0)
(910)
(991)
(n, n - 1,0)
(980)
Angle of cut from
terrace along zone line
toward step
*
Q r i
I I l
6.45
_j / 2\/2 \
tan 1 1
5.57
ten-
1
I I
4.25
tan"
1
( - I
6.34
U n
\2(2n-l))
4.49
-1 /
1
\
3.37
generalizing the mathematical fo rmulas, as sho wn in Table 3, six
sectio ns have to be co nsidered.
Fo r stepped surfaces in the cubic system, the designatio n,
Miller indices, and the "angle of cut from the terrace alo ng the
zo ne line to ward the step" are related, as shown in Table 3 (for
the six sectio ns, six examples are given). Any face can be imagined
with this mo del.
One may ask if these ideal faces actually exist. The evidence
is that they do no t exist; even at thermal equilibrium there are
diso rders at the surface and mo re kinks are present than necessary
for the average specified co . Ho wever, we shall see that this mo del
do es fit in with some experimental results of dl studies; it explains
o ther electro chemical results, such as lead underpo tential depo si-
tio n on go ld faces.
19
5. S tructure of M etal S urfaces
(i) Atomic Aspects
At present the detailed kno wledge of the o utermo st layers of
a clean metal surface is based o n electro n spectro sco py o r scattering
of neutral ato ms. Low-energy electro n diffraction (LEED) and
helium (for instance) scattering give structural info rmatio n abo ut
the to p of the surface in ultrahigh vacuum (UHV). Are the surfaces
o bserved in UHV close to the mo dels described in Section III. 4?
In so me cases they are, but for platinum, iridium, and go ld a
reconstruction of the first o utermo st layer of ato ms was o bserved
for some faces of simple indices. Of these three metals, only gold
is within the sco pe of this chapter. Numero us papers were written
abo ut the surface reco nstructio n of go ld which, ho wever, happens
o nly under certain co nditio ns of cleanliness and temperature.
It is co nventio nal to describe the real surface by a no tatio n
which co mpares it with the ideal o ne.
20
The surface net is indexed
with respect to the bulk net as a p x q unit cell. A to p layer, which
is just a bulk terminatio n, is deno ted l x l .
The Au(100) face surface is appro ximated by a 20 x 5 (o r
1x5) unit cell; this implies a bo nd-length reductio n of a few
percent. Then there is a mismatch between the to pmo st layer and
the substrate (the bulk) that wo uld increase the strain energy at the
surface. A buckling of the surface is accepted as an explanatio n of
24 A . H amelin
some LEED o bservatio ns. At least four different surface structural
mo dels were pro po sed.
The Au(lll) face, which is the closest packed fee structure, is
known to have the lowest surface energy amo ng all po ssible fee
crystal faces. The clean Au(lll) face surface was first appro ximated
to be a \/3 x V3..R30
0
unit cell.
21
A mo del with a uniaxially co ntrac-
ted to p hexago nal layer was pro po sed
22
and a charge-density-wave
(CDW) structure was also pro po sed as an explanatio n of the LEED
o bservatio ns.
22
The Au(llO) face surface has a 1 x 2 structure suggested
21
'
2325
to co nsist pro bably of alternately missing rows pro ducing micro -
facets having the clo se-packed arrangement of the (111) face.
This no tatio n is extended to the case of a foreign substance
on a well-defined substratefo r instance, for oxygen on co pper,
26
Cu(100) + c(2 x 2)O (c stands for centered mesh), and for gold on
silver,
27
Ag(lll) +/?(1 x l)Au (p stands for primitive mesh).
It seems that for all clean metals the case of stepped faces is
different from that of lo w-index faces. The mo no ato mic steps wo uld
be stabilized by repulsive fo rces; therefo re they wo uld be less stable
for a large width of terrace than for a small width of terrace.
28
In this sectio n we have tried to show that the surface may no t
be a perfect bulk terminatio n structure. But do these reco nstructio ns
exist at an electro chemical interphase as they are o bserved in UHV?
Pro bably no t; but with the variatio n of the electric field at the
interphase and with the adso rptio n and deso rptio n of io nic (o r
neutral) substances, some reco nstructio n of the surface may o ccur.
(ii) Electronic Aspects
Up to now we have co nsidered only the po sitive io ns of the
metals, neglecting the electro n distributio n. Fo r sp and sd metals
the "jellium" mo del is accepted as a go o d representatio n of this
distributio n: the po sitive io ns are immersed in a "gas" of appro xi-
mately unifo rm density of free electro ns. The attractio n of the
po sitive and negative charges ho lds the structure to gether and
balances the repulsive forces of the po sitive (o r negative) charges
for o ne ano ther. The moving electro ns are subjected to a perio dically
varying po tential as a result of the presence of the io ns in the lattice.
(The moving electro n behaves as if it were a system of waves
diffracted by crystal planes. ) The electro ns are described by Bloch
functio ns asso ciated with waves extending thro ugho ut the entire
crystal.
The reader is referred to textbo o ks
14
'
29
for further info rmatio n.
At the surface, the electro n density dies off gradually, the
electro ns spilling over the po sitive-io n lattice. The charge density
is negative o n the o uter side and predo minantly po sitive just inside
the metal (when there is a deficiency of electro ns); an electric
do uble layer is created. The dipo le mo ment of this do uble layer
will vary with the nature of the metal and with the co for a given
metal.
This last po int is well within the sco pe of this chapter because
the variatio n of the electro nic work functio n with the co for a given
metal is due to this do uble layer. The electro nic work functio n
represents the difference in energy between the highest no rmally
o ccupied electro nic energy level inside the metal and the state of
an electro n at rest o utside the uncharged surface. The work functio n
of a metal depends bo th o n its bulk pro perties and on the charac-
teristics of its surface, the latter being influenced by the surface
ato mic structure. The magnitude of the do uble-layer dipo le mo ment
was co mputed for several metals and it varies from tenths of a volt
to several vo lts;
31
for different co 's of a given metal it can vary by
amo unts which are sizable fractio ns of itself.
In additio n to the wave functio ns of unifo rm amplitude
thro ugho ut the crystal, wave functio ns may exist which have
appreciable amplitude o nly in the surface regio n; they represent
lo calized electro nic states at metal surfaces.
Fo r an actual surface the po sitive charge is no t unifo rmly
distributed over a half-space. Fo r steps at the surface o r co rrugated
surfaces (o n an ato mic scale), the co nto urs of co nstant electro nic
density have ridges and valleys co rrespo nding to tho se of the
distributio n of po sitive io ns at the surface but they are smo o ther
and less bumpy.
Smo lucho wski
30
attempted to calculate the "smo o thing. " Fo r
the most closely packed crystal faces, mo re co mplete smo o thing is
expected and the co nstant electro n density co nto urs are fairly flat;
this lowers the do uble-layer mo ment (negative co rrectio ns to values
witho ut smo o thing). The amo unt by which the "smo o thing"
decreases the do uble-layer mo ment will be greater the ro ugher (o n
26 A . H amelin
an ato mic scale) the surface. Smoluchowski demo nstrated that for
peaks and valleys a few ato m spacings apart eno ugh smo o thing
will o ccur to make the ro ugher crystal faces have the lower work
functio n. In summary, all irregularities will tend to lower the work
function because each irregularity creates a po int dipo le with its
po sitive directio n o utward.
31
In electro chemical co nditio ns, a change of density of charge
at the metal surface, i.e., a change of po tential, pro duces a shift of
the electro n distributio n.
(iii) Surface Energy Aspects
The increase in energy asso ciated with an increase in the surface
area of a metal arises from the fact that surface ato ms have fewer
neighbo rs than bulk ato ms and hence co ntribute less to the to tal
binding energy of the crystal. Surface free energies y were calculated
assuming sho rt-range interactio ns for binding o ne surface ato m
with either its nearest o r its seco nd-nearest-neighbo r (and so o n)
ato ms.
32
The co nto ur lines of co nstant free energy, based on the
nearest bro ken-bo nd mo del, for a fee crystal are shown (Fig. 12)
only in a unit pro jected stereo graphic triangle.
32
Obvio usly, there
is o ne turning po int on the (lll)-(lOO) and (100)-(110) zo nes and
mo no to nic variatio ns o n the (lll)-(HO) zo ne as we o bserved (see
Fig. 10).
When using the TLK mo del, the surface free energy is calcu-
lated by adding the surface free energy for the terraces and the line
free energy of the steps.
33
Then the variatio ns of the surface free
energy with the co can be drawn (it is called a y plot). In the
neighbo rho o d of singular faces [such as (100) and (111) for the fee
system], an inward-po inting cusp is o bserved and maxima are
o bserved for the ro ughest faces [the (210) face for the fee system,
for instance; see Fig. 12].
These theo retical predictio ns are confirmed by experiment but
very few results are available at the present time.
As we shall see, no t only will the ato mic aspect of the face
surfaces be reflected by electro chemical results but the electro nic
and surface energy aspects as well, the three being related as wo uld
be expected.
0.775 (111)
0. 894
(100) 0.95 0.99 (210) (110)
(a)
0. 949
1.00
0. 90
0.80
(b)
1.00
0. 90
0.80
(c)
Figure 12. Fo r a fee crystal (fro m Ref. 32): (a) co nto ur lines o f the surface free
energy y based o n the nearest-neighbo r bro ken-bo nd mo del and (b) and (c) co rre-
spo nding y plo tsthe ho rizo ntal axis is scaled taking into acco unt the angular
distances between the faces; the free surface energy relative to the (210) face is
plo tted o n the vertical axis.
In electro chemical co nditio ns, in the case of no adso rptio n,
when the density of charge is zero at the metal surface the work
functio n is linearly related to the po tential, and the pzc varies with
the co in parallel with the y plo t (see Sectio n V. I).
(it?) Defects
Even in the best crystals some defects exist; they are a necessary
co nsequence of the thermo dynamic equilibrium of the crystal. At
28 A . H amelin
ro o m temperature, at least 10
6
-10
7
cm""
2
dislo catio n lines exist
5
at
a metal surface which has a density of ato ms of abo ut 10
15
cm"
2
.
Actual crystals which have been manipulated have certainly
mo re defects; furthermo re, evidently, they have edges which are
no t sharp o n an ato mic level.
Fo r advanced studies of the subjects of Sectio n III. 5 and the
no tatio n, the reader may refer to the chapter of Oriani and Jo hnso n
5
in this series.
I V. P R E P A R A T I O N O F S I N GL E -C R Y S T A L -FA C E
E L E C T R O DE S
1. Growing S ingle C rystals
Books abo ut crystal-gro wing pro cedures are available.
34
"
36
It is difficult to assess the relative merits of the different metho ds
used for gro wing crystals on acco unt of the following facto rs:
1. The cho ice of the shape of the crystal (cylinder, disc, thin
layer) depends o n the techniques which will be used. (Thin
layers are necessary for resistance measurements of the
surface layer during electro chemical adso rptio n, while
some o ptical measurements require large surface areas. )
2. Some facilities are available in o ne labo rato ry but no t in
o thers.
3. An incidental advantage, which can be useful for elec-
tro chemists, is the "perfect" surface fo und on crystals
gro wn from the vapo r o r from electro lytic so lutio ns.
4. What is po ssible for o ne metal might be impo ssible for
ano ther.
The metal crystal gro wth co uld take place from:
1. The metal melt.
2. The metal vapo r.
3. Metal electro lyte so lutio ns.
These different po ssibilities will be illustrated by examples used in
electro chemistry.
(i) Growth from the Metal Melt
This is by far the most impo rtant technique. A seed is formed
in the melt o r added but the so lid-melt interface must remain planar
29
during so lidificatio n from the seed. Metho ds develo ped from this
principle are:
1. The crystal-pulling metho d.
37
2. The Bridgman metho d.
3. The zo ne-melting metho d.
4. The flo ating-zo ne metho d.
Hitherto , the last two metho ds have no t been used by elec-
tro chemists. They have either melted the tip of a wire so as to o btain
a small sphere which in some cases is a single-crystal (platinum)
o r used a modified Bridgman metho d.
Fo r the Bridgman metho d the melt is co ntained in a crucible
(graphite for gold or silver); the freezing must co mmence at a
po intused as a seedfrom which the so lidificatio n pro ceeds (a
co nical tip of the crucible pro duces a "natural" but unco ntro lled
selectio n of the seed). The so lidificatio n pro ceeds either by moving
the crucible o r by regulating the temperature gradient, i.e., the rate
of mo vement of the freezing plane. This last po ssibility was used
for go ld, silver, and co pper, for example.
Vacuum
Quartz tube
D
o.
c
o
Water
az
GZ
~ - ^ \ _ Copper
/tube
ZX5
^__ Graphite
Metal
Figure 13 One of the po ssible ways of growing a gold
(or silver) crystal in a crucible placed in the helix of an
inductio n oven
30 A . H amelin
Fo r go ld o r silver, the graphite crucible was placed in a quartz
tube; the quartz tube was po sitio ned in the helix of an inductio n
o ven; and the tube was evacuated (Fig. 13) and the temperature
gradient regulated. Mechanical vibratio ns must be avo ided during
so lidificatio n (2-20 min for a cylinder 20 mm lo ng). The experimen-
ter has to know whether the sample is an individual crystal o r no t
when it is remo ved from the crucible. Its macro structure (its general
gross structural distributio n in the who le) has to be determined.
Therefo re the ingo t has to be macro etchedt; then grain bo undaries,
if they exist, are visible to the naked eye.
The size of the crystal thus o btained may be 2-20 mm in
diameter and 5-200 mm in length.
(if) Growth from the Metal Vapor
The co llecto r [po lished glass, cleaved mica, (100) face of a
so dium chlo ride crystal, face of a metal, face of the metal] is
maintained at a temperature below the melting po int of the metal
(in vacuum o r in a neutral gas) so that crystal nuclei can be fo rmed.
The area of the film can reach several square centimeters.
The metal is either evapo rated o r sputtered, so that either very
thin layers o r thicker layers are o btained. In the following para-
graphs, so me examples are given.
Thin layers of go ld, evapo rated on po lished glass (10-80 nm
thick) give monooriented polycrystalline electrodes; the film is made
of grains, the surfaces of which are (111) faces. The [111] axes of
the grains are nearly perpendicular to the substrate and the
azimuthal o rientatio n is rando m.
Layers of go ld (100-150 nm thick) sputtered o n cleaved mica
give monooriented polycrystalline electrodes. The grains are a few
tenths of micro meters in area; they are (111) o riented, but the
azimuthal o rientatio n is rando m. Since the who le electro de surface
is no t made of o ne grain, there are grain bo undaries. At present
the co ntributio n of these to dl parameters do es no t seem impo rtant.
The behavio r of these layers is close to that of massive co nventio nal
single crystals which are (111) o riented.
38
t Macroetching is do ne by dipping the ingot in an etching reagent (for gold a few
seconds in warm aqua regia, for silver a few seco nds in tepid 50% nitric acid,
etc.) and rinsing.
Hetero epitaxial layers of gold (100-150 nm thick) evapo rated
o n cleaved mica give nearly monooriented crystalline electrodes; with
big (lll)-o riented grains (a few micro meters to a few tenths of a
micro n in area), nearly no azimuthal diso rientatio ns are o bserved
at the surface. Their electro chemical behavio r is close to that of
massive co nventio nal single crystals.
38
Hetero epitaxial layers of go ld sputtered on po lished (100) faces
of so dium chlo ride crystals were made. The first depo sited layers
of go ld o n the substrate have its to po graphythey are go ld single
crystals which are (100) oriented. A supplementary depo sit of go ld
(abo ut 2 jum thick) makes them "easy" to manipulate and to remo ve
from the NaCl crystal. The first layer built o n the substrate was
used as an electro de surface for dl measurements; the results are
close to tho se of massive co nventio nal single crystals which are
(100) o riented.
39
Ho mo epitaxial layers of o ne metal o n a substrate of the same
metal impro ve the quality of the surface.
The surfaces grown from the metal vapo r do no t require cutting
and po lishing. However, iso latio n of the face of interest and electric
co ntact must be ensured.
(iii) Growth from Metal Electrolyte Solutions
The questio n of why electro chemists have so seldo m used a
technique which is their own is of interest. First, only the faces of
the lowest surface energies can be o btained [the (111) and (100)
faces for the fee system]. Seco nd, if an epitaxial gro wth is o bservable
o n some metals it is no t o n o thers. Up to the present, dl measure-
ments were do ne on faces grown from the metal electro lyte so lutio ns
only in the case of silver.
40
"
42
These silver faces were grown in glass
o r Teflon capillaries o n a substrate which was a massive silver
crystal grown from the melt (o riented, cut, and po lished acco rding
the desired face).
After electro lytic gro wth, only o ne crystal face fills the sectio n
of the capillary. The surface of the face co nsists of terraces and
gro wth steps; by co nvenient catho dic treatment, o ne can change
the gro wth-step density and can thus partly modify the ato mic
surface structure of the electro de altho ugh its co remains
unchanged.
4042
t The po ssibility to change this density at will is the
t Screw dislo catio n free faces are o btained.
32 A . H amelin
main advantage of this type of electro de. It sho uld be emphasized
that, by this metho d, the imperfectio ns of the surface seem to be
minimized. Furthermo re, the influence of these ato mic irregularities
on dl measurements was studied by using silver (111) and (100)
faces with a definite gro wth-step density (2-20. 10
4
cm~
1
).
The wo rking area of these electro des is a few tenths of a square
millimeter.
2. C utting the C rystal
Crystals grown from the melt are removed from the crucible and
have to be reco gnized as individual crystals [see Section IV. l(i)]
befo re being o riented by the X-ray back-reflectio n Laiie metho d
(see Sectio n III. 3). At the end of this pro cedure, the desired co is
perpendicular to the X-ray beam; therefo re the crystal must be cut
perpendicularly to this beam.
The cutting can be do ne either with a saw (thread saw, with
carbo rundum, electro lytic saw, spark ero sio n), o r by eliminatio n
of part of the crystal by abrading (grinding o n emery paper of fine
grade, for instance, o r spark ero sio n). The po sitio n of the crystal
when cutting and the angle of cut have to be maintained with
precisio n. Either the crystal has to be left in the go nio meter or some
precise guidemark has to be drawn on the crystal. t
Any face of determined co can be o btained by this metho d
and thus the variatio n of dl parameters can be investigated from a
general viewpo int; but a disturbed layer is made at the surface
which has to be remo ved by po lishing (see Section IV.3).
In some cases the cylindrical crystal (of small diameter) can
be cleaved successfully in liquid nitro gen alo ng the most densely
packed face. This is the case for the basal face of zinc
44
; then no
po lishing is necessary.
t If the desired face, which is elliptical in shape, is parallel to the film and the major
axis of its ellipse ho rizo ntal, a guide mark (a thin line) can be drawn ho rizo ntally
on the crystal, i.e., along the major axis. In the ho lder (Teflon or ano ther material)
a hole of the diameter and the cut angle of the crystal is driven. A line, as a
guidemark, is also drawn alo ng the major axis of the elliptical hole (at the surface
of the ho lder). The lines drawn on the crystal and on the ho lder are bro ught into
co incidence. The bulging part of the crystal is then abraded flat. The crystal must
sometimes be fixed in the ho lder with a wax melting below 100C. This technique
was used for gold crystals.
43
To intro duce a perso nal co mment, it is surprising that this part
of the work is co nsidered as a menial task and every time, when
visiting a labo rato ry, I asked to see how the crystals were cut,
I felt that I was being indiscreet. Ho wever, any erro r intro duced
at this stage will entail erro rs in the electro chemical results.
3. P olishing and I solating the Face of Interest
After cutting alo ng the desired crystal face, the surface is left with
a disturbed layer on to p. The physical state of the electro de surface
must be that of an ato mically flat face described abo ve (see Sectio n
III. 4). Therefo re the experimenter must try, by all means available,
to create a disturbed layer as thin as po ssible, o r absent. Eliminatio n
of this disturbed layer can be do ne either directly by electro chemical
po lishing (e.g., po ssible for silver) o r by mechanical po lishing,
followed by electro chemical o r chemical po lishing.
(i) Mechanical Polishing
Any bo o k of metallo graphy pro vides go o d info rmatio n for this
step of preparatio n of the surfaces.
The cho ice of the ingredients used for mechanical po lishing
(felt or clo th, alumina po wder o r diamo nd paste, etc.) is dictated
by the hardness of the metal and its chemical pro perties. Soft metals
(such as go ld) are mo re difficult to po lish than hard metals because
the po lishing material can po ssibly be "buried" into the metal and
co nsequently modify the chemical co mpo sitio n of the electro de
surface (see Section IV.6).
Mechanical po lishing is generally first do ne with fine emery
paper. Care must be taken to work acro ss the lines (scratches)
formed o n the surface by co ntinual rando m ro tatio n of the sample.
Then alumina po wders of different grades (o n different felts) o r
diamo nd pastes of different grades (o n different clo ths) are used
to remo ve, as well as po ssible, the disturbed layer. t A mirro r finish
sho uld be o bserved; for instance, no trace of the lines due to the
po lishing sho uld appear when o bservatio n is magnified 20 times.
t A lapping wheel is generally used; the sample can be held by hand but an auto matic
apparatus is now available.
34 A . H amelin
The eliminatio n of the disturbed layer can be checked by X-ray
pho to graphs.
Ho wever, electro chemistry takes place o n the o utermo st layer
of ato ms which was in co ntact with the pro ducts; therefo re anneal-
ing, chemical o r electro chemical po lishing, and then further anneal-
ing are necessary, t
(11) Electrochemical (or Chemical) Polishing of the Face
Books have been published abo ut electro chemical and
chemical po lishing.
46
Of co urse, the pro cedure depends o n the
nature of the metal, the size of the electro de, and the skillfulness
of the experimenter.
Only the face of interest must be in co ntact with the po lishing
bath; therefo re the iso latio n of the face (see further: resin, O-ring,
and ho lder) is necessary. Creeping of po lishing so lutio n between
the crystal and the iso lating material co uld ro und the edge of the
face and change the geo metric wo rking area; therefo re creeping
must be avo ided.
Electro chemical o r chemical po lishing, whatever is the rinsing
pro cedure, leaves traces of chemicals at the surface (cyanide in the
case of go ld o r silver, for instance). These po lishing stages are
followed either by annealing o r by o ne of the final surface prepar-
atio ns (see Sectio n IV.4).
(M I ) Isolating the Face of Interest
The pro blem is to leave only the face of interest in co ntact
with the so lutio n and to do it in such a way that the geo metric
wo rking area can be kno wn and to avoid co ntaminatio n of the face
which co uld no t be remo ved by a final preparatio n (see Section
IV.4). Of co urse, creeping between the ho lder and the walls modifies
the wo rking geo metric area of the electro de and then o ther co 's
than the desired o ne are in co ntact with the so lutio n.
The crystal was often po sitio ned in a Teflon ho lder (which has
been tho ro ughly cleaned) and the face was limited with a RTV
t For silver, we succeeded in making good electro chemical dl measurements after
mechanical po lishing just by annealing and cooling in argon and putting the crystal
in co ntact with the so lutio n witho ut co ntact with air.
45
(ro o m-temperature vitrificatio n) silico ne resin (Fig. 14a). Po lythene
disso lved in to luene is also used. In any case, it sho uld be a
no nco ntaminating material. When using films, a vito n O-ring can
be po sitio ned on the face (Fig. 14b); this type of ho lder was also
used for faces of large geo metric area. Fo r crystals grown in capil-
laries no further iso latio n is necessary.
Kel-F
Wire for
electric
connection
Kel-F S
Stainless
steel
.->f Teflon
\~~- Non-contaminating
O-Ring
(a)
- Crystal
(b)
Figure 14. Three po ssibilities of
iso latio n of the face of interest are
by: (a) a no nco ntaminating resin
and ho lder; (b) an O-ring and ho l-
der;
38
and (c) a hanging electro lyte
metho d.
47
Only the face of interest
sho uld be in co ntact with the sol-
utio n.
Wire
36 A . H amelin
Where the "hanging electro lyte" metho d is used,
47
no iso lating
material is necessary; just after annealing the crystal in a to rch
(to wn gas and oxygen) and co o ling it in a clean medium (water
48
o r argo n
45
) and to uching the surface of the so lutio n, a no nco ntami-
nated interphase can be o btained witho ut any interference of the
co 's of the walls of the crystal (which have to be dry and smo o th)
(Fig. 14c).
Once mo re, for each metal, so lvent, and cho sen technique, the
sequence of pro cedures will differ.
4. Final S urface P reparation
The final aim is to have an electro chemical interphase chemically
clean bo th o n the so lutio n side (water, chemicals, gas) and o n the
metal side (no o xide, no sulfide, no traces of the po lishing so lutio ns),
and physically well-defined at the o utermo st layer, o r layers, of ato ms
being as they are in the bulk metal in a plane parallel to the surface.
We shall discuss two examples.
1. Fo r silver faces, mo unted as in Fig. 14a, befo re each series
of dl measurements a few seco nds of electro chemical po lishing are
necessary; therefo re traces of cyanide are left at the surface which
are no t eliminated by rinsing tho ro ughly with so lvent (very pure
water). In the aqueo us so lvent, excursio ns, in a range of po tentials
more negative than the do uble-layer regio n, pro duce a slight hydro -
gen evo lutio n as a co nsequence, which carries the impurities existing
at the metal surface away into the vo lume of the so lutio n, if the
latter is stirred. Then the so lutio n has to be renewed. This pro cedure
can be applied several times until the C(E) curves are stable and
satisfacto ry. Of co urse, o ne must avo id by all means excessive
hydro gen evo lutio n which co uld substantially disturb the first layers
of ato ms of the electro de surface o r work the resin lo o se.
It must be po inted o ut that o xides formed on silver canno t be
reduced electro chemically.
2. Fo r go ld faces, mo unted as in Fig. 14a, no annealing and
co o ling as described in Section IV.3(iii) is po ssible. In the aqueo us
so lvent a slight hydro gen evo lutio n co uld be used (as for silver,
with the same disadvantages, altho ugh electro chemical po lishing
was no t do ne at this stage). But for go ld, with no or slight adso rptio n,
a mo no layer of o xide can be co mpleted at the surface and remo ved
electro chemically in the aqueo us so lvent; the fo rmatio n and
remo val of this o xide layer can be used as a cleaning pro cedure.
Do these fo rmatio ns and remo vals of o xide disturb the o utermo st
layer of gold ato ms? Yes, if the variatio n of the applied po tential
with time is fast (mo re than 100 mV s"
1
),
49
but it do es no t seem to
be the case for slow sweep rate (lOmVs"
1
). Fo r the (100) face,
co mpariso n of C(E) curves o btained after numero us cycles of
fo rmatio n and removal of o xide and o btained just after annealing
and co o ling [see Section IV.3(iii)] are identical.
50
If there is io nic
adso rptio n (bro mide, io dide so lutio ns), there is o xidatio n of the
anio n befo re o xidatio n of go ld and this final preparatio n has to be
do ne in ano ther so lutio n (perchlo ric acid, for instance) befo re dl
study of io nic adso rptio n.
Fo r each metal and each so lvent a final preparatio n of the face
has to be ado pted. In some cases this final surface preparatio n is
at the same time a check of the quality of the electro chemical
interphase.
5. Ex situ C heck of S tate of E lectrode S urface
Ex situ checking of the electro de surface is do ne first by o ptical
micro sco py, electro n micro sco py, and scanning micro sco py. When
a UHV chamber is available in the labo rato ry then mo re so phisti-
cated metho ds can be used, altho ugh the state of the surface in
vacuum is no t necessarily what it is in co ntact with a so lvent at the
electro chemical interphase. t Ho wever, the new powerful metho ds
used to pro vide info rmatio n o n the chemical state of surfaces,
namely, AES (Auger electro n spectro sco py) and XPS (X-ray pho to -
electro n spectro sco py) [also called ESCA (electro n spectro sco py
for chemical analysis)], and o n the physical state of the uppermo st
regio n of the surface, namely, LEED (lo w-energy electro n diffrac-
tio n) and RHEED (reflection high-energy electio n diffractio n), are
certainly of great help for the erectro chemist wo rking on single-
crystal-face electro des. The "gap" between o bservatio ns in the UHV
chamber and o bservatio n at the electro chemical interphase due to
transfer is smaller every day, altho ugh it may never be co mpletely
t After the present chapter was submitted, studies on emersed electro des consisting
of single crystal faces were published; they give info rmatio n on the dl.
38 A . H amelin
clo sed. Therefo re co nclusio ns drawn from o bservatio ns in UHV
can, to some extent, be valid for the electro chemical situatio n.
The reader can refer to References 5 and 51-53 for further
info rmatio n.
6. In situ C heck of S tate of E lectrode S urface
In fact, all that follows in this chapter co uld be co nsidered, in a
way, as an "in situ check" of the electro de surface, because, while
o bserving the desired electro chemical dl parameters, questio ns of
the chemical cleanliness of the electro de surface (and of the inter-
phaset) and the physical state of the o utermo st layer of ato ms at
the metal surface are always o pen.
In situ checks are abso lutely necessary. Either they are pro -
vided by the experimental electro chemical results themselves o r by
o ther metho ds such as o ptical techniques.
Fo r instance, at the present, by o ptical measurements (by in
situ electro reflectance) it was shown that the symmetry pro perties
of the crystal faces were no t perturbed by co ntact with aqueo us
so lutio ns. Fo r copper, all faces studied present their azimuthal
aniso tro py with respect to the plane of po larizatio n of the incident
light, except for (100), (111), (211), and some neighbo ring faces of
(111) for which no azimuthal aniso tro py is o bserved.
54
Fo r silver,
the twofold symmetry of the (110) face was o bserved: the electro re-
flectance spectra at no rmal incidence differ markedly when the
electric field vecto r of light is parallel or perpendicular to the surface
ato mic "rails. " This is no t the case for the (111) and (100) faces
55
which have higher symmetry. Fo r gold, no azimuthal aniso tro py
was o bserved for the (111) and (100) faces with respect to the plane
of po larizatio n of the incident light, while the (110) and (311) faces
present an azimuthal aniso tro py.
56
'
57
It do es no t necessarily mean
that the o utermo st layer of surface ato ms is 1 x 1, because a surface
reco nstructio n such as 1 x 2 for Au (110) wo uld have the same
symmetry o rder as l x l . These are already studies of the metal
surface in the presence of the electro chemical dl.
t For further discussio n of techniques required for o btaining ultraclean co nditio ns,
see the chapter by H . A . K ozlowska in Comprehensive Treatise of Electrochemistry,
Ed. by E. Yeager, J. O'M. Bo ckris, and B. E. Co nway, Plenum Press, New Yo rk,
1984, Vo l. 9.
Most electro chemistry labo rato ries have no o ptical setup and
therefo re are limited to electro chemical o bservatio ns. Furthermo re,
the po tentialities of i(E) curves and C(E) curves seem larger
every day; this means that under rigo ro usly clean and well-defined
co nditio ns, the wealth of info rmatio n co ntained in these curves is
no t yet fully explo ited.
Fo r any metal in a given so lutio n, at a given temperature, the
range of po tential E over which only a change (with po tential
applied) of the electro static charge o n the metal (and co rrespo nd-
ingly in so lutio n) is o bservable, is the "dl region."
In the dl regio n, co mpariso n of the i(E) and C(E) curves can
be used as a first test [o ne sho uld be able to deduce o ne from the
o ther, the current being o nly capacitive, (i = C dE/ dt)"\. The shape
of the minimum (co rrespo nding to the capacity of the diffuse part
of the electro chemical dl) o n the C{E) and i(E) curves (Fig. 15)
for the case of no adso rptio n in dilute so lutio n, is ano ther criterio n;
it sho uld no t be to o different than that o bserved for mercury, but
its po sitio n in the range of po tential can be co mpletely different.
The shape of the adso rptio n peak is ano ther criterio n (in the case
of adso rptio n); it sho uld be sharp and repro ducible. Of co urse, the
stability and repro ducibility of the curves are impo rtant and sho uld
be o bserved no t only in the dl regio n but over all the range of
po tential explo red.
On the i(E) curves, the dl regio n is limited at negative po tential
by a faradaic current co rrespo nding to the reductio n of the so lvent
(o r of the catio n); the o bservatio n of the foot of the wave of this
current gives an indicatio n of the cleanliness of the interphase.
Undo ubtedly, a steep foot of the wave of current (Fig. 16) is
indicative of a cleaner (o r less dirty) surface-than a curve that rises
slowly because the electro chemical reactio n rate is slowed do wn
by some impurities (for instance, carbo naceo us species) at the
surface. Slight hydro gen evo lutio n will clean the surface; but care
must be taken to avo id stro ng hydro gen evo lutio n which co uld
modify the o utermo st layer of metals ato ms irreversibly.
On the i(E) curve the dl regio n is limited at po sitive po tentials
by o xidatio neither of the anio n, the so lvent, the metal, o r of
impurities. Fo r some metals, o xidatio n of the metal o ccurs at
po tentials less po sitive than o xidatio n of the so lvent. When the
o xygenated co mpo und formed can be to tally reduced at the
40
A . H amelin
- 0
r
/
5
y~
/
50
i
50
100
i
-
/
\
V
\
\
(yA.cnf
2
)
'' \
/
/
/
i ^ x l O
-A
\
+0.5 *
**'. \ .7
\" 1
/
/ _y
^
E
s c e <
V
>
^ ^ (210)
I i l l ;
Figure 15. i(E) curves for the (111) and (210) faces of gold in contact
with an aqueous solution of K B F
4
(lO mM ); sweep rate = 20mVs~
1
,
temperature = 25C , and pH = 3. 5. For the (210) face, in the dl region,
the i(E) curve enlarged 10 times shows clearly the shape of the C(E)
curve, in particular, the minimum corresponding to the contribution of
the diffuse part of the dl.
58
electro chemical interphase, the o bservatio n of the currents of o xida-
tio n and reductio n (number, shape and po sitio n of the peaks) gives
some indicatio ns; thus, the sharper (the less ro unded) the peaks
are the cleaner the interphase is, and the mo re details are o bservable
the cleaner the surface is (then the structural details of the surface
are available for bo nding). This is the case for gold in so lutio ns
Doable-L ayer P roperties at M etal E lectrodes
E (V) _
L 0
_
0 > 5
41
50
100
l ( y A. c r
Figure 16. i(E) curves for the (311) face of silver in a stirred
aqueo us so lutio n of NaF (5 mM); sweep rate = 20 mVs"
1
.
Curve 1 represents a partially deaerated so lutio n and curve
2 a dearerated so lutio n at a temperature of 21C; the begin-
ning of the reductio n of the solvent is visible on curve 2.
witho ut stro ng specific adso rptio n (Fig. 15). Cyclic vo ltammetry is
a co nvenient technique in this case; i(E) curves give info rmatio n
o n the physical state of the surface because the number, the po ten-
tials, and the shape of the o xidatio n peaks, in a given so lutio n, are
characteristic of each co .
59
Fo rmatio n of mo no layer of o xide and
reductio n pro cesses of go ld faces can clean the surface; perfo rmed
at to o high a sweep rate (larger than 100mVs"
1
) they can modify
the metal surface irreversibly and then change the co .
49
Worse still
may be po tential steps, but the effect of these on the o utermo st-layer
surface ato ms has no t been carefully studied.
When some electro active species exist in so lutio n or at the
surface of the metal, in the range of po tential co rrespo nding to the
42 A . H amelin
dl regio n, a current due to the electro chemical reactio n is o bserved.
Fo r instance, the o bservatio n of the current co rrespo nding to reduc-
tio n of oxygen (from the air) in aqueo us so lutio n on gold (o r silver)
electro des gives a good indicatio n of the cleanliness of the inter-
phase; the foot of the wave sho uld be steep (as for so lvent reduc-
tio n), while in stirred so lutio n the current sho uld be diffusion
co ntro lled (Fig. 16).
We co nsider next ano ther example. Years ago , gold faces were
cut, mechanically po lishedeither with "alumina" o r with
"diamo nd paste"and then electro po lished. No AES was available
to check the final chemical state of the faces. When so lutio ns
co ntaining only io ns, which adso rbed slightly, were deaerated with
nitrogen, curves for all samples were of the type exemplified by the
so lid line of Fig. 17. When molecular hydrogen was bubbled in these
so lutio ns, for samples prepared with "alumina", curves were of the
type shown in curve 1 of Fig. 17; for samples prepared with
"diamo nd paste", curves were typically as sho wn in curve 2 of Fig.
17. The results o btained with the faces po lished with "alumina"
were co mparable (as far as o xidatio n of mo lecular hydro gen is
co ncerned) to the results o bserved with a go ld sphere o btained by
just melting a go ld wire.
60
The results of the faces po lished with
"diamo nd paste" (altho ugh also electro lytically po lished) showed
that some co nstituents of the so -called "diamo nd paste" remained
buried in the go ld, which is a soft metal, and were respo nsible for
the catalytic o xidatio n of mo lecular hydro gen. Nevertheless, the
pzc's o bserved for all these faces were satisfacto ry when nitro gen
was used to deaerate the so lutio ns, and co mparable to the o nes
o bserved with samples prepared with "alumina".
These examples are given to show that so metimes great experi-
mental experience and acumen are necessary to detect the cause
of unexplained results and their o rigin may be in o ne of the steps
of surface preparatio n.
Fo r o ther materials, o ther types of arguments sho uld be
develo ped, acco rding to the known pro perties of the electro de.
The autho r must apo lo gize for talking mo re abo ut gold and
silver than abo ut o ther metals; but it sho uld be po inted o ut that
to o much work on o ther metals is being published witho ut giving
significant detail on the preparatio n of the crystal faces and the
checking of the state of their interphases. Therefo re, it is no t po ssible
43
- 0 5
Figure 17. i(E) curves for two different samples of the (110) face of gold in
stirred HC1O
4
(lOmAf): deaerated with nitro gen (so lid line) and deaerated
with hydrogen (do tted line represents sample 1 and dashed line represents
sample 2). Temperature = 22C; sweep rate = 20mVs~
1
.
to describe the techniques that may have been used with those other
metals.
V. E L E C T R O C H E M I C A L R E S UL T S
T he range of potential in which only the change of the electrostatic
charge on the metal (and correspondingly in solution) is observable,
44 A . H amelin
is the dl region; it depends in a given so lutio n, at a fixed temperature,
on the nature of the metal.
From experimental o bservatio ns in a given medium the dl
region is nearly the same for all co's of a given metal and for a
po lycrystalline electro de of this metal in the same medium, it
depends o n the chemical nature of the metal. In this regio n the
interphase is "ideally po larized" o r "blo cked"; in an equilibrium
situatio n the thermo dynamic analysis of the dl behavio r can be
perfo rmed in this po tential regio n.
6
Altho ugh the sho rtage of data for the dl on single-crystal faces
was already po inted o ut,
10
we may no te that:
1. No results co ncerning cadmium, indium, etc., are kno wn.
2. Nearly all measurements have been o btained at "ro o m
temperature. "
3. Nearly all experiments were carried o ut in aqueo us
so lvent.
4. In most cases o nly the three lo w-index faces were studied;
o nly for gold has a large number of high-index faces been
investigated, etc.
Some trends in o ur current understanding of dl can be discussed.
Co nsidering the way in which the io ns present in so lutio n
interact with the electro de, a successful appro ach was develo ped
for liquid metal electro des: the so lutio n side of the dl was divided
by a plane parallel to the electro de surfacethe "o uter Helmho ltz
plane" (o Hp). On the so lutio n side of the o Hp, only lo ng-range
interactio ns o beying classical electro static and distributio n laws
arise; this is the so -called diffuse layer [lo ng-range interactio ns are
described by the Go uy-Chapman (G-C) theo ry]. On the metal side
of the o Hp, sho rt-range interactio ns as well as lo ng-range o nes
exist. These sho rt-range interactio ns change the so lvent pro perties,
while interactio ns between the io ns and the metal electro de take
place. This is the so -called inner part of the dl (Stern o r Helmho ltz
layer). It has a thickness of mo lecular dimensio ns. The who le dl is
represented by the Go uy-Chapman-Stern (G-C-S) mo del.
When there is substitutio n of the so lvent mo lecules, by an
o rganic neutral substance, in the do uble-layer regio n the adso rp-
tio n-deso rptio n of this substance can usually be o bserved on the
C(E) curves.
When using this appro ach for different crystal faces, o ne might
expect that the diffuse layer will pro bably no t be influenced by
ato mic arrangement of the surface for a given metal, while the co
will stro ngly influence the inner part of the dl. But the co ntributio n
of the diffuse part of the dl varies with the density of charge at the
electro de surface, acco rding to the G-C theo ry, and the density of
charge at a given po tential impo sed to the electro de depends on
the co . Therefo re we have to discuss first the influence of the co
on the so lutio n side of the o Hp; then we will discuss sho rt-range
interactio ns o n the metal side of the o Hp and the validity of the
G-C-S mo del. However, for the sake of clarity, it is better first to
analyze the pzc values published in the literature
10
and then to
co nsider the behavio r of the so lutio n and the metal sides of the
o Hp. Separatio n of the results into tho se for co nditio ns with and
witho ut specific adso rptio n has been avo ided because many bo rder-
line cases are o bserved.
Some mo no graphs may be fo und useful in co nnectio n with
this sectio n; see References 3, 6, and 9.
1. The pzc' s
Most of the pzc values published in the literature were determined
by o bservatio n of the minimum due to the co ntributio n of the
diffuse part of the dl to the C(E) curves. See, for instance for
Ag(100), Ref. 62 and Fig. 18. Ho wever, depending o n the metal,
for a given so lvent and for given io ns, the po tential at which the
density of charge is zero at the metal surface may be in the dl regio n
for all co 's o r for only some of them, o r for no ne of them. When
a pzc canno t be o btained by this direct metho d, an indirect metho d
has to be used,t as was the case for co ppert
63
and zinc.
64
Most of the pzc values are summarized (Fig. 19) as a functio n
of the melting po int of the metal
65
; the length of the so lid lines
show to what extent the pzc varies with the co for each metal. It
t The scraping metho d canno t be used fo r crystal faces o bvio usly.
$ Altho ugh it seems po ssible to o btain the pzc by a direct metho d fo r co pper (111)
and (100).
Fo r go ld, the extent the pzc varies is given here fo r 10 mM NaF; it is smaller in
10 mM HC1O
4
.
46
A . H amelin
50
C (yF.cnf
2
)
KPF
C
0
- 1 5
50
- 1. 5
- 1. 0
- 0. 5
(a)
- 1. 0 - 0 . 5
(b)
Figure 18. C(E) curves fo r the (100) face of silver in aqueo us
so luto ns of (a) KPF6 and (b) NaF for different co ncentratio ns
of electro lyte: ( ) 100, ( ) 40, ( _ . ) 20, ( )
10, and ( ) 5 raM Sweep rate = 5 mVs"
1
; frequency =
20 Hz (Ref. 62)
is clear that the co influences largely the pzc for high-melting metals
and has little o r no influence for lo w-melting metals. This is pro bably
due to the mo bility of the surface ato ms at ro o m temperature for
lo w-melting metals.
As the pzc (in the case of no adso rptio n) is linearly related to
the electro nic work functio n of the metal surface
66
'
67
and as the
MP
C
-1000
Ag
-500
Zn -
Pb
Sn
Cu
Au
E
sce
(V)
Figure 19. Aniso tro py o f the pzc
o f different metals as a functio n o f
their melting po int; the so lid lines
sho w to what extent the pzc varies
with the co fo r each metal.
65
Bismuth, which is a semimetal, is
no t plo tted. - 1 0 - 0 5 0 + 0 5
work functio n depends on the metal surface do uble-layer dipo le
mo ment [see Section III. 5(ii)] which varies with the co , the pzc
sho uld vary with the co as the work functio n. Unfo rtunately, the
general influence of the co was experimentally shown for the elec-
tro nic work functio n for co pper
68
and for the pzc for go ld; ho wever,
the parallelism of these two experimental variatio ns is excellent.
69
The relative surface energy [see y plo t of Sectio n III. 5(iii) for
the fee system; Fig. 12] varies with the co ; the co mpariso n estab-
lished between the relative surface energy [relative to the (210) face
for the fee system] and the pzc of go ld faces is surprisingly go o d
if we keep in mind that the former parameter is calculated from
a mo del (in the nearest-neighbo r bro ken-bo nd appro ximatio n)
[see Sectio n III. 5(iii)] and the latter parameter is experimental
10
(Fig. 20).
As fo reseen from the discussio n of Sectio n III. 5, the co ntribu-
tio ns to the surface po tential from the "o verspill" of the electro ns
perpendicularly to the metal surface and the "smo o thing" by a
lateral flo w of electro ns from high-io nic-density regio ns to low-
io nic-density o nes, explain the decrease of the electro nic work
functio n and the pzc from smo o th to ato mically stepped surfaces.
Obvio usly, the most densely packed face sho uld have the most
po sitive pzc because it has the highest work functio n, and the
ro ughest face on an ato mic scale sho uld have the most negative
pzc because it has the lowest electro nic work functio n. This is
o bserved experimentally for metals.
When there are irregularities (o n an ato mic scale) at the metal
surface, they sho uld lo wer the work functio n and shift the pzc
negatively. It was o bserved experimentally that mo no ato mic steps
48 A . H amelin
tf(hko/y(
0.8
0 9
\
-
1
-Vr
210)
X
60
h-
Y
i
8
,
\
\
\
A
/ 1 A
1
1 1
\
x x V
20
i \ i i i
1
lAO
+0.3-
-.0.2-
V
/O-
. y -0.1-
I degrees
O O O O OO *- ^
r
'
r ) i r )
Or >- - ' ^^^' ^r ^^_o O O O .
* CNJ o
r
~ ' ^~* cr^ * *^ LO co CNJ r o t o ^ ^ * * _
Figure 20. Variatio n of the relative surface energy ( ) and pzc (x) of gold faces
in 10 mM NaF at room temperature
69
with the co plo tted as a co ntinuo usly varying
parameter. Here (hkl) is a family of planes.
10
on terraces of singular faces shift the pzc negatively. Fo r a (100)
face of go ld, the 1 x 1 ato mic arrangement [see Section III. 5(i)]
sho uld have a mo re negative pzc than a reco nstructed o ne mo re
densely packed in ato ms, if bo th can exist at the electro chemical
interphase.
This aniso tro py of the pzc tends to increase with the melting
po int of the metal. Therefo re the influence of ato mic steps and
irregularities is less o bservable in electro chemical results o btained
with lo w-melting metals than for results o btained with high-melting
metals.
When adso rptio n takes place, if the adso rbate is po sitively
charged it lowers the work functio n but the pzc is shifted po sitively
with increasing co ncentratio n of adso rbate; if the adso rbate is
negatively charged it raises the electro nic work function but the
pzc is shifted negatively with increasing co ncentratio n [see Fig. 21
for adso rptio n of Cl~ on Ag (110)
70
]. There is no lo nger a parallelism
between the pzc and wo rk-functio n data. In vacuum the adso rbate
is part of the surface and, for instance, po sitively charged adso rbate
allows the electro ns to leave mo re easily from the metal surface (it
lowers the work functio n) and the surface dipo le is o riented to ward
the vacuum (Fig. 22a). At the electro chemical interface the sur-
face dipo le is o riented to ward the metal (Fig. 22b) because for a
-1. 2
-1. 0
-0.8
-0.6
(110)
-3 -2
Figure 21. Variatio ns of the po tential with the
logarithm of the co ncentratio n of the electrolyte at
co nstant density of charge at the metal surface for
the (110) face of silver in so lutio n x mM NaCl +
(40-x) mM NaR
70
metal _
vacuum
metal
( " ) electrolyte
dipole
(a)
Figure 22. Representatio n of (a) the metal-vacuum interface and (b) metal-
electrolyte interface in the case of adso rptio n of a positively charge species.
50 A . H amelin
po sitively charged adso rbate negatively charged io ns come into the
dl to ensure electric neutrality of the interfacial regio n.
Co nsidering the who le set of pzc values published,
10
there are
some discrepancies and some inco nsistencies; how much are they
due to po o r co ntro l of the surface's actual structure and cleanliness
is the questio n.
2. T he S olution S ide of the oH p
The variatio ns of the capacity of the diffuse part of the dl with the
po tential at the electro de surface has the shape of a hyperbo lic
co sine (G-C theo ry for a symmetrical electro lyte); the minimum
of capacity co rrespo nds to zero -charge density on the metal. This
density of charge co rrespo nds to a po tential impo sed on the elec-
tro de. This po tential of zero charge (pzc) varies with the co (see
Section V. I).
The so lutio n side of the o Hp, in the case of no (o r slight)
adso rptio n and for dilute so lutio ns, gives rise to a depressio n o n
the experimental C(E) curves, deepening with the dilutio n of the
so lutio n (Fig. 18). Even if the density of charge is uniformly dis-
tributed at the metal surface, the shape of the experimentally
o bserved depressio n is no t exactly a hyperbo lic co sine because of
the co ntributio n of the inner part of the dl (see Section V.3).
Furthermo re, co mplete no nspecific adso rptio n exists only for a very
small number of systems and over restricted po tential ranges. The
co ntributio n of the diffuse part of the dl (the hyperbo lic co sine)
appears o n the C(E) curves (for low co ncentratio ns of the so lutio n)
mo re distinctly when:
1. The adso rptio n is weak (o r no nexistent).
2. The inner-layer capacity existing on the metal side of the
o Hp is high in this range of po tential.
3. The co ncentratio n of the io ns in so lutio n is low (Fig. 18).
All of this is summarized in o ne well-known relatio n
71
:
1/C = 1/C + 1/C
d
(l + da
1
/da) (1)
where C is the inner-layer capacity, C
d
the diffuse-layer capacity
(if C
d
is very large, 1/C = 1/C), a the charge on the metal surface,
and or
1
the charge due to adso rbed io ns. (If da
1
/da = 0, 1/C =
1/C + \/C
d
\ if da
1
/da = - 1 , 1/C = 1/C).
The last two parameters are definitely o n the metal side of the
dl, but they also influence the co ntributio n of the diffuse part to
the to tal dl capacitance.
All this is clear as lo ng as the charge is unifo rmly distributed
on the surface of the so lid metal electro de (as it is for mercury)
and then the thermo dynamic analysis can be reaso nably carried
o ut. t
But if there are defects on the metal surface (dislo catio n lines,
pits due to electro po lishing, etc.) the charge is no t uniformly dis-
tributed o n the surface. The influence of these irregularities will be
all the mo re visible on the C(E) curves when their relative area is
larger and their pzc is far from the pzc of the ato mically smo o th
part of the electro de (o r mo re generally if their co ntributio n arises
in a range of po tential in which the curve co rrespo nding to the
smo o th part of the electro de do es no t have a large feature which
co uld mask it).
This last po int requires some co mments. Small pits (o n a
smo o th face) can be represented by a co mbinatio n of mo no ato mic
steps and kinks
15
(see Sectio n III. 4). Therefo re their behavio r, if
they are large eno ugh, is close to that of the ro ughest face o n an
ato mic scale. Also their interference will be mo re visible, on the
C(E) curves, for an ato mically smo o th face than for an ato mically
ro ugh o ne. Fo r instance, their effect is mo re visible in the fee system,
for the (111) face than for the (210) face. On the co ntrary, for the
fee system, a small facet, (111) o riented will alter the C{E) curve
of a ro ugh face mo re than that of a smo o th face.
When making lo w-index faces, a slight diso rientatio n, which
co uld be due to cutting (see Section IV.2), will create some steps
and kinks. The co ntributio n of these co uld be no ticeable in the
electro chemical results.
These ideas on the effects of no nunifo rmity of charge density
on the C(E) curves were checked years ago for an extreme case
po lycrystalline silver in dilute so dium fluo ride so lutio n^
15
(Fig.
23)in the following way. Fo r a model po lycrystalline electro de,
t The work required at a solid metal surface to form a unit area of new surface by
stretching under equilibrium co nditio ns is no t equivalent to the surface tensio n
and for some faces is obviously an aniso tro pic quantity (see p. 21 of Ref. 9).
+ Later it was shown that there was a slight adso rptio n of the fluoride ion on silver
electro des,
62
but this does not alter the co nclusio ns.
52
A . H amelin
60
20
(110)
(100)
(111)
calculated
-1. 0 - 0. 5
(V)
Figure 23 Experimental C(E) curves for silver (111),
(100), and (110) faces in lOmMNaF (frequency of the
alternating signal = 20 Hz, sweep rate = lOmVs"
1
) and
calculated C(E) curve for a model po lycrystalhne elec-
tro de
15
made up of only the three faces of simplest indices, acco rding to
the stereo graphic pro jectio n (Fig. 5), there are at the surface 46%
(110) o riented, 23% (100) o riented, and 31% (111) o riented; the
calculated C(E) curve [taking into acco unt these pro po rtio ns for
the co ntributio ns of the three experimental curves of the (110),
(100), and (111) faces and assuming a parallel capacito r equivalent
circuit] is very close to that o bserved experimentally for po lycrystal-
line silver. The following features are to be no ted:
ftM &le-L ayer P roperties at M etal E lectrodes 53
1. The diffuse-layer minimum is bro ader than for lo w-index
faces (o n which charge can be tho ught of as unifo rmly
distributed).
2. The capacity minimum is very clo se to that of the (110)
face, because the diffuse-layer minima for the (100) and
(111) faces appear in ranges of po tential where the two
o ther faces have high capacity values.
3. The capacity peak for po sitive density of charge is less
high than for lo w-index faces (Fig. 23).
Fo r high-index faces a number of steps and kinks are necessary
for the average specified co . They alter the distributio n of charge
at the surface [see Sectio n III. 5(ii)] and o n the C(E) the part of
the curves which reflects the co ntributio n of the diffuse part of the
dl. Unfo rtunately, the study of high-index faces was perfo rmed only
for go ld. Fo r this metal, "seco ndary" effects
72
were o bserved!; they
have to be discussed first for lo w-index faces and are as fo llo ws:
1. Fo r the (100) face, there is an influence of the negative
limit of the explo red range of po tential o n the pzc and on the
hysteresis existing between bo th sweeps of the C(E) curves
73
(Fig. 24).
2. Fo r the (111) face, no influence of the negative limit arises
but an hysteresis of the C(E) curves in the range of po tential of
the pzc
72
is o bserved, the o rigin of which is at slightly po sitive
density of charge (Fig. 25).
3. Fo r the (110) face, there is no hysteresis and no effect of
the range of po tential explo red but a seco ndary effect was also
o bserved. It is easier to o bserve in co ncentrated so lutio ns and in
the case of specific adso rptio n (see Sectio n V.2); it do es no t seem
to alter the co ntributio n of the diffuse part of the dl on the C{E)
curves.
72
These seco ndary effects are less and less impo rtant as the co 's
of gold faces are further from tho se of the lo w-index faces. They
will be discussed in mo re detail in Sectio n V.3(ii).
Besides these "seco ndary effects" there is slight adso rptio n of
the fluo ride io n on go ld
74
and most of the studies for high-index
faces were do ne in fluo ride. Last, but no t least, the dl regio n for
go ld [for which the C(E) curves sho uld show no dispersio n over
* They were no t o bserved fo r silver faces and are no t mentio ned in the literature
fo r o ther sr metals
54
A . H amelin
C (yF. cm"
2
)
40
20
0
U
E (V)
see
x
'
- 0. 5
+0.5
Figure 24. C(E) curves for the (100) face of gold in
10 mM N aF (frequency of the alternating signal = 20 H z;
sweep rate = 10 mV s"
1
) for different negative limits of the
range of potential explored.
73
a large range of frequency] is difficult to define (see Fig. 26a). These
o bservatio ns explain the C{E) curves of the three faces of lowest
indices (Fig. 26b).
Ho wever, for high-index gold faces, the co ntributio n of the
diffuse part of the dl appears clearly. Fo r the sake of clarity, the
po tential scales for the different C(E) curves
75
have been aligned
to the pze's (all pze's are "at zero ") and the capacity minima are
adjusted so that the scale for capacity is given 5% (Fig. 27).
Obvio usly, for the (210) and (311) gold faces, the depressio n on
the C(E) curves is narro w and nearly the same as for the (110)
Doble-L ayer P roperties at M etal E lectrodes
55
60
40
20
C (pF. cnf
2
)
- 0. 5 0
E
(v)
see
v
'
Figure 25. C(E) curves for the (111) face of gold in 10mM
KBF
4
(frequency of the alternating signal = 20 Hz; sweep
rate = 10 mVs"
1
) for two po sitive limits of the explo red range
of po tentials.
58
face. Fo r faces which have the most po sitive pzc's there is already
interference of some faradaic pro cess for the po sitive density of
charge; this is the case for (533) and (755) (Fig. 27a) and (332)
(Fig. 27b). However, for a systematic change of surface structure,
(311), (211), and (533) [which are 2(lll)-(100), 3(lll)-(100),
4(lll)-(100)], the capacity depressio n beco mes bro ader and
bro ader as the charge density seems to be less unifo rmly distributed.
The same explanatio n wo uld be valid for the series (110), (551)
56
A . H tmelin
C (uF. cm"
2
)
-40
i (uA.cm"
2
)
-20
-0
(a)
-0.5
-50-
-100-
+0. 5
E (V)
see
v
'
+ 1.0
60
40
20
C (yF. cm"
2
)
(110) / -
(b)
(111)
-0.5 (V)
Figure 26. (a) C(E) curves for a (210)
gold face in 40 mM NaF: ( ) 15,
( ) 20, ( ) 40, and ( )
80 Hz; sweep rate = 10 mV s"
1
. Cyclic
voltammogram of the face in
lOmMNaF; sweep rate =
20mVs"
!
.
74
(b) C(E) curves for the
(111), (100), and (110) faces of gold
in 10 mM NaF (frequency of the alter-
nating signal = 20 Hz; sweep rate =
SmVs"
1
) for the positive sweeps,
witho ut co rrectio n for the ro ughness
factor. For (100), curves are given for
two different negative limits.
45
22.5
C (yF.cnf
2
)
14 (755)
' /' (533)
'/! \
(a)
-0.5
-0.5
45
22.5
n
C (yF.cr
5%
(b)
n" )
^ \
/
->
/
/
.
/
-(332)
(221)
(331)
I
1
45
22.5
C (yF.cnf
2
)
5%
, 13311
(c)
- 0. 5
45
22.5
C (yF. cm"
2
)
5%
(d)
-0.5
Figure 27. (a), (b), (c), and (d) C(E) curves for different faces of gold in 10 mM N aF. S weep rate = 5 mV s~
l
;
frequency of the alternating signal = 20 H z.
75
For atomic arrangement of the faces, see Figures 9-11.
58 A . H amelin
[which is 3(110)-(lll)], and (331) [which is 2(110)-(l 11)] (Fig.
27c). Fo r ato mically very ro ugh faces the "smo o thing" effect (see
Section III. 5) is such that the density of charge has nearly the same
uniform distributio n at the surface; this wo uld be the case for (110),
(210), (320), and (310) (Fig. 27d), and (311) (Fig. 27a) which show
a capacity depressio n of the same shape on the C(E) curves.
Therefo re it seems that, in some cases, the ato mic no nunifo r-
mity of the surface entails a disto rtio n of the shape of the C(E)
curves in the part due to the co ntributio n to the diffuse part of the
dlf; then blind applicatio n of the G-C-S theo ry wo uld be a mistake,
but for lo w-index faces (and furthermo re for lo w-melting metals)
the applicatio n of the G-C-S theo ry is no t questio nable, as lo ng
as it is used in a true d\ regio n.
3. T he M etal S ide of the oH p
On the metal side of the o Hp, there is the so -called inner layer (the
co mpact layer, o r Stern o r Helmho ltz layer) which is a mo lecular-
diameter thick and in which sho rt-range interactio ns as well as
lo ng-range interactio ns exist.
When there is no adso rptio n, only so lvent mo lecules are present
in this layer. Then the variatio n of the inner-layer capacity vs. charge
density gives info rmatio n on the metal-so lvent interactio ns [see
Section V.3(i). The sho rt-range interactio ns change the so lvent
pro perties.
When there is io nic adso rptio n, there are io ns on the metal
side of the o Hp (substitutio n for the water mo lecule). These metal-
io n interactio ns canno t be described by the G-C theo ry [see Section
V. 3(ii)]; they alter the metal-so lvent interactio ns.
When there are o rganic neutral substances on the metal side
of the o Hp, there is also substitutio n of so lvent mo lecules by neutral
mo lecules and metal-neutral substances interactio ns are o bserved,
they co uld also alter the metal-so lvent interactio ns; in some cases
the adso rptio n-deso rptio n peaks can be o bserved [see Sectio n
These three cases will now be briefly reviewed.
tThe po ssible nonuniform distributio n of charge for some faces is controlled,
whereas for polycrystals no nunifo rm distributio n of charge is uncontrolled.
59
(i) Metal-Solvent Interactions
Altho ugh, o bvio usly, there is a co ntinuo us change of structure
and co mpo sitio n in the dl, from the metal surface to the bulk of
the so lutio n, the mo del which has explained successfully many
results for mercury, was assumed to be valid for o ther metals. In
the case of no adsorption this mo del leads to the co nclusio n that
the variatio ns of the inner-layer capacity C
1
with charge density a
sho uld be independant of the co ncentratio n of the io ns in so lutio n.
In the case of no adso rptio n, there are o nly so lvent mo lecules on
the metal side of the o Hp. Only for water are there available results
o n metal crystal faces.
Fo r bismuth faces these water-metal interactio ns are represen-
ted by the C
l
(a) curves of Fig. 28.
76
At significantly negative
charges, C
1
depends very little on the co , while at zero and po sitive
charge density the most densely packed (ato mically) face has lo wer
values. No co rrectio n for the ro ughness facto r (see Section V.4)
was perfo rmed when plo tting these results.
Fo r silver faces, years ago ,
15
these C'(a) curves were fo und,
for the three faces of lo west indices, to be nearly independent of
the co ncentratio n of the fluo ride io ns (after co rrectio n for the
28
20
C
1
(yF.cm"
2
)
-15 -10
-5 0
Figure_28. C
l
(a) curves for bismuth faces: (O) (111) face; (A) (Oil) face;
() (211) face, and ( ) po lycrystalline bismuth. From experimental results
in KF so lutio ns.
76
60 A . H amelin
100
60
20
C
1
(uF. cnf
2
)
-10 0 + 10 +20
a (uC. cm )
Figure 29. C'(cr) curves fo r silver faces (111), (100), and (110)
fro m experimental results in NaF so lutio n co rrected by the
ro ughness facto r.
15
ro ughness facto r) (Fig. 29). Fo r negative-charge density, the vari-
atio ns are identical. Fo r zero charge and small po sitive charges,
the most densely packed face has the lowest value (the co ntrary
was o bserved by o ther autho rs
77
). Later, it was shown that there is
slight adso rptio n of fluoride io ns
62
and the absence of influence of
the co ncentratio n of the io ns in so lutio n was demo nstrated for the
(100) and (110) faces of silver in KPF
6
62
'
78
(Fig. 30) (after co rrectio n
for the ro ughness facto rt). Therefo re the mo del is valid at least for
these faces of silver. This is why we have divided Section V into
two subsectio ns on the so lutio n side and the metal side of the o Hp.
t Fo r the (100) face the curves are also co rrected fo r inco mplete disso ciatio n o f
KPF
6
.
62
100
50
. c
1
(a)
-20
#">
K
0.04 M
* 0.02 M
x 0.01 M
o 0.005 M
M
-2,
100
50
n
C
1
(
(b)
UF.CM-
2
)
/
/
i
$
8
X
o
\
\
%
\ > \
\
KP
\ ^
F
6
0.04 M
" 0.02 M
A
0. 01 M
0.005 M
<7/(^C.CM"
2
)
20 -20 -10
10 20
Figure 30. C'(o -) curves fo r silver faces fro m results in KPF
6
so lutio ns: (a) (100) face co rrected fo r ro ughness facto r and
inco mplete disso ciatio n o f the electro lyte
62
and (b) (110) face co rrected fo r the ro ughness facto r o nly.
78
62 A . H amelin
Altho ugh C
l
(cr) curves were published for gold faces
73
'
74
they
were no t fo und to be independent of the co ncentratio n of the io ns
in so lutio n; this can be due either to specific adso rptio n of io ns o r
to the existence of some faradaic pro cess in the range of po tentials
used, i.e., this range of po tential was no t really a "dl regio n," o r
the G-C-S theo ry is adequate at low but no t at higher co ncentra-
tio ns. Unfo rtunately, the co rrectio ns pro po sed for the G-C-S theo ry
have no t yet been used by practicing electro chemists.
Fro m so few results it is difficult to draw precise co nclusio ns
on the influence of the co o n the metal-so lvent interactio ns. It was
fo reseen
79
that Ag(dip), the change of the co ntributio n to the
metal-so lutio n electro de po tential dro p due to preferential o rienta-
tio n of water dipo les, increases as the wo rk functio n of the metal
surfaces decreases, i.e., is larger for the (110) face than for the (100)
face (of the fee system); this was o bserved for silver faces in KPF
6
(Fig. 30).
(I I ) Metal-Ion Interactions
Mo st papers published on single-crystal-face behavio r
10
deal
with this situatio n because most io ns adso rb on so lid electro des of
sp and sd metals. Adso rptio n depends o n the nature of the io ns
and the metal, the interactio n between io ns and so lvent in the dl,t
the interactio ns between electro de metal and so lvent, and the
influences of these interactio ns on each o ther. All this exists already
for electro des which are no t single-crystal faces, but the situatio n
is co mplicated by the fact that the charge is distributed at the surface
in an unco ntro lled way. This is no t the case for single-crystal faces
for which the strength of adso rptio n, as well as its variatio n with
charge density at the electro de surface, co uld depend on the ato mic
structure of the face which is the electro de. Ho wever, despite these
co mplicatio ns, some pro gress has and can be made.
Any species, the surface excesses of which are no t to tally
described by the diffuse-layer theo ry, are said to be specifically
adso rbed. cr\ the quantity of charge, that canno t be acco unted for
by the diffuse-layer mo del, is the charge at the electro de surface
t The io ns are no more in a symmetrical situatio n as they are in the bulk of the
so lutio n.
Dtlb!e-L ayer P roperties at M etal E lectrodes
C (uF. cnf
2
)
60
63
20
E
sce
- 1. 6
-0.8
Figure 31. C(E) curves for co pper faces in
50mMNa
2
SO
4
+ 5mMTBAI: curve 1,(111),
curve 2, (100); and curve 3, (110).
81
due to the specifically adso rbed io ns; for anio ns
a
1
= zFT' - zFT'
d
(2)
where z is the valence of the anio n, F the Faraday co nstant, T the
anio n relative surface excess, and T~
d
the anio n relative surface
excess in the diffuse layer.
Fo r faces of a given metal, the pheno meno lo gy of specific
adso rptio n is the fo llo wing.t
(a) Type of ions
Alkali and alkaline-earth catio ns have less tendency to adso rb
than anio ns on metal faces, as was o bserved on o ther metal
electro des. Ho wever, in general, large catio ns do adso rb; Cs
+
was
demo nstrated to adso rb o n Ag(100).
80
TBA
+
was demo nstrated to
adso rb o n Cu(lll), Cu(100), and CuCllO)*
63
'
81
(Fig. 31) and o n
t The effect of temperature on specific adso rptio n was no t studied on single-crystal
faces.
$ It was used as an indirect metod to determine the pzc's.
64 A . H amelin
Zn(OOOl), Zn(lOlO), and Zn(1120).
82
'
83
Fo r TBA
+
, there is a po ssi-
bility of fo rming catio n-anio n pairs which may be co nsidered as
appro ximating to neutral mo lecules in their adso rptio n behavio r
[see Sectio n V. 3(iii)]. Underpo tential depo sitio n (UPD) of a fo reign
metal o n crystal-face substrates is an extreme case of the adso rptio n
of catio ns; then the adso rbate beco mes part of the substrate surface.
Therefo re it is no t included in the dl pro perties of single-crystal
faces. Ho wever, as for the understanding of adso rptio n of anio ns
o n stepped faces, co mpariso n with these results is very helpful,
so me results for UPD of lead o n go ld faces will be given in the
paragraph o n stepped faces.
(b) Dependence on charge density
The amo unt of specifically adso rbed io ns increases with
increasing density of charge of the o ppo site sign o n the electro de
(altho ugh negative io ns begin to adso rb already at low negative-
electro de-charge densities). When experimental results are precise
eno ugh and when the dl regio n is sufficiently extended, cr
l
(cr) curves
can be plo tted for different crystal faces at a given co ncentratio n
of anio n in so lutio n (Figs. 32a-32c).
The variatio ns of the strength of the metal-to -io n interactio n
depend o n the ato mic structure of the face and of the charge density
o n the face. At low charge densities o n the face, for silver for
instance (Fig. 32c), the charge density due to adso rbed anio ns is
larger for the (111) face than for the (100) face, which is no t the
same at high charge densities (Fig. 32a).
Co mpariso n of faces is difficult; when reading papers attentio n
must be paid to the fact that so me autho rs co rrected their results
by a ro ughness facto r (see Sectio n V.4) and o thers did no t.
(c) Effect of concentration of anions in solution
Fo r a given face of a metal at a given charge density, the
amo unt of adso rbed io ns increases with co ncentratio n of the io n
in so lutio n. The way the amo unt of adso rbed io ns increases with
bulk co ncentratio n is described by an iso therm.
The practicing electro chemist o bserves o n the C(E) curves,
with increasing co ncentratio n of the anio n in so lutio n, pro gressive
disappearance of the co ntributio n of the diffuse part of the dl and
160
120
80
40
-a
1
(yC. cnf
2
)
Ag
(100)
//(110)
- ( a ) , >
-20 0 40 80
a (uC. cnf
2
)
30
20
10
(b)
(yC.cm )
Au
/
. " . (100)
(no)
i
-
2 0
-
1 0
o (pC. cn-
2
)
Figure 32. cr
l
(a-) curves for the (111), (100),
and (110) faces of: (a) silver in x raM NaCl +
(40-x) mM NaF so lutio ns (x = 40);
70
(b)
gold in x raM KBr + (40-x) mM KC1O
4
for
x = 0. 4mM;
84
and (c) silver in
x mM NaCl + (40-x) mM NaF so lutio n (x =
20).
70
cr and a
1
are corrected for the ro ughness
factor.
12
-a
1
(uC.cnf
2
)
Ag
din
(100;
//
// .-
-10 0
a (yC. cm"
2
)
a negative shift of the adso rptio n capacity peaks (Fig. 33). A
criterio n used for co mpariso n of different faces of o ne metal for
adso rptio n has been the disappearance, with increasing co ncentra-
tio n, of the co ntributio n of the diffuse part of the dl. Ano ther
criterio n was the shift of po tential A = A(
o
.
=0
,x ~ <r=o,>>) (assum-
ing no adso rptio n of y and x being the adso rbate), at a given
co ncentratio n. Generally, acco rding these criteria, for different faces
of o ne metal, at zero -charge density, adso rptio n of anio ns tends to
be the stro ngest on the face with the mo st densely packed ato ms. t
f From results o btained in the case of co adso rptio n of anio ns and neutral mo lecules,
o ther info rmatio n can be o btained [see Section V.3(iii)].
150
100
50
C (uF. cnf
2
)
(110)
-1. 2
-0.8 -0.4 - 1 . 2
(in)
-0.8 -0.4
350
300
250
100
50
(100)
.J J liJ L _
- 1. 2 -0.8 -0.4
see
(V)
Figure 33. C(E) curves for the (111), (100), and (110) faces of silver in x N aC l + (40-x) mM N aF for x = (A ) O , (O ) 0. 2, ( )
0. 5, ( ) 1, ( ) 2, ( ) 5, ( ) 10, ( ) 20, and ( ) 40. S weep rate = lO mVs'
1
; frequency = 20 H z.
70
>
i
40 -
20-
0
- a
1
;
(yC.cm'
2
)
(111)
(110)
ln(x/mol. r^+Alnx
-20 -10 0
Figure 34. Co mpo site curves of a
1
(In x) built on the isotherm
at a = 0, for faces of gold in x mM KBr + (40-x) mM KC1O
4
so lutio ns.
84
A In x = f(cr).
By building on the iso therm at zero charge, a co mpo site curve
can be o btained; for instance, for faces of go ld
84
the results are as
given in Fig. 34. Are the differences between these results of the
different faces significant?
(d) Effect of the size of the ions
The bigger the io n is, the mo re it tends to adso rb at the
electro de. t This is also true for single-crystal faces. Fo r instance,
for go ld faces, the shift of the dl regio n for the sequence of anio ns
F~, Cl~, Br~, and F is to mo re negative po tentials to gether with
higher and higher values of the capacity of the adso rptio n peaks
and decrease of their widths (Figs. 35 and 36). This is in agreement
with expectatio ns and with what is o bserved for po lycrystals. Fur-
thermo re, the shift in po tential is the same for all faces: the relative
adso rptio n strengths are the same for all faces of o ne metal.
(e) Analysis of the C{E) curves
Most of the studies of anio n adso rptio n o n metal faces were
do ne by C(E) curves. Acco rding to the metho d used to o btain
these curves, there are slight differences. Fo r the bridge metho d, it
t The strength of adso rptio n is also co nnected with the hydratio n of the io ns: small
ions like F~ tend to retain their primary hydratio n sheaths so that they adso rb
weakly or not at all.
106
Electro nic factors involved are the do nating ability of the
electro n pair and the po larizability.
68
A . H amelin
320
240
160
80
C (uF. cnf
2
)
C11O
200
120
40
C (yF.cnf
2
)
' v-Br
C1OO)
- 0. 8
+0.8
- 1. 0 - 0. 5 0 E
s c e
(V)
150-
100
50
0
C (yF
/
I
cm"
2
)
\
/
/
/
I
I
I
f
/
r
V
-
\r
i
y
^ F
C11O)
-<^ \
E
sce
1
<o
4
(V)
-1. 0 -0.5 +0.5
Figure 35. C(E) curves for different anions in solutions for the (111),
85
(100)
72
and
(H O )
10
faces of gold. For K I , K B r, and K C 1, concentration of the electrolyte is
100 mM , frequency of the alternating signal is 80 H z, and sweep rate is 5 mVs"
1
.
For K
2
S O
4
, the same items are 200mM , 130 H z, and 100mVs"
1
, respectively; for
N aF, 500 mM , 20 H z, and 5 mV s"
1
; and for H C 1O
4
,1000 mM , 20 H z, and 10 mV s"
1
.
is necessary to remain several minutes at o ne po tential in o rder to
balance the bridge. Therefo re the results can be affected by adso rp-
tio n of impurities (which is a slow pro cess). Fo r the sweep metho d,
o ne has to be careful that the interphase is in adso rptio n equilibrium.
In bo th cases an alternating signal is used for the measurements.
r
C (yF.crrf
2
)
(110)
(H I )
(100)
S
-1. 5 -1. 0 -0. 5 -1. 5 -1. 0 -0. 5 -1. 5 -1. 0 -0. 5
(V)
Figure 36. C(E) curves for the (111), (100), and (110) faces of silver for different anions in 10mM solutions.
Frequency = 80 H z; sweep rate = 10 mV s"
1
.
70
(uA .cnf )
Figure 37. C(E) curves for the (a) (100) and (b) (311) faces of gold in 2 mM bromide solution (frequency = 20 H z, and sweep
rate = 5 mVs"
1
) and corresponding i(E) curves (sweep rate = 20mVs~
1
).
10
Fo r an ideal-po larized electro de, the capacity values sho uld be, in
a large range, independent of the frequency of this alternating signal.
Fo r a given metal in a given medium, the shape of the C(E)
curves differs significantly from o ne face to the o therquite distinc-
tive patterns are o bserved experimentally (Figs. 35-37). A general
pattern (number, relative amplitude of the capacity peaks, and their
relative po sitio ns in the range of po tential) is o bserved at a given
face for different sizes of the anio nsf (Figs. 35 and 36).
The o rigin of these peaks can be discussed. Obvio usly, when
metal-io n interactio ns are weak, the effects of the metal-so lvent
interactio ns sho uld still be o bservable. On the co ntrary, when the
metal-to -io n interactio ns are stro ng, the metal-so lvent interactio n
effects beco me o bscured. Intermediate cases will be difficult to
analyze.
Three capacity peaks may be o bserved in the dl regio n: for
some co 's they merge, then o ne peak can be only a sho ulder on
ano ther peak. We now discuss some cases.
1. Fo r silver, in chlo ride so lutio n, a co mplete thermo dynamic
analysis was do ne for the (110) face (Fig. 33).
70
The most negative
peak (which shifts negatively with increasing co ncentratio n of
anio ns) was shown to be po ssibly due to o rientatio n of water
mo lecules in the inner layer and is derived from the o ne o bserved
witho ut adso rptio n [see Sectio n V. 3(i)]. The middle peak o ccurs
in the range of half-co verage and has been interpreted as being
caused by the usual type of adso rptio n effect. The third very narro w
capacity peak appears at mo re po sitive po tentials where the chlo ride
co verage is almo st co mplete; it diminishes with increasing co n-
centratio n of Cl~ (Fig. 33) and it is frequency dispersive. It co uld
be due to reo rganizatio n of the adso rbate o r charge transfer.^:
2. Fo r much stro nger adso rptio n, for which we have some
quantitative data, the metal-to -io n interactio ns are much stro nger.
This is the case of bro mide o r io dide o n gold faces. This is clear
from the charge due to adso rbed io ns at charge-density zero on the
metal; for bro mide, in a 1.25 raM so lutio n, it is abo ut 5 /JLC cm"
2
t Furthermo re, when comparing the same face of two different metals (crystallizing
in the same system) the general patterns are nearly the same; therefo re co nclusio ns
o btained for one metal might be cautio usly extended to ano ther.
70
$ Later it was demo nstrated that fluo ride ion (used in this mixed so lutio n) adso rbs
also on silver; these co nclusio ns are, however, still valid and they can be extended
to adso rptio n of bro mide ion on silver.
86
i (yA . cnf
2
)-
11
(a) (b)
Figure 38. C(E) curves for gold faces for continuous cycling; K I (concentration = 100 mM , sweep rate = 3 mVs"
1
, and frequency =
20 H z) and corresponding i{E) curves (sweep rate = H rnVs"
1
). (a) (100) face for three negative limits of the range of potential
explored; i(E) curve for a stop of 30 s at -0. 78 V ( ) is added for comparison.
72
(b) (111) face for two positive limits of the range
of potential explored.
72
(c) (110) face for different frequencies of the alternating signal: ( ) 12 ( ) 20 ( ) 40 and
( ) 80 H z.
72
X
I
for Ag(llO)
86
, and abo ut 25 fiC cm"
2
in an o nly 0.4 mM so lutio n
for Au(l 10).
84
Then the peak o bserved at the most negative po tential
is no lo nger due only to water reo rientatio n but also to adso rptio n
of anio ns.
The middle peak, which is co nnected to the inflection po int
of the iso therm, appears clearly for all faces, while the third peak,
in the mo st po sitive part of the po tential range of the dl regio n, is
visible for some faces. Fo r the (111) face, the general pattern
(Figs. 35 and 36) is that of a huge do uble peakwhich co rrespo nds
to the middle peak (its do uble shape is no t yet explained).
The results of Fig. 37 can be discussed as fo llo ws; for the (100)
gold face o ne peak is a sho ulder o n ano ther and for the (311) face
the three peaks are visible (the cyclic vo ltammo grams are given for
co mpariso n [in fact, they are a C() curve at very low frequency].
The understanding of the C(E) curves for gold faces is co mpli-
cated by the "seco ndary effects" (already described for slight
adso rptio n in dilute so lutio ns; see Sectio n V.2):
a. Fo r the (100) face of go ld, for all anio ns, hysteresis of
the C(E) curves, which diminishes when the negative limit of
the explo red range of po tential is shifted po sitively (Fig. 38a),
is o bserved. This effect is still visible for the (311) face which
is 25.26 from (100) (Fig. 37). Fo r all anio ns at the po int at
which the C(E) curves of po sitive and negative sweeps merge,
the difference of density of charge, Ah
yst
, is nearly that of the
extra peak o bserved o n the cyclic vo ltammo gram, Ao-p
eak
, at
these po tentials.
72
Is this due to stro ng adso rptio n of the anio ns,
reco nstructio n of the adso rbate and/o r the substrate?
b. Fo r the (111) face of go ld, for all anio ns, an hysteresis
of the C(E) curves, which is no t influenced by the negative
limit of the explo red range of po tentials, but diminishes when
the po sitive limit of the explo red range of po tentials is limited,
was o bserved, as sho wn in Fig. 38b. It co uld be explained as
for (100).
c. Fo r the (110) face of go ld, for mo st anio ns, in additio n
to the general pheno mena described for all faces, an extra
frequency-dispersive peak is o bserved [clearly visible from 12
to 60 Hz in KI so lutio n (Fig. 38c)]; it was explained either by
surface reco nstructio n
72
o r co mplexatio n of the gold face
87
o r
reco nstructio n of the adso rbate.
84
It remains o pen to questio n.
74 A . H amelin
Understanding of the C(E) of gold faces is easier when co n-
sidering the influence of the co in a general way; to systematic
changes of co co rrespo nd systematic changes of the pattern of the
C(E) curves for anio n adso rptio n (see further).
3. Fo r sulfate io ns, which adso rb less than chlo ride io ns on
gold faces, o nly the mo re negative part of the C(E) patterns is in
the dl regio n (Fig. 35); o xidatio n of the go ld surface o ccurs for all
faces befo re co mplete co verage by sulfate io ns (this is clearly visible
for Au(llO), Fig. 35). This example shows that it is not always
possible to see a dl region, which extends from the region of potentials
in which there is no metal-ion interaction, all the way to the region
of complete coverage of the surface by the adsorbed ions.
(/) Influence of systematic changes of the co on the C(E) curves
High-index faces were studied only for gold. Fo r chlo ride on
go ld, which adso rbs less than bro mide on go ld, the three peaks are
(111)
- 1221)
( 331)
100
60
20
_ _ (no)
-0.5 +0.5
Figure 39. C(E) curves for gold faces on the (lll)-(HO) zo ne,
in 10 mM KC1 so lutio ns. Frequency = 12 Hz; sweep rate =
HrnVs-
1
.
88
300
200
100
C (uF. cm"
2
)
300
C (uF.crrf
2
)
-1. 0 -0. 5
(a)
-1. 0 -0. 5
(b)
300
200
100
C (uF. cm"
2
)
(210)
(430) > A (HO)
-1. 0 -0. 5
(c)
300
200
100
C
-
(yF.cnf
2
)
r
(210) /
Y
V
(100)
<f (310)
\
-1. 0
(d)
-0.5 ,
E
sce
Figure 40. C(E) curves for io dide adso rptio n on gold faces distributed on
the three main zones of the pro jected unit stereo graphic triangle
(co ncentratio n = 100 mM KI, frequency = 80 Hz, and sweep rate =
SmVs"
1
): (a) (lll)-(HO) zo ne; (b) (lll)-(lO O ) zo ne; (c) from (110) to
(210) on the (100)-(110) zo ne; and (d) from (210) to (100) on the (100)-(110)
A.H*atlfti
-100
i-iuA.cm'
-50
i (yA.
-100
- 50
cm"
2
0.
")
3
i.i
'i
\i
III
i .
i! i
1
l
:>i
j
!A 1
i ii
0 E (V)
(a)
(311)
/ ' /"
:
>^'(533)
- 0 . 2
(b)
Double-L ayer Pro perties at M etal E lectrodes
i (yA.
40
20
:. < :' . '
cm"
2
)
/ / ^ <
/Oil)
| !
1)
-0. 2 0
(c)
(210)
-0.2
(d)
i
40
20
(yA.
/
en"
2
)
\
/ ; ^
(
2i o)
' " ' , , " ^ = - -
-0.2
(V)
Figure 41. Voltammograms for stripping of lead adso rbed on gold
faces the co 's of which are o n: (a) the (lll)-(HO) zo ne; (b) the
(111)-(311) section of the (lll)-(lOO) zo ne; (c) the (311)-(100)
section of the (lll)-(lOO) zo ne; (d) the (100)-(210) section of the
(100)-(110) zo ne; and (e) the (210)-(110) section of the (100)-(110)
zo ne. Sweep rate = 20 mV s"
1
; 10 raM HC1O
4
+ 1 mM PbF
2
sol-
utio ns deaerated with nitro gen and stirred. Although the UPD of
oxygen was also included in each cycle, this is not shown on the
figure because it occurs at more po sitive po tentials. Depo sitio n and
stripping profiles of lead are similar for nearly all faces.
78 A . H amelin
visible o n the C(E) curves for some faces. Fo r systematic changes
of the co o n the (111)-(110) zo ne (making stepped faces; see Section
III. 4) (Fig. 39), a systematic change of the C{E) curves was
o bserved for the first time:
88
the mo re negative capacity peak
increases with the number of ato mic steps at the gold surface; in
parallel, the middle peak decreases and the more po sitive peak
shifts negatively. The mo st negative capacity peak seems co nnected
to adso rptio n of chlo ride io n on mo no ato mic steps at the surface
and the middle peak to adso rptio n on the terraces (see TLK mo del,
Section III. 4).
Fo r io dide adso rptio n on gold faces,
89
metal-to -io n interactio ns
are very stro ng because the anio n is very large. The middle peak
for the (111) face (Fig. 35) has (as for chlo ride, bro mide, and
co ncentrated sulfate o r fluo ride) the shape of a do uble peak; this
shape remains unexplained. The most po sitive peak is no t o bserv-
able for mo st of the faces (pro bably charge transfer takes place
over all the po tential regio n o bserved). The situatio n is such for
io dide adso rptio n o n go ld faces that, for faces distributed on the
three main zo nes of the stereo graphic triangle
89
(see Fig. 10b), the
mo re negative capacity peak increases systematically as the number
of mo no ato mic steps at the gold surface increases (Fig. 40), while
the middle peak decreases (i.e., increases with the width of the
terraces at the go ld surface) and the most po sitive peak is hardly
no ticeable and o nly in some cases. The evo lutio n of the general
pattern of the C(E) curves with systematic changes of the structure
of the faces was explained by the TLK mo del (see Section III. 4).
88
'
89
The case of io dide adso rptio n o n go ld can be fruitfully com-
pared to that of lead adso rptio n o n gold faces
19
which takes place
with co mplete charge transfer,
90
i.e., by so -called underpo tential
depo sitio n (UPD).
Fo r faces distributed on the three main zo nes of the pro jected
unit stereo graphic triangle (see Section III. 2), systematic changes
of the co exist; they were described by the TLK mo del (see Section
III. 4). As in fact the three main zo nes have to be divided into five
sectio ns to o bserve mo no to nic variatio ns of the surface energy (Fig.
12) and mo no to nic changes of surface no tatio n (Fig. 10), it is no t
surprising that the results for UPD of lead on gold faces have to
be divided into five gro ups to observe mo no to nic changes: from
(111) to (110) (Fig. 41a), from (111) to (311) (Fig. 41b), from (311)
Double-L ayer Properties at Metal Electrodes
50
50
(vjA.cnf
2
)
- 0. 4
* 0.3
^. 0-3
Figure 42. Cyclic voltammograms for the (111) face of go ld. Sweep rate = 20 mV s
l
;
10 mM HC1O
4
+ 1 mM PbF
2
so lutio ns deareated with nitro gen and stirred, for
different ranges of the po tential scan. Although not shown on the figure, the formation
of a monolayer of oxidized co mpo unds was included in each cycle.
to (100) (Fig. 41c), from (100) to (210) (Fig. 41d), and from (210)
to (110) (Fig. 41e). Fo r an increase of the density of mo no ato mic
steps at the electro de surface, the large po sitive peak increases;
co rrespo ndingly, as the width of the terraces diminishes, the large
negative peak decreases. Obvio usly, the TLK mo del is valid,
altho ugh several details of these curves are no t yet co mpletely
explained.
The TLK mo del is valid as well for anio n adso rptio n as for
lead UPD; furthermo re o ther features are o bserved in bo th cases
for instance, for the (111) face of go ld, the huge do uble peak with
its hysteresis (Fig. 42).Thus it can be understo o d that such features
are directly co nnected to the go ld surface structure and pro perties.
Fro m this paragraph o n the general influence of the co , and
ideas develo ped previo usly, it can be understo o d that co mpariso n
of interactio ns for two different metals can be do ne only for the
same co of two metals crystallizing in the same system, if that!
(g) Influence of growth steps on the C(E) curves
Only for the (100) and (111) faces of silver was the influence
of gro wth-step density [see Sectio n V. l(iii)] o n the C(E) curves
80 A . H amelin
40
30
20
C (uF. cnf
2
)
( I l l ) + L
- 1. 3
- 1. 1 -0. 9
see
(V)
Figure 43. C(E) curves o f an electro lytically gro wn (111) face o f
silver fo r different gro wth-step densities L in 5 mM Na
2
SO
4
:
curve 1, L = 2.0 x 10
4
cm"
1
; curve 2, L = 4.2 x 10
4
cm"
1
; curve 3,
L = 7.0 x 10
4
cm"
1
; curve 4, L = 9.2 x 10
4
cm"
1
; curve 5, L =
12.3 x 10
4
cm"
1
; curve 6, L= 15.3 x 10
4
cm"
1
. C(E) curves o btained
by bridge metho d at 210 Hz.
92
examined. Altho ugh, in fluo ride so lutio n, this parameter do es no t
influence the pzc and the C(E) curve of the (100) face
91
and of
the (111) face,
92
in sulfate so lutio n it is no t the same. The shift to
more negative po tentials of the capacity minima (Fig. 43) was
explained by adso rptio n of sulfate io ns on the gro wth steps and
no t on the flat terraces which are (100) o r (111) o riented. The value
of the capacity at the minimum of the curves increases with the
density of gro wth steps for the same reaso n. Sulfate io n wo uld
adso rb o n gro wth steps but no t on terraces in the case of silver,
acco rding to these results.
(h) Energy of adsorption
Besides this pheno meno lo gical review of the metal-to -io n inter-
actio ns, some values for the influence of the co on the free energy
of adso rptio n (referred to as zero charge o n the metal and standard
states: 1 mol dm~
3
in so lutio n and 1 io n cm"
2
o n the surface) are
given: for io dide on Bi (111), (Oil), and (2ll), 112, 116, and
114 kj mo l"
1
;
93
for bro mide on Au (111), (100), and (110), 120,123,
and 122 kj mo l"
1
;
84
and for chlo ride on Ag (111), (100), and (110),
100, 95, and 93 kj mo P
1
.
70
No ne of the autho rs was so audacio us
as to give experimental uncertainty of these values!
In this sectio n, an attempt was made to give some clear trends
for the metal-io n interactio ns for better understanding of already
published results and future research.
(iii) Neutral Molecules-Metal Interactions
The reader may refer to Chapter 8 of Reference 9 for general
backgro und material.
Fo r the electro chemical study of adso rptio n of an uncharged
species, a base electro lyte is necessary. When neither the anio n no r
the catio n of the base electro lyte adso rbs at the metal electro de,
the simplest situatio n is achieved. When o ne of the io ns of the base
electro lyte adso rbs, it no t only changes the chemical po tential of
the neutral substance but also the structure of the dl, decreasing
(o r increasing) the adso rptio n of the neutral mo lecule. Most of the
time it is suppo sed that the io ns of the base electro lyte do no t
adso rb at the electro de. But this is no t always the case and further-
mo re the anio n adso rbs in a different way o n the different faces of
o ne metal (see Section V.3). Fo r some metal faces, studies of
neutral-mo lecule adso rptio n may be co mplicated by the fact that
the anio n of the base electro lyte, as well as the neutral mo lecule,
adso rb at least at the most densely packed faces. But if the adso rp-
tio n-deso rptio n capacity peak o ccurs in a range of po tential in
which the charge due to adso rbed anio ns is very small, the analysis
of the adso rptio n of the neutral species is valid in this range.
Neutral adso rbate mo lecules replace so lvent mo lecules on the
metal side of the o Hp acco rding to the quasichemical equatio n:
Ad(so ln) + rH
2
O(ads) ^ Ad(ads) + rH
2
O(so ln)
Ad refers to the adso rbate and r is the number of water mo lecules
replaced by o ne mo lecule of adso rbate.
82 A . H amelin
This simple relatio n co rrespo nds to a co mplicated
pheno meno n, because the so lubility of the salt may be changed in
the interfacial regio n (mo re than in the bulk so lutio n) and bo th
activity coefficients of the salt and the neutral substance are altered.
The mo dificatio ns of these may be different o n the different faces.
We shall discuss o nly the case in which the adso rbate retains
its chemical individuality, then adso rbed mo lecules are tho se which
are in so lutio n.
Electro de-adso rbate, electro de-so lvent, and adso rbate-
so lvent interactio ns (which are no mo re as they are in the bulk
so lutio n) are involved in the pro cess of adso rptio n; the first two
depend directly on the density of charge at the metal surface.
Fo r data o btained at equilibrium of adso rptio n on faces,
thermo dynamic analysis is po ssible and is mo re valid than for
po lycrystalline electro des because the distributio n of the charge
density is co ntro led (unifo rm) at the electro de surface (see Sectio ns
V.I and V.2).
As for po lycrystalline electro des, adso rptio n of neutral species
on faces depends on the nature of the metal, and adso rbate and
on the different interactio ns mentio ned abo ve. The surface excess
F and the co verage 6, as well as their variatio ns with charge density
at the electro de surface, can depend on the ato mic arrangement of
the face.
Fo r faces of a given metal, the pheno meno lo gy of adso rptio n
of neutral substances is the following.
(a) Effect of tempera ture
Only for bismuth faces has the temperature effect been studied
(for cyclo hexano l adso rptio n in 50mM/Na
2
SO
4
and H
2
SO
4
aqueo us so lutio ns) from 281 to 321 K.
13
The different behavio r of
the (111) face from that of the (Oil) and (2ll) faces, suggested
that the chemical interactio ns between bismuth ato ms and cyclo-
hexano l are reinfo rced by temperature for the two last faces but
that, for (111), there is o nly physical adso rptio n. This co uld explain
why F
max
(surface excess at saturatio n) diminishes with increasing
temperature for (111) and increases for the two o ther faces. Bismuth
crystallizes in the rho mbo hedral system, the (111) face is less
densely packed in ato ms than the two o ther faces, and bismuth is
a semimetal, no t a metal.
83
(b) Dependence on potential
Representatio n of the variatio ns of the surface excess with the
po tential of the electro de is mo re usual than with charge density.
Generally, only o ne part at the expected T(E) curve is o bservable
in the dl regio n. Fo r instance, for cyclo hexano l adso rptio n on zinc
faces, co mpariso n of the three lo w-index faces for o ne co ncentratio n
of cyclo hexano l in 100 mM KC1 + 0.1 mM H
2
SO
4
is represented
in Fig. 44 ;
94
the surface excess is the highest for the most densely
packed face.
(c) Effect of the concentration of adsorbate in solution
With increasing co ncentratio n of adso rbate in so lutio n, for a
given charge o r a given po tential, the surface excess increases.
Co mpariso n of the coverages for different co ncentratio ns of cyclo-
hexano l, at the po tential of maximum adso rptio n, for different faces
of zinc (Fig. 45)
94
show that the situatio n is co mplex: at low
co ncentratio ns coverage is higher for a no ndense face, while at
higher co ncentratio n of adso rbate the co verage is higher for the
most densely packed face. Fo r lead the similarity of the co verage-
co ncentratio n variatio ns for the (111), (110), and (112) faces but
no t for the (100) face, in the case of adso rptio n of cyclo hexano l,
95
is surprising. How much this is due to experimental uncertainty o r
po o r co ntro l of the surface state remains an unanswered questio n.
The effect of the co ncentratio n of adso rbate was o bserved for
gold faces for the case of diethyl ether adso rptio n.
96
It is represented
Figure 44. Surface excess o f cyclo -
hexano l at zinc faces as a functio n o f
po tential: curve 1, (0001), curve 2,
(1010), and curve 3, (1120) at co nstant
co ncentratio n 150 mM in 100 mM
0. 1mMH
2
SO
4
.
94
0.3
0.2
0. 1
r x 10
10
(mo i. arf
2
)
- 1. 4 - 1. 2 E
(V)
84 A . H amelin
0.8
0.4
l g(c/mol . l
-3 -2
- 1
Figure 45. Coverage as a function of
co ncentratio n for adso rptio n of cyclo-
hexano l at zinc face: curve 1, (0001),
curve 2, (lOlO), and curve 3, (1120) at
po tential of maximum adso rptio n.
94
by the variatio ns of the surface pressuret with co ncentratio n
(Fig. 46). Surface pressure increases with co ncentratio n for all faces.
The co mpo site curves represented in Fig. 46 were based on the
surface pressure vs. co ncentratio n curve o bserved for the po tential
for the maximum of adso rptio n (Alnc is the quantity that the surface
pressure curve, for a given po tential, has to be shifted to be superim-
po sable o n that co rrespo nding to the po tential of maximum adso rp-
tio n). This work was do ne in 10 mM NaF; the fluo ride may adso rb,
for instance, mo re on the (111) gold face then o n the (110) face.
Ho wever, analysis from the capacity peak in the negative range of
(100)
Inc + Aln(c/mol.l"
1
)
Figure 46. Surface pressure vs. co ncentratio n curves for adso rp-
tio n of diethyl ether on gold faces (in 10 mM NaF).
96
t By integratio n of the charge-po tential plo ts, the difference between the surface
tensio n at zero coverage and at a given coverage is o btained; it is the surface
pressure.
85
po tential o r from densities of charge vs. po tential curves (o btained
by chro no co ulo metric metho d) in a range of po tential which co rre-
spo nds to this peak is valid.
(d) Effect of the structure of the nonionic adsorbate
Fo r the (0001) face of zinc, a systematic change of the chain
length of the adso rbate was analyzed. Fo r n-pro pyl, n-butyl, and
n-amyl alco ho ls (in 100 mM KC1 + 0.1 mM H
2
SO
4
), the co verage
varies with the co ncentratio n (at po tential of maximum adso rptio n),
as shown in Fig. 47.
97
Fo r the three alco ho ls, the two -capacito r mo del (see further)
is valid. The attractio n co nstant (in the Frumkin iso therm) and the
maximum surface excess vary with the chain length as for mercury
and po lycrystalline cadmium. The adso rptio n energy of the alco ho l
increases with chain length for Zn (0001), mercury, and cadmium.
From the preceding discussio n it is easy to understand that
the pheno meno lo gy on crystal faces is qualitatively the same as for
a po lycrystalline electro de.
(e) Analysis of the C{E) curves
As adso rptio n of a no nio nic substance at a metal electro de
pro ceeds by replacement of so lvent mo lecules at the surface by the
adso rbate, following the G-C-S mo del, it is sufficient to co nsider
the inner-layer capacity:
98
1/C
1
= dipjda = (d<pjd<r)
v
+ (dq>JaY)
a
(dTI d*
(3)
l. Or
0.6
0.2
-2 - 1 0
lgtc/mol.T
1
)
Figure 47. Co verage as a functio n o f co ncentratio n
fo r: curve 1, n-C
3
H
7
OH, curve 2, n-C
4
H
9
OH, and
curve 3, n- C
5
H
n
OH at po tential o f maximum
adso rptio n o n the (0001) face o f zinc.
97
86 A . H amelin
where (p
t
is the po tential dro p in the inner layer. Each term of the
equatio n varies with the quantity adso rbed and the density of charge
o n the metal. When the adso rptio n is maximum, dT/da = 0; then
all the effects of adso rptio n are described by the first term of Eq.
(3) and C is a minimum.
Fo r single-crystal faces, as for all metal electro des, in the
po tential regio n where adso rptio n of neutral species prevails, the
capacity is decreased (surface tensio n is diminished). When the dl
regio n is large eno ugh, adso rptio n-deso rptio n capacity peaks are
o bservable o n bo th sides of the maximum of adso rptio n; they are
due to the seco nd term of Eq. (3) (Fig. 48). In some cases, only
the adso rptio n-deso rptio n capacity peak which o ccurs in the mo re
negative range of po tential of the dl regio n is o bservable because
o xidatio n of the metal face takes place at mo re po sitive po tentials
(Fig. 31). By changing the base electro lyte, the range of po tential
of the dl regio n may be shifted; then the range of o bservatio n of
the C(E) curves is extended and, in some cases, bo th adso rptio n-
deso rptio n capacity peaks are o bservable (in different base elec-
tro lytes) (Fig. 49). If thermo dynamic analysis of the adso rptio n
pro cess from the C(E) curves is planned, co incidence of the C(E)
curves in base electro lyte and for different co ncentratio ns of the
neutral substance sho uld be o bserved in the dl regio n in o rder to
give the integratio n co nstant. Fo r most metal faces only this co in-
cidence and o ne adso rptio n-deso rptio n peak were o bservable.
In the range of po tentials of an adso rptio n-deso rptio n capacity
peak, the extent of adso rptio n changes so rapidly with po tential
that the superpo sitio n of an alternating signal (for measurements)
of different amplitude o r frequency pro duces different values of
the differential capacity. t Therefo re, the po tential of the adso rp-
tio n-deso rptio n capacity peak and po tential (o r density of charge)
at the maximum of adso rptio n are often used as parameters charac-
terizing adso rptio n because they are less subject to erro r.
From a model
100
based o n the summatio n of capacitance due
to adso rbate (0 = 1) and so lvent (0 = 0), the charge density is
a = (T
e=0
(\ - 0) + cr
e=l
(0) (4)
t Here the case of equilibrium adso rptio n is discussed; of co urse, the amplitude of
the capacity peak depends also on the rate and po tential dependence of the
adso rptio n pro cess.
70
50 -
30 -
10 -
~ C (yF.
-
-
1000
-
cm"
2
)
(111)
mM
. 500
- /: 50^ 10
5
I ;
1
/ '
3 J
- ^ ~. - ^
X
f.
if 1- ;
1 ' 1
< ' .
-1. 0
-0.6
60
40
20
C (viF.cm"
2
)
(100)
1000 mM
. 500
"; \ 50
7
:
. .<
- . \ /
\ i
/ / '
- - . j ^
10
/
/ .
\
\
5
! i
I
I
i
\
\
V.
0/
/ 2
3
A 1 '
f i
V >
:
I-
Al ' -
;
/: i | ' :
V' ';
J\\' .'
i i
1 ' ' / '
'H ! H
i
- 1. 2 -0. 8
I
E
sce
E
sce
(a) (b)
Figure 48. C(E) curves for adsorption of n-isobutanol (in 50 mM N a
2
S O
4
) on silver faces: (a) (111) and (b) (100) for
seven different concentrations although nine were investigated by the authors. C(E) curves obtained by bridge method
at 210 H z.
91
88 A . H amelin
150
100
50
. 2
C/pFcm
1
OOmM
KF
! I
5 0
] i
i ii
! ll
1 I'
j \ l \ 20
J^\\'\0
20
/
lOOmM
50
1
'i i
n i
! li
!
I .'
\'
J y''
i
1
^ 1
i
-15 10 -05 0
Figure 49. C() curves for the (111) face of bismuth in
two different base electrolytes (lOOmMKF and
50 mM H
2
SO
4
) for different co ncentratio ns of cyclo-
hexano l. C(E) curves o btained by bridge method at
210 Hz. "
Fo r this two -capacito rs-in-parallel mo del,
C = C
e=0
(l -6) + C
d
^(e) + (a
e
^ - <r
e=o
)(d0/dE)
c
(5)
The third term of the right-hand-side of Eq. (5) is always po sitive.
This mo del is often used for co mpariso n with experimental results.
Let us examine three cases:
1. Fo r iso butano l adso rptio n on silver (111) and (100) faces
(in 50mMK
2
SO
4
)
91
(Fig. 48), obviously the two adso rptio n-
deso rptio n capacity peaks are o bservable in the dl regio n on bo th
sides of the maximum of adso rptio n. The capacity peak at negative
po tentials shifts negatively with increasing co ncentratio n of
iso butano l while the capacity peak at po sitive po tentials shifts
po sitively. Fo r a given co ncentratio n of adso rbate, the maxima of
the capacity peaks are o bserved at less negative po tentials for the
(111) than for the (100) face, pro bably because the pzc of (111) is
less negative than that of (100). t The attractio n co nstant and the
standard (standard states are no t quo ted) free energy of adso rptio n
(at zero charge) were fo und to be independent of the co . The same
o bservatio ns were made for adso rptio n of n-hexyl alco ho l al these
silver faces.
91
2. Fo r cyclo hexano l adso rptio n o n the three faces of lowest
indices of zinc (in 100 mM KC1 + 0.1 mM H
2
SO
4
), C(E) curves
are given in Fig. 50.
97101
Obvio usly, o nly o ne of the adso rptio n-
deso rptio n peaks is o bservable in the dl regio n. These results were
shown to fit the two -parallel-capacito rs mo del (dashed lines). Fo r
a given co ncentratio n of adso rbate, the po tentials of the peak and
of the maximum of adso rptio n shift in the same o rder as the pzc's
in base electro lyte. Fro m the co mplete analysis of the curves, all
adso rptio n parameters were fo und to be co dependent4
3. Fo r adso rptio n of pyridine o n silver faces (in
100 mM NaF), the C{E) curves are given in Fig. 51
102
for three
co ncentratio ns (altho ugh the autho rs published data for five co n-
centratio ns). It is clear that the peak o bserved on the C(E) curve
in base electro lyte still shows o n the C(E) curves of (111) silver
face. It disappears for the higher co ncentratio ns at the (100) silver
face and disappears already for the lo west co ncentratio n at the
(110) silver face. If this capacity peak is due to fluo ride adso rptio n,
io n-silver interactio ns are stro nger on (111) than on (100) than o n
(110); if the capacity peak o bserved in base electro lyte is due to
water-silver interactio ns, these are stro nger on (111) than on (100)
than on (110); if the capacity peak is due to water-silver interactio ns
on (110) and to fluo ride-silver interactio ns o n (100) and (111),
then there is adso rptio n of fluo ride io n thro ugh the film of pyridine
on the (111) face. In such a case, altho ugh the situatio n is clearer
for single-crystal faces than for po lycrystalline silver (Fig. 51d), the
analysis of the C(E) curves and determinatio n of the adso rptio n
parameters are difficult. But the adso rptio n-deso rptio n capacity
peak increases with co ncentratio n of adso rbate and shifts negatively
t The same sequence of co was observed for adso rptio n of TBAl on faces of co pper
in 50 mM Na
2
SO
4
(Fig. 31).
81
X For adso rptio n of TBAI on zinc faces, the adso rptio n parameters are also depen-
dent on the co .
As was observed for sulfate adso rptio n on a gold (111) face thro ugh pyridine
85
(Fig. 52).
C (uF. crrf
2
)
(0001)
150mM
- 1 . 7 - 1 . 5 - 1 . 3
(a)
60
40
20
C (pF. cnf
2
)
(1120)
-1. 5 - 1. 3
(b)
-1. 1 -1. 5 - 1. 3
(c)
Figure 5O . _C () curves for adsorption of cyclohexanol (in 100 mM K C 1 + 0.1 mM H
2
S O
4
) on faces of zinc, (a) (0001), (b) (1120), jj
and (c) 1010), for five different concentrations although the authors investigated a greater number of concentrations. C urves calculated 3
from E q. (5) represented by dashed lines.
97
'
101
K
91
100
50
C (uF.cm"
2
)
(100)
|100mM
150h
3 0 \
50
C (yF.cm"
2
)
|l
100mM
(110)
-13 -09 -07 -13 -09
(a)
100-
50
-13
C (uF
r
.cm"
2
)
100mM
(m)
^ \
v ^
-03 -07
(c)
100
50
C (uF.cm"
2
polyc.
|O00mM
1
\
y
)
.30,
-13 -09
( - )
E
-
( v )
Figure 51. C(E) curves for silver faces and po lycrystal-
line silver for adso rptio n of pyridine for three co ncentra-
tio ns altho ugh the autho rs studied 5 co ncentratio ns.
Frequency = 40 Hz; sweep rate = 4 mV s~V
02
as is generally o bserved; ho wever, its co mplicated shape, for (111)
for instance, is no t yet explained.
Fro m these three examples and the disparity of the studied
systems, it is difficult to draw co nclusio ns. One co uld co nclude that
for a given metal and adso rbate the adso rptio n capacity peak shifts
in the same way as the pzc in the range of po tential and that its
shape is simpler for single-crystal faces than for a po lycrystalline
electro de. This is no t always the casefor instance, for adso rptio n
of pyridine o n gold faces
85
the capacity peaks are no t distributed
in the same range of po tentials as the pzc's and the capacity peak
92 A. Hamelin
60
20
n
C/
H
F.cm"
2
A
'/ "K ^
/ /
sphere _
(111) -
(110) -
(100) -
f\
, \
A ^
t
-05 +05 E
sce/
V
Figure 52. C(E) curves fo r adso rptio n o f pyridine (in
200 mM K
2
SO
4
) o n go ld faces
85
and po lycrystalline go ld
sphere
103
. Co ncentratio n o f pyridine = 6.15 mM, frequency =
380 Hz, and sweep rate = 25 mV s~
l
.
of the (100) face
85
has a mo re co mplicated shape than that of a
po lycrystalline sphere
103
(Fig. 52).
(/) Coadsorption of anions and neutral molecules
A base electro lyte is always necessary for study of adso rptio n
of neutral mo lecules. We have already mentio ned that in some
cases an extra capacity peak appears at po tentials less negative
than the adso rptio n-deso rptio n capacity peak and that it co uld be
due to io n-metal interactio ns thro ugh the film of adso rbate o r to
very stro ng so lvent-metal interactio ns. Fo r extreme cases of co ad-
so rptio n, e.g., pyridine o n silver faces in KC1 electro lyte
102
and
pyridine o n go ld faces in K
2
SO
4
electro lyte,
85
a capacity peak at a
less-negative-charge density than the capacity peak due to adso rp-
tio n of neutral mo lecules co uld be explained in such a way. These
studies can give info rmatio n on the nature of the capacity peaks
o bserved in pure electro lyte, i.e., how much they are due to so lvent
reo rientatio n o r to anio n adso rptio n (Fig. 51).
Ano ther puzzling cases of co adso rptio n is that o bserved for
adso rptio n from 300 mM n-C
5
H
n
OH (in 50 mM Na
2
SO
4
) o n faces
of silver o n which a well-co ntro lled density of gro wth steps exists;
C (yF.cm"
2
)
93
150
100
50
Ag (100) + L
- 1 . 2
-0.8
Figure 53. C(E) curves for adso rptio n of 300 mM w-amyl
alco ho l (in 50mMNa
2
SO
4
) on the (100) face of silver with
different densities of growth steps: curve 1, L = 1.5 x 10
4
cm~
1
;
curve 2, L = 2.7 x 10
4
cm"
1
; curve 3, L = 5.9 x 10
4
cm~
1
; curve
4, L = 8.1 x 10
4
cm"
1
; curve 5, L = 19.8 x 10
4
cm~
1
; and curve
6, L = 30 x 10
4
cm~
1
. C(E) curves o btained by bridge metho d
at 210 Hz.
91
the capacity at the maximum of adso rptio n increases with the
density of gro wth steps (Fig. 53).
91
This effect do es no t exist when
the electro lyte is 100 mM KF.
91
It was explained that there is
adso rptio n of sulfate io ns o n the gro wth stepst and adso rptio n of
the o rganic mo lecules o n the smo o th ato mic terraces and that
fluo ride do es no t adso rb on the gro wth steps. The most puzzling
o bservatio n remains that, in the case of sulfate used as base elec-
tro lyte, the adso rptio n equilibrium of the o rganic mo lecules was
established only after 1.5-3 h, while it was established in lOmin
when the base electro lyte was fluo ride.
t Adso rptio n of sulfate ion on growth steps of (111) and (100) faces was already
mentio ned in Section V.3(ii).
94 A . H amelin
4. T he R oughness Factor
Practicing electro chemists who , for years, have wo rked with dro p-
ping or hanging mercury dro ps never had to face this pro blem,
because the ro ughness facto r for the very smo o th surface of the
mercury is unity. On the co ntrary, for so lid electro des, the surface
is never perfectly smo o th and a ro ughness facto r has to be intro -
duced in calculatio ns.
It was pro po sed, for determinatio n of the ro ughness facto r,
that the value of the capacity at very negative density of charge
(where there is no lo nger adso rptio n of anio ns) be co mpared to
that of mercury. This do es no t take into acco unt that at such negative
density of charge there are metal-so lvent interactio ns and these are
no t only metal specific but also face specific.
In the case of no adso rptio n of io ns and co mplete disso ciatio n
of the electro lyte, it is po ssible to determine the ro ughness facto r
by o bservatio n (at co nstant density of charge, for instance, zero )
of the inverse of the slo pe of the variatio ns of 1/C (C is the capacity
o bserved experimentally) as a function of 1/C
d
(C
d
is the capacity
of the diffuse layer calculated acco rding to the G-C theo ry), for
different co ncentratio ns of electro lyte
104
(Fig. 54). t This so -called
Parso ns-Zo bel plo t gives the capacity of the inner layer by extrapo l-
ating to infinite co ncentratio n. Slight adso rptio n o r inco mplete
disso ciatio n of the electro lyte will vitiate the determinatio n of the
ro ughness facto r by this metho d. $ This was discussed in detail for
the (100) silver face in KPF
6
.
62
Ano ther way of determining the ro ughness facto r was pro po sed
by Valette and Hamelin
15
when there is no adso rptio n. Fo r this case,
R(C)-
1
= (C
d
y
l
+ (C
1
)"
1
(R = ro ughness facto r) (6)
The plo t of C
l
(a) (a charge density) has to be made for several
suppo sed values (for instance, 1.00, 1.05, 1.10, etc.) of R. Fo r unity
(o bvio usly a to o -small value) the diffuse-layer part is co mpensated
to o much and gives rise to a sharp maximum o n the C'(cr) curve
t It was already mentioned for gold faces of Fig. 21 that blind application of the
G-C theory is obviously a mistake.
$ O f course, nonuniform distribution of the charge density at the surface of the
electrode (as for a polycrystalline electrode) spoils this plot.
15
'
105
95
60
40
20
\T=0
20 40 60
Figure 54. P lot of reciprocal of experimental measured capacity vs.
reciprocal of calculated diffuse-layer capacity at constant charge zero,
for different concentrations of solution: C
x
> C
2
> C
3
> C
4
> C
5
.
for density of charge aro und zero . Fo r a to o -high value of R, the
co ntributio n of the diffuse part of the dl is no t co mpensated eno ugh
and a minimum appears o n the C
l
(a) curves. The Valette-Hamelin
metho d po stulates that the variatio ns of C
l
vs. a are mo no to nic
aro und zero charge. The value of R is adjusted to o btain such
behavio r (Fig. 55).
Most of the time the experimenter has to use these two last
metho ds to have an idea of the situatio n.
When reading papers, o ne must pay attentio n to how the
ro ughness facto r was determined, if it was used for co rrectio n of
the curves, and if some o ther co rrectio ns, for example, for inco m-
plete disso ciatio n of the electro lyte, were also made.
It is ho ped that in the near future o ther mo re co nvincing
metho ds will be pro po sed to disentangle the ro ughness facto r from
the effect of defects which intro duce also the effect of o ther co 's.
96
A . H wffUn
-150
C
1
(uF.cm"
2
)
- 100
- 50
-10 + 10
a (yC . cnf
2
)
Figure 55. C
l
(cr) curves for different values of the roughness factor:
R
Y
< R
2
< R
3
. R
2
is in agreement with the postulated monotonic shape
of the curve.
5. C onclusions
1. Sectio ns V.1-V.4 were no t written as a biblio graphical
review of electro chemical results on metal crystal faces. Po ssibly,
the present autho r has no t quo ted some excellent papers and may
have put to o much emphasis on results that are no t always reliable.
The wo rks, which are no t in the references, were, ho wever, used
to determine the general trends described for the behavio r of single-
crystal faces. In some cases the trends were no t clear o r were no t
able to be detected.
All results were analyzed with the help of the G-C-S mo del
for the interfacial regio n, altho ugh for this mo del the surface is
assumed to be "flat" do wn to an ato mic level and its ato mic
arrangement is no t taken into co nsideratio n. This last parameter
sho uld be a crucial o ne in the mo del of this regio n.
2. The status of data at the beginning of 1984 is as fo llo ws.
Fo r the pzc, the situatio n is well advanced (Figs. 19 and 20)
and the aniso tro py of this parameter for high-melting metals
is in agreement with the kno wledge of the structure of the metal
surface.
Fo r the inner-layer capacity and its variatio ns with charge
density at the metal surface, results are very scarce and much
debated. It seems that, in aqueo us so lutio ns witho ut specific
adso rptio n, C
l
is maximum no t far from zero -charge density
(Figs. 28-30); on single-crystal metal faces, the general shape of
the curve wo uld include only o ne maximum and wo uld be nearly
symmetrical.
Fo r adso rptio n, the pheno meno lo gy is qualitatively what it is
for po lycrystalline electo des. Of co urse, the shift of the pzc with
the co (which increases with the melting po int of the metal) entails
differences which are no t entirely reduced when the experimental
results are analyzed as a functio n of charge density at the metal
surface. Anyway, analysis of adso rptio n (especially for high-melting
metals) is mo re valid for metal single-crystal faces than for po lycrys-
tals (which have a patchy, unco ntro lled density-o f-charge distribu-
tio n at their surface).
3. Co mpariso n (and therefo re understanding) of the results
wo uld be easier if autho rs had some respect for the IUPAC reco m-
mendatio ns and were tho ughtful eno ugh to mentio n such things as
the reference electro de when giving a po tential, in the text and on
all figures, and the standard states when quo ting a free energy of
adso rptio n.
4. Theo reticians who wish to use published experimental data
on single-crystal metal faces sho uld co nsider that experimental
interfacial electro chemistry o n so lid metal faces is still in its infancy
and a sizeable pro po rtio n of the results are meaningless, even when
they are printed. They sho uld read carefully Sectio ns IV.2-IV.5 and
po nder. Then the great difficulties faced by the experimenters will
be clear to them.
98 A . H amelin
ACKNOWLEDGMENTS
The autho r is pleased to ackno wledge her indebtedness to the Centre
Natio nal de la Recherche Scientifique (France). She is also grateful
for co mments, discussio ns, and co rrectio ns from Dr. R. Parso ns
who tho ro ughly went over the entire manuscript written in a
language which is no t her mo ther to ngue. Also thanks are due to
Dr. M. Bo nnemay for suggesting, in 1955, the impo rtance of work
with metal single-crystal electro des.
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2
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G. Valette and A. Hamelin, J. Electroanal Chem., 45 (1973) 301.
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106
B . E . C onway, in Ionic Hydration in Chemistry and Biophysics, E lsevier, A mster-
dam, 1981, Chap. 32, p. 637.
The Temperature and P otential
Dependence of E lectrochemical R eaction R ates,
and the R eal Form of the T afel Equation
Brian E. Co nway
Department of Chemistry, University of Ottawa, Ottawa, Ontario K\ N 9/?4, Canada
I. I N T R O DUC T I O N
1. S cope and S ignificance of this A rticle
The Tafel equatio n rj = a + b In i, where b, the so -called Tafel
slo pe, co nventio nally written in the form b = RT/aF, where a is
a charge transfer coefficient, has formed the basis of empirical and
theo retical representatio ns of the po tential dependence of
electro chemical reactio n rates, in fact since the time of Tafel's own
work.
1
It will be useful to recall here, at the o utset, that the
co nventio nal representatio n of the Tafel slo pe as RT/aF arises in
a simple way from the suppo sitio n that the free energy of activatio n
AG* beco mes modified in an electro chemical reactio n by some
fractio n, ~~0.5, of the applied po tential expressed as a relative
electrical energy change rjF, and that the resulting co mbinatio n of
AG* and 0.5rjF are subject to a Bo ltzmann distributio n in an
electro chemical Arrhenius equatio n invo lving an expo nent in 1/ RT.
Hence we have the co nventio nal ro le of T in b = RT/aF, as will
be discussed in more detail later.
Despite the almo st universal ado ptio n of the form in which b
is written abo ve and the implicit assumptio n therefo re that b is
pro po rtio nal to temperature T, there now exists a sufficient number
103
104 B rian E . C onway
of qualitative exceptio ns to this assumed behavio r that a major
reassessment of the form of the Tafel equatio n is required with
regard to the way T enters into the behavio r of the po tential
dependence of rates.
Co nway et al.
2
in 1970 made the first detailed study of this
situatio n experimentally and also discussed co mparatively several
pertinent theo retical aspects of this pro blem regarding the com-
monly o bserved actual behavio r where a is itself a functio n of T
o r b is represented as a f(T) in some way o ther than by the
co nventio nal definition given abo ve. No twithstanding the treatment
of this pro blem in Ref. 2, already some 14 years ago , very little
attentio n has been given to it since, except in discussio n co ntribu-
tio ns of Yeager at meetings (see p. 129) and some private co mmuni-
catio ns between Gileadi and the present autho r and o thers during
the past year. This situatio n is surprising since the pro blem of the
pro per form of the temperature dependence of Tafel's b facto r is
central in the understanding of effects of po tential on
electro chemical reactio n rates and the mo lecular mechanism of
activatio n in charge-transfer pro cesses.
This paper examines this whole pro blem in a co mprehensive
way and repo rts some new examples of no nco nventio nal behavio r
of b with respect to temperature.
First, we establish some preliminary definitio ns and summarize
the histo rical backgro und.
2. P reliminary Definitions
Co nventio nally, the Tafel equatio n represents the po tential depen-
dence of electro chemical reactio n rates, expressed as currents (/)
o r current densities (/), acco rding to the following empirical
relatio n:
1
'
2
r] = a + b\ni (1)
where rj is an o verpo tential defined as the difference o f elec-
tro de/so lutio n po tential difference, V, when a current o f / Acm"
2
is passing fro m that, V
n
when the electro de pro cess is at equilibrium:
i = 0, rj = 0. The net current density / can be defined generally as
the difference o f fo rward (i) and backward (/) co mpo nents:
i=i-i (2)
E lectrochemical R eaction R ates and the T afel E quation 105
and, at equilibrium, this leads to the definitio n of the exchange
current density, i
0
:
*o = 1(77=0) = r
(77=O
) whe n i = 0 (3)
This definitio n, using Eq. (1), leads to an alternative form of
the Tafel equatio n, written expo nentially as
i = i
o
exp(iy/fc) (4)
from which it is evident that a = -bin i
0
. Co nventio nally, 17 is
taken po sitive for an ano dic reactio n with b po sitive.
Initially, the parameter b which defines the slo pe of the 17 vs.
In 1 relatio n (the 'Tafel slo pe" for this relatio n) was taken as an
empirical quantity, usually fo und to be a multiple o r simple fractio n
of RT/F.
Tafel's o riginal work in 1905
1
was co ncerned with o rganic
reactio ns and H
2
evo lutio n at electro des, and Eq. (1) was written
as an empirical representatio n of the behavio r he first o bserved. A
particular value of b = RT/2F has co me to be asso ciated specifi-
cally with Tafel's name for the behavio r of the catho dic H
2
evo lutio n
reactio n (h.e.r.) when under kinetic co ntro l by the reco mbinatio n
of two (adso rbed) H ato ms following their discharge from H
3
O
+
o r H
2
O in a prio r step.
3
Such kinetic behavio r of the h.e.r. is o bserved
under certain co nditio ns at active Pt electro des
4
and in ano dic Cl
2
evo lutio n at Pt.
5
(We no te here, in parentheses, that an alternative
o rigin for a Tafel slo pe of RT/2F for the h.e.r. at Pt has been
discussed by Breiter
4
and by Schuldiner
6
in terms of a quasiequili-
brium diffusion po tential for H
2
diffusing away from a very active
Pt electro de at which H
2
supersaturatio n arises).
The empirical representatio n of electro de pro cess rates acco rd-
ing to a relatio n such as Eq. (1) o r its expo nential form, Eq. (4),
takes into acco unt that, for many electro de pro cesses, In i is linear
in 77 over an appreciable range (> ~0. 2 V say) of po tentials. Mo re
will be said abo ut this later with regard to specific examples;
ho wever, it must be stated here that for some pro cesses such as
rapid redo x reactio ns
7
(high i
0
values) and some o rganic electro de
reactio ns,
8
a quadratic term in rj may also arguably appear in Eq.
(4), giving a curved 17 vs. In i relatio n, the o bservatio n of which
has been claimed experimentally. Such behavio r follows theo reti-
cally (see Section IV.7) from a harmo nic po tential energy rep-
reservatio n, e.g., of Marcus,
9
of the co urse of the energy change of
the reactio n alo ng its reactio n co o rdinates rather than from the
anharmo nic representatio n used in earlier wo rks.
10
"
12
3. T he T afel-S lope P arameter b
While the form of the Tafel equatio n with regard to the po tential
dependence of i is of major general interest and has been discussed
previo usly bo th in terms of the ro le of linear and quadratic terms
in 7]
7
"
9
and the dependence of the form of the Tafel equatio n o n
reactio n mechanisms,
13
the temperature dependence of Tafel slo pes
for vario us pro cesses is of equal, if no t greater general, significance,
as this is a critical matter for the who le basis of ideas of "activatio n"
and "reo rganizatio n" pro cesses
14
in the kinetics of electro de reac-
tio ns.
The co nventio nal form of fe, which follows from the recent
IUPAC reco mmendatio n for the so -called transfer coefficientt a,
is
b = RT/anF (5)
where n is the electro n charge number for the reactio n. In terms
of the derivative of the current / with po tential V, a/v =
(RT/nF)(d\n I/dV)
T
.p.c where v is the sto ichio metric number.^
Fo r simplicity, in some of the material that follows, we shall write
the co nventio nal form of b (with n and v = 1) simply as b = RT/ aF,
i.e., with the commonly assumed linear dependence on T. This form
for b, with the transfer coefficient a to be discussed in Section II
with respect to its po ssible linear dependence o n T, is, ho wever,
rarely fo und to be fo llo wed
2
experimentally, so that very basic
ideas, extant and accepted for many years, abo ut the mechanism
of activatio n and po tential dependence of electro chemical rates are
t In this article, the symbo l ft is used fo r the barrier symmetry facto r and a fo r the
charge transfer co efficient. Fo r a l e pro cess, ft = a in the usual way (see Sectio n
II. 2). In vario us places in the text, where generality is implied and the pro cess
co ncerned is no t necessarily a l e , single-step reactio n, the transfer co efficient a is
written. In the latter case, e. g. , when charge transfer is invo lved in a rate-co ntro lling
deso rptio n step, a ft facto r is included in the relevant value o f a (see p. 115).
$ Intro ductio n o f the sto ichio metric number v, with a and n, in b is so metimes
co nfusing. So me discussio n o f this matter is to be fo und in Ref. 13 and in Gileadi's
co ntributio n in Chapter 8 o f the present autho r's mo no graph, Theo ry and Principles
o f Electro de Pro cesses, Ref. 25.
put at issue. Attentio n was first directed to this rather remarkable
situatio n in the paper by Co nway et al. in 1970.
2
The main purpo se of this paper is to examine the real tem-
perature dependence of the Tafel-slo pe parameter b for vario us
pro cesses and to discuss the mechanisms of activatio n in electro de
pro cesses in the light of the o bserved behavio r of b as a functio n
of temperature.
Before pro ceeding to direct attentio n to the real temperature
dependence of Tafel slo pes as fo und experimentally for a number
of systems, it will be necessary to review the co nventio nal behavio r
usually assumed and describe its theo retical and histo rical o rigins.
The remarkable co ntrast of the behavio r actually o bserved, to be
described in Sectio n III, to that co nventio nally assumed will then
be apparent and thus the present major gap in o ur understanding
of the fundamental aspect of po tential dependence of electro de
reactio n rates will be better perceived.
I I . O R I GI N O F P O T E N T I A L DE P E N DE N C E O F
E L E C T R O C H E M I C A L R E A C T I O N R A T E S A N D T H E
C O N VE N T I O N A L R O L E O F T E M P E R A T UR E
1. T heoretical R epresentations of R ates of E lectrode P rocesses
Here, for o bvio us reaso ns, we confine the discussio n to activatio n-
co ntro lled pro cesses thus avo iding co mplicatio ns due to co ncentra-
tio n and nucleatio n o verpo tentials which are no t relevant to the
present discussio n.
The first attempts at deriving a theo retical rate equatio n for a
hetero geneo us electro chemical pro cess invo lving only electro n
transfer were given by Gurney
15
and Gurney and Fo wler.
16
Gurney's
treatment reco gnized the essential quantum-mechanical aspect of
electro n transfer at electro des, a feature rather neglected sub-
sequently for some 30 following years. The electro n transfer rate
was calculated in terms of the integral of the pro duct of pro babilities
of electro n states, and accepto r or do no r states as functio ns of their
energy distributio ns. A quantum-mechanical tunneling of electro ns
was invo lved. This paper pro vided the basis of later treatments of
electro n transfer but did no t explicitly give an acco unt of the
significance of the a parameter in b [Eq. (5)]; in fact, a is added
so mewhat as an "aftertho ught" (as a parameter y = I/a) in this
o therwise impo rtant and seminal paper.
Almost simultaneo usly, Erdey-Gruz and Volmer
17
and Butler
18
wro te a generalized kinetic equatio n for a o ne-electro n transfer
pro cess co rrespo nding to the form of Eq. (2), namely
i = i
o
{exp(a
V
F/RT) - exp[-(l - a)r,F/RT]} (6)
which to o k into acco unt: (1) bo th the forward and backward
reactio n directio ns of the pro cess co rrespo nding to net i; and (2)
the expo nential po tential dependence of the fo rward and backward
current co mpo nents thro ugh the transfer coefficients a and 1 - a,
respectively. [The representatio n in Eq. (6), with the a and 1 - a
facto rs, only applies to the o ne-electro n pro cess co nsidered here
and in the o riginal papers. More complex relatio ns must be written
for multielectro n, multistep pro cesses; see Ref. 13. Fo r the o ne-
electro n case in Eq. (6), a = /3, the symmetry facto r (see Sectio n
H.2).]
Fro m Eq. (6), it is o bvio us that for appreciable po larizatio ns
where i i
0
, the Tafel equatio n in the form of Eq. (4) is o btained
so that b is defined as RT/aF, as in Eq. (5). This is the essential
o rigin of the co nventio nal representatio n of b in terms of a transfer
coefficient a. t
While the derivative drj/d In i is used co mmo nly to character-
ize the dependence of current density o n po tential and is referred
to as the Tafel slo pe, b = RT/aF, we suggest that there is some
advantage to using its recipro cal, d In i/ dr] = aF j RT, as this co rre-
spo nds directly to the expo nential term in the electro chemical free
energy of activatio n [Eq. (9)]. Then reciprocal Tafel slo pes^ can
co nveniently be referred directly to facto rs that affect the activatio n
pro cess in charge transfer reactio ns [Eqs. (4) and (9)].
A mo re explicit physical significance of the a facto r and the
po tential-dependence functio ns at]F/RT o r (1 - a)r]F/RT in Eq.
(6) is given when the energy co urse of the reactio n is represented
t A useful general review on the to pic of transfer coefficients has been given by
Bauer
19
but does not cover the impo rtant questio n of temperature dependence of
b or a discussed in the present paper.
t If a name is required for this recipro cal quantity, it might be suggested that it be
called the "Lefat" slo pe.
E lectrochemical R eaction R ates and the T afel E quation
b) BUTL ER
109
a) GURNEY
H
+
/H
2
O
H
+
/H
2
O
H/H-,0
Figure 1. Po tential energy profile diagrams for a charge transfer
process as in H
+
ion discharge with co upled atom transfer (based
on representatio ns by Gurney
15
and Butler
21
. In (b), curve / rep-
resents the H
+
/H
2
O pro to n interactio n po tential and m that for
discharged H with the metal M. R is the repulsive interactio n of H
with H
2
O and A the resultant interactio n curve for H with M.
in terms of a po tential (o r free) energy profile o r surface diagram
(Fig. 1). Such an appro ach was given qualitatively in the papers of
Gurney
15
and Ho riuti and Po lanyi,
20
and mo re quantitatively in
Butler's 1936 paper
21
where the impo rtance of metal-to -H adso rp-
tio n energy as well as so lvatio nal interactio ns in the kinetics of the
h.e.r. was also deduced. This paper, it may be no ted, pro vided the
fo undatio n for future work o n the dependence of "electro chemical
catalysis" o n electro de pro perties, e.g., the ro le of H adso rptio n
energy and work functio n. Histo rically, it sho uld be no ted that the
ro le of so lvatio nal activatio n in the kinetics of electro de reactio ns
was already reco gnized in papers by Gurney,
15
Gurney and
Fo wler,
16
and Butler
21
(Butler also intro duced quantitatively the
effect of chemiso rptio n energy, as mentio ned abo ve, e.g., of H in
the h. e. r. ), and was given mo re detailed treatment in vario us papers
of Bockris with Parso ns and with Co nway in the 1950s. The solva-
tio nal activatio n factor is what became kno wn later as the "reo r-
ganizatio n energy" in Marcus's representatio ns
14
of the activatio n
pro cess.
110 B rian E. Co nway
A fo rmally mo re explicit representatio n of the effect of elec-
tro de po tential and asso ciated ro le of temperature o n
electro chemical reactio n rates follows from the transitio n-state
theo ry applied by Glassto ne et al.
22
so o n after the appearance of
Butler's paper.
21
The rate co nstant A of a chemical pro cess is written
as
kT
A = K exp(-&G
ot
/RT) (7)
h
where k is Bo ltzmann's co nstant and K a transmissio n coefficient
for passage of activated co mplexes, $, over the energy barrier; K
is no rmally taken as near 1.
Fo r an electro chemical rate pro cess, the rate co nstant A is
determined by an electro chemical free energy of activatio n, AG*,
related to AG*, the "chemical" free energy of activatio n, by
kT
A= K exp(-AG7tfr) (8)
n
where
AG* = AG*-0VF (9)
and j3 is a barrier symmetry facto r, analo go us to Br0nsted's a facto r
in linear free-energy relatio nships and V is the metal/so lutio n
po tential difference acro ss part of which electro n transfer no rmally
takes place. The significance of /3 is illustrated in the well-known
way by reference to the wo rking diagram, Fig. 2, which shows how
an electrical energy VF applied to the initial state of an electro n
transfer reactio n, e.g., H
3
O
+
+ e + M -> MH
ads
, changes the relative
energy of the transitio n state by (1 - fi)VF and hence the activatio n
energy for the forward directio n of the pro cess by ($VF as in Eq.
(6). t Fo r a symmetrical barrier, based o n two appro ximately anhar-
mo nic po tential energy curves (cf. Refs. 10 and 21), as sho wn
schematically in Fig. 2, it is o bvio us that p 0.5 over an appreciable
range of change of V. Fo r the H
2
evo lutio n reactio n at Hg, the
range of co nstancy of (3 is surprisingly large (cf. the work of
Nurnberg). Fo r a barrier based o n harmo nic curves (see p. 150), /3
is no t co nstant with changing V.
t Equatio n (6) is written in a general way with a transfer co efficient a. Here a = (S
(see later discussio n in Sectio n II. 2).
ADSORBED
STATE
INITIAL STATE
WITH e IN METAL
Figure 2. Working diagram showing how the "linear
free-energy relatio nship," common in electro de pro -
cess kinetics, arises from changes in electro de po ten-
tial. j8 is a symmetry factor. An extreme case of an
anharmo nic o scillato r energy profile is shown in sche-
matic form (cf. Ref. 25). This representatio n assumes
changes in V affect only the energy of electro ns in the
initial state at the Fermi level.
The principles involved in expressing /3 in this way are
evidently quite analo go us to tho se that define Br0nsted's a facto r
23
(cf. Ref. 2). Ho wever, o ne matter requires special mentio n: in the
case of electro de reactio ns, the free-energy change of the initial
state of a catho dic electro chemical reactio n o r of the final state of
an ano dic o ne asso ciated with a change of po tential has, in previo us
wo rk, been almo st entirely attributed to the change the Fermi level
of electro ns:
eV (10)
Thus the form of the energy hypersurface itself is no t no rmally
co nsidered to vary with the po tential o r co rrespo nding field acro ss
the do uble layer. Hence the effect of po tential in electro de kinetics
has usually been represented simply by "vertical mo vement" on
the energy axis of po tential energy curves witho ut much o r any
change of their shape.f Ho wever, we shall see that the co nclusio ns
t In a recent paper by Kuznetsov, discussed later on p. 153, some change of shape
is attributed to the interactio n of medium fluctuatio ns on the partially charged,
transferred H atom in the case of the h.e.r.
112 B rian E . C onwav
of the present paper and of recent new experimental work in this
Labo rato ry (see p. 179) indicate that the entropy of activatio n of
some electro de pro cesses is materially dependent on electro de
po tential in additio n to the usual effect of po tential on the energy
of activatio n thro ugh changes in the electro n Fermi level energy
(Eq. 10). Thus electro de po tential evidently can have a substantial
effect on the structure and/o r so lvatio nal enviro nment of the react-
ing mo lecular species in the interphase as reflected in this entro py
functio n, in additio n to changing the energy of electro ns.
In Br0nsted linear free-energy relatio ns for ho mo geneo us
acid/base pro to n transfers, modification of p^' s of a series of acids
reacting with a given base no rmally changes no t only the depth of
the pro to n's energy but also the shape of the po tential energy curve
for its transfer since force co nstants for BH
+
bo nds are appro xi-
mately pro po rtio nal to bo nd strength, hence pJTs, reflecting
Badger's rule. Because the main effect of electric energy change is
on O
v
(Eq. 10), the "linear free-energy relatio ns" for electro de
pro cesses (Tafel behavio r) are often linear over wider ranges of
energy change (but belo w, of co urse, tho se co rrespo nding to
appro ach to the diffusio n-co ntro lled limit
24
) than are Br0nsted
relatio ns for acid/base pro cesses over co mparable ranges of pK;
see e.g., Refs. 23 and 24.
Intro ductio n of Eq. (9) into ~A [(Eq. (8)] gives
t=K êxp[-(AG* - f3VF)/RT] (11)
n
Equatio n (11) is the transitio n-state equatio n for electro chemical
rates (i is, of co urse, pro po rtio nal to ~k and co ncentratio n of reactants
in the do uble layer at the electro de interface in the usual way
25
)
and is o bvio usly equivalent to the Tafel equatio n in expo nential
form [Eq. (4)]. From Eq. (11) it is seen that the Tafel slo pe for a
simple electro n transfer pro cess is RT//3F, i.e., b is linear in tem-
perature. We shall return later to a more critical examinatio n of
Eq. (11) inso far as energy and entro py co mpo nents of the free
energy of activatio n are co ncerned.
It was mentio ned that manipulatio n of energy profile diagrams
(Fig. 2) gives a simple significance to /3. Ho wever, this is a grossly
oversimplified representatio n since the co urse of activatio n in a
charge transfer pro cess involves intermo lecular and o rientatio nal
fluctuatio ns in the so lvatio n shell of the reacting io n or mo lecule
at the electro de, as well as some physical transfer of an ato m do wn
a single reactio n co o rdinate in the case of ato m transfer reactio ns,
as with ano dic Cl
2
evo lutio n, metal depo sitio n, o r the h.e.r. (in the
latter case, the ato m transfer co mpo nent may be no nclassical
26
'
28
).
Other representatio ns
19
'
25
of the significance o f/3 must acco rd-
ingly be included here.
In the case of multico o rdinate redo x pro cesses, Hush
29
has
suggested that /3 can be represented as the fractio nal charge transfer-
red when the transitio n-state co nfiguratio n is attained: for sym-
metrical redo x reactio ns such as Fe(CN)6~/Fe(CN)e~ o r
Fe(aq)
3+
/Fe(aq)
2+
, p is then o bvio usly 0.5 except for any asym-
metry that may be intro duced by a different degree of specific
adso rptio n of the ox (o xidized) form from the red (reduced) form
of the co njugate redo x pair.
30
This representatio n, now no lo nger
believed to be co rrect (cf. Marcus
914
), also gives an indicatio n of
how (3 is related to the way in which the transitio n-state configur-
atio n may be more similar to the initial state than to the final state,
o r vice versa, in the case of unsymmetrical redo x pairs. The po tential
energy diagram representatio n also gives similar indicatio ns, as
may be seen for limiting cases of highly exo energetic o r highly
endo energetic electro n transfers.
Alternatively, in a related qualitative sense, /3 can be inter-
preted as measuring
25
'
35
fractio nally "ho w far alo ng" the reactio n
co o rdinate is the transitio n state attained and hence over what
fractio n of the po tential difference, A V, acro ss the Helmho ltz layer
do es the electro n charge have to be transferred to this transitio n
state. This interpretatio n is related to the "half-jump distance"
characterizing activated charge transfer acro ss, e.g., o xide films.
31
Fo r symmetrical pro cesses, each of these ways of representing
the significance of fi gives the latter quantity a value of 0.5. However,
the unsymmetrical pro cesses, the different representatio ns do no t
lead to identical values of /3 for a given reactio n; no te that ato m
transfer pro cesses are no rmally highly unsymmetrical, so how /3 is
co nsidered from the theo retical po int of view is especially impo rtant
for such types of electro de reactio n.
The significance of ]8 as a measure of the fractio n of the
interface p. d. involved in the fo rmatio n of activated co mplexes is
formally explained as fo llo ws. In terms of a suppo sed quasiequili-
brium between initial-state ions i and transition-state co mplexes $
in a discharge reactio n,
where ty
x
is the po tential at the outer Helmho ltz plane and <* is
the lo cal po tential in the co mpact double layer at which activated
co mplexes begin to pass over to pro duct co nfiguratio ns. AG
o t
is
defined as
/4-M, and nf-tf + RTln^/c^^-zFi^-^)
Then </>* - <Ai may be written as some fractio n p of <
M
- </>i, where
<
M
is the electro de metal Galvani po tential. The same result, but
no t having the same physical significance, is o btained if a fractio n
(3 of a unit e charge is envisaged as being transfered to $ as it is
formed from the initial state.
29
This representatio n is no t, ho wever,
co nsistent with that sho wn abo ve in terms of lo cal po tential <*;
no r can bo th types of representatio n be intro duced simultaneo usly
since then evidently (3 wo uld be 0.25!
It is clear from the fo rego ing pro po sitio n that p co uld be |,
that a representatio n of the appro ach to the transitio n state in
terms of traversal of a charged reactant particle acro ss an electrical
po tential profile to </>* (appro ximately half the p. d. A</> acro ss the
Helmho ltz layer) canno t be co mbined with an adiabatic readjust-
ment of electro n distributio n giving (cf. Hush
29
) a charge of appro xi-
mately e/2 o n the transitio n state for a o ne-electro n transfer pro cess.
Thus, the representatio n of the pro cess of attainment of the transi-
tio n state in which activatio n of the reacting particle takes place
thro ugh so lvatio n-shell reo rganizatio n and/o r ligand co o rdinatio n-
shell disto rtio ns in the case of io nic redo x reactio ns o r, for ato m
transfer pro cesses, thro ugh a co upled bo nd stretching and so lvatio n-
shell reo rganizatio n, implies that the transfer of the electro n takes
place by a tunneling pro cess, as pro po sed by Gurney,
15
to (o r from)
the reactant particle when the latter has attained, multidimensio n-
ally, the required transitio n-state co nfiguratio n so that a radiatio n-
less electro n transitio n arises in the usually suppo sed manner.
The discussio n given abo ve serves to indicate that the questio n
of "ho w" the electro n transfer event actually takes place, if such
a micro sco pic and no rmally no nclassical pro cess can be co nsidered
in tho se terms, is no t yet fully answered.
2. R elation of p to a
In Section II. 1 the transfer coefficient a was intro duced in the usual
general way in relatio n to the definitio n of 6, the Tafel slo pe. In
electro de reactio n mechanisms invo lving two o r mo re co nsecutive
steps, the dependence of a time-invariant current density o n po ten-
tial must be evaluated by o ne of the fo llo wing:
1. The steady-state metho d in which differential equatio ns
are set up defining the time dependence, d[x]/dt, of co ncentratio ns
of intermediates x invo lved in the pro cess. In the steady state,
d[x~\/dt = 0 giving a rate equatio n co ntaining po tential-dependent
terms.
2. Using the quasiequilibrium hypo thesis, for steps prio r to
the rate-determining o ne, to enable an explicit relatio n between
(surface) co ncentratio n of x species and po tential to be substituted
in a rate equatio n for the velo city of the rate-determining step which
itself may o r may no t be directly dependent on po tential.
No rmally,
25
'
32
metho d 1 do es no t give a rate equatio n that
leads to a simple explicit expressio n for po tential dependence of
the current density and hence no simple-valued Tafel slo pe arises.
Numerical evaluatio ns of the dependence of In i o n rj can, ho wever,
usually be made, e.g., for a range of assumed o r evaluated rate
co nstants. Bo ckris
32
has given the mo st so phisticated applicatio n
of metho d 1, using Christiansen's appro ach;
33
the multistep O
2
evo lutio n reactio n was taken as an example. It must be stated that
experimentally meaningful results from this metho d only arise after
limiting assumptio ns are made abo ut relative values of the rate
co nstants for the co mpo nent steps (in fo rward and backward direc-
tio ns) and asso ciated surface co verages by adso rbed intermediates.
Usually, the assumptio ns required to derive the electro de-kinetic
behavio r for the limiting cases are equivalent to tho se that are
ado pted in the quasiequilibrium metho d 2; then, the Tafel slo pes
for most kinetically significant cases can be evaluated "by inspec-
tio n" after a little experience with writing the equatio ns.
Fo r a reactio n scheme invo lving n charge transfer events prio r
to the rate-determining step (for most electro de reactio ns n > 3),
the Tafel slo pes work o ut to be
b = RT/(n + P)F (i.e., a = n + 0) (12)
116
B rian E . C onway
o r
b = RT/nF (i. e. ,a = n) (13)
depending on whether [Eq. (12)] or no t [Eq. (13)] charge transfer
is involved in the final rate-co ntro lling step. "Chemically" co ntro l-
led rate-determining steps thus have Tafel slo pes determined by
even fractio ns of RT/F, while tho se that involve a charge transfer
pro cess in the rate-co ntro lling step have slo pes that are odd fractio ns
of RT/ F, depending on the value n and of /3. It will be impo rtant
for the subsequent discussio n to no te that pro cesses of the former
type [slo pes characterized by Eq. (13)] are independent of any
barrier symmetry factor o r of its po ssible temperature dependence.
Po ssible values of b for steps in the h.e.r. have been discussed
by vario us wo rkers and the limiting cases have been co nsidered in
detail by Bo ckris,
13
Parso ns,
3
and Co nway;
34
similar treatments
have been given for the O
2
evo lutio n reactio n,
32
the Ko lbe reac-
tio n,
36
and some metal-depo sitio n pro cesses.
35
Finally, here it sho uld be no ted formally that a is, of co urse,
identical with /3 in cases where the initial step in a reactio n sequence
is a o ne-electro n charge transfer pro cess and is itself the rate-
co ntro lling pro cess. Also b can be related to the to tal number of
electro ns passed in the o verall reactio n o r in the rate-co ntro lling
step thro ugh a and the sto ichio metric number v. This matter has,
ho wever, been treated in vario us earlier works by, e.g., Ho riuti and
Ikusima,
37
Bo ckris,
13
and Gileadi,
38
and so need no t be examined
again here since no invo lvement of the temperature variable arises
apart from that in b itself.
I I I . T H E E XP E R I M E N T A L S I T UA T I O N R E GA R DI N G T H E
T E M P E R A T UR E DE P E N DE N C E O F T A FE L S L O P E S
1. General R emarks
Co ntrary to common belief, the Tafel equatio n as represented by
Eqs. (1) o r (4), with b given by Eq. (5), virtually never represents
the electro de-kinetic behavio r of electro chemical pro cesses (except
pro bably simple io nic redo x reactio ns that have minimal chemical
co upling of o ne kind o r ano ther, p. 125) in particular with reference
to : (1) the suppo sed linear pro po rtio nality of b to T (i. e. , a is a
co nstant, temperature-independent parameter); and/o r (2) the form
of b with respect to T. These experimental facts are central to the
to pic of the present paper.
In this sectio n the bases of the abo ve remarks are do cumented
from previo us literature and from new results recently repo rted.
2. Documentation and E xamples of the E xperimentally O bserved
Dependence of b on T and the B ehavior of a with T
(i) The H
2
Evolution Reaction at Hg
Histo rically, the h.e.r. has often been taken as a pro to type
pro cess for discussio ns of the principles of electro de
kinetics;
I317
'
18
'
2O
'
21U
ho wever, the behavio r of this pro cess at
vario us metals is far from that represented by Eqs. (1) o r (4) with
(5). Fo r the h.e.r. at Hg, four sets of relevant data that are to be
co nsidered reliable from the po int of view of system purity and
experimental technique,
39
'
40
and cover a wide range of temperature,
are available for discussio n: the wo rk of Post and Hiskey
41
in
aqueo us HC1; the work of Conway et al
2
in methano lic HC1 from
173 to 353 K; the work of Bockris et al
43
in methano lic HC1 abo ve
and below the mp of Hg; and the wo rk of Co nway and Salo mo n
42
in methano lic HC1 and MeOD/DCl, also do wn to low temperatures.
Fo llo wing the first indicatio n in the wo rk of Sto ut
48
that b can
be independent of temperature, Bockris and Parso ns,
11
and Bockris
et al
43
sho wed that a similar effect aro se in the h.e.r. at Hg in
methano lic HC1 between 276 and 303 K; belo w these temperatures,
b apparently varied in the co nventio nal way with T. Ho wever, the
derived a values showed a co nsiderable spread. Variatio ns of the
temperature effect in b were discussed in terms of the po ssible
influence of impurities but an o verall assessment of all o ther, mo re
recent, o bservatio ns of the dependence of b o n T for vario us types
of reactio ns leads to the co nclusio n that the "unco nventio nal"
dependence is not due to some incidental effect of impurities. In
fact, in ano ther paper, Bockris and Parso ns
11
suggested that the
temperature dependence of fi for the h.e.r. at Hg aro se because of
expansio n of the inner regio n of the do uble layer with temperature.
They also no ted that, fo rmally, for b to be independent of T, the
entro py of activatio n sho uld be a functio n of electro de po tential,
0 13
(a)
0 10
0 07
005
H
2
EVOL UTION AT Hg
MeOH/HC
(CONWAY et ol)
b(CLASSICAL)'2 3RT/O5F
H
2
O/HCI(POST* HISKEY)
Br
2
EVOLUTION AT C/CH5CN
L
180 200 220 240 260 280 300 320 340 360
T/K
0 62
0-60
(b)
0 54
052
011
010
0 09
0 08
0 07
b and a as f(T) at Hg
Solid Hg
0 06
203
. Solid Hg
223 243 263
T/K
283 303
but the matter was no t pursued further until the treatment of
Co nway et al
2
referred to in mo re detail elsewhere in this article.
In Fig. 3a, the Tafel slo pes from these autho rs' wo rks are
plo tted co mparatively as a functio n of temperature T. It is evident
that the Eq. (5) fo r b as/ ( T) , co mmo nly assumed, is no t fo llo wed,
and the T dependence of b is fitted
2
by an equatio n of the form
RT
0+*
rather than that of Eq. (5) with a s p. (No te, that fo r Hg, almo st
all autho rs, with the exceptio n of Ho riuti,
44
agree that the rate-
co ntro lling step in H
2
evo lutio n at Hg from acidic so lutio ns is the
discharge of the hydro nium io n, H
3
O
+
, o r the related species H
9
C>4,
so that a = fi; cf. Sectio n II. ) The data of Bo ckris et al
43
are
so mewhat different (Fig. 3b) and (3 appears to be dependent o n T
o ver part of the T range investigated.
Thus from Refs. 2,41, and 42, b has a temperature-independent
co mpo nent, X, which fo r the h. e. r. at Hg has the value 40 mV. Here,
in Eq. (14), /3' is the symmetry facto r which must be evaluated
from the derivative of b with respect to T; thus
db/dT= R/p'F (15)
so that
P' = (R/F)[l/(db/dT)] (16)
The data of Fig. 3a sho w that p' is constant with T but has a value
appreciably different from 0.5 0.05 usually o btained using Eq. (5)
at T =* 298 K. It is evident, and impo rtant to no te, that for the h. e. r.
results at Hg it is inco rrect to evaluate j3 from Eq. (5) at so me
particular values of T since, in fact, that equatio n erro neo usly
represents the fo rm of b with T; it is Eq. (14) that must be emplo yed,
using Eq. 16.
It is certainly a remarkable co incidence that (3 evaluated from
Eq. (5) at the "labo rato ry temperature" 298 K co mes o ut very
Figure 3. (a) Tafel slopes b for the h.e.r. at Hg in aqueo us and methano lic acid
so lutio ns as a function of temperature (from data of Post and Hiskey, Conway et al.,
2
and Conway and Salo mo n
42
). Co mpariso n with behavio r for Br
2
at graphite also shown
(see Fig. 8). (b) Tafel slopes b for the h.e.r. at liquid and solid Hg from the results of
Parsons and Bo ckris
11
in methano lic HC1 (from Ref. 43).
near the co nventio nally "expected" value of 0. 5; a similar po int
has been emphasized by Yeager et al.
45b
(see belo w) with regard
to his results fo r O
2
reductio n at Pt in H
3
PO
4
o ver a wide temperature
range. Ho wever, it evidently just is a co incidence since it is quite
evident that the true "/3", written as j3' in Eq. (14), must be evaluated
from Eq. (16) rather than from Eq. (5). If /3 is evaluated from Eq.
(5) it has an apparent temperature dependence, the o rigin of which
is clear if Eq. (5) is co upled with Eq. (14), which truly represents
the results of Fig. 3a, namely
! ?
Then j8 is evidently given by
1//3 = l/p' + KF/RT (18)
o r
(19)
so that p is apparently T dependent; thus it is seen that fi apparently
increases with T as has been no ted empirically in so me earlier
wo rks using Eq. (5) with experimental b values. We emphasize
again that the symmetry facto r fo r the h. e. r. at Hg must be evaluated
from Eq. (14); then the true /3, written as /3', is fo und to be
independent o f T and the Tafel slo pe has the fo rm represented by
Eq. (14) which is fundamentally different from that no rmally
assumed [Eq. (5)]. We shall co mment o n po ssible no ntrivial expla-
natio ns fo r the fo rm o f Eq. (14), including the significance of K,
in Sectio n IV.
() The H
2
Evolution Reaction at Ni
Co nway et al.
2
also studied the h. e. r. at Ni under high-purity
co nditio ns in methano lic HC1 o ver a wider range of temperature.
Under these co nditio ns, the "Tafel lines" appear as two linear
segments,t the slo pes of each of which depend o n T as sho wn in
Fig. 4. Co mparative data fo r the D
2
evo lutio n reactio n (d. e. r. ) from
MeOD/DCl are sho wn in Fig. 5.
t In aqueo us HC1, lines with a small degree o f curvature are usually o bserved with
b = 0.10 0. 005 Vat 298 K.
-0.6
-0.5
-0.4
Ni/HCI-MeOH
L og [CURRENT DENSITY] amp cm"
Figure 4. Tafel relatio ns for the h.e.r. at Ni in methano lic HC1 over a wide range
of temperature (from Ref. 2). No te that upper-regio n slo pes increase with increasing
T, while lower-region slopes decrease for the same electro de pro cess.
The two linear Tafel regio ns at Ni in methano lic HC1 vary
with T in a co ntinuo us and co mplementary way: o ne has a slo pe
that increases with T while the slo pe of the o ther simultaneo usly
decreases with T (Fig. 4), so there is a singular temperature at
which the Tafel relatio n is o ne line over the who le c.d. range.
2
The
directio ns of change of the slo pes of the two Tafel lines at each
temperature, o ther than at the singular temperature, co rrespo nd
apparently to reactio n mechanisms that are co nsecutive ( ^ ^ 0
o r parallel ( /"""") . Ho wever, we believe, based on new data
o btained from po tential-decay experiments,
77
that the two regio ns
co rrespo nd to deso rptio n mechanisms in the h.e.r. taking place
thro ugh different po pulatio ns of adso rbed H which have different
dependencies of their co verage on T and rj.
It is evident that the 7-dependence of b again do es no t follow
that co nventio nally assumed [Eq. (5)] and, mo reo ver, for the same
reactio n at the same metal, Ni, the two Tafel-line segments have
slo pes that vary in opposite directio ns with temperature; Fig. 4
shows that this is a systematic variatio n and no t the result of some
122
B rian E . C onway
0 26 -
022 -
O
CL
o
0.14 -
0.10 -
"bv_ D(Ioweri)
D(upperTT^?S
^DC! MeOD
( a) Ui
^HCI-MeOH
X
^^^^^S^Mupper ' O \
^^" ^^^^- ^ a
H (lower i) " ^
160 220
T/K
260 300
C/) 0. 09 -
150 190
230 270 310
T/K
Figure 5. Tafel slopes for the d.e.r. at Ni in d-methano lic DC1 over a wide
range of temperature in co mpariso n with tho se for the h.e.r. in ethano lic HC1
(from Ref. 2).
arbitrary co mpariso n of the behavio r at say just two different
temperatures. It is interesting that in methano lic HC10
4
, made up
from the 70% aqueo us acid, so that the methano lic so lutio n co ntains
an unavo idable small mo le fractio n of H
2
O, two Tafel regio ns are
no t o bserved. Hence the behavio r in anhydro us methano lic HC1
may be co nnected with anio n adso rptio n effects in that so lvent [see
Section IV.9]. As will be discussed in that sectio n, the influence of
temperature o n the effects of adso rbed anio ns o n the kinetics of
an electro de pro cess must always be reco gnized as a po ssible reaso n
for unco nventio nal temperature variatio n of Tafel slo pes, unless
co nditio ns o therwise preclude the po ssibility of such effects, e.g.,
as at Hg at appreciable o verpo tentials in the h.e.r. where anio n
adso rptio n is known to be insignificant.
93
'
94
(Hi) The H
2
Evolution Reaction at Cd
Data for the h.e.r. at Cd were also fo und
2
to behave unco nven-
tio nally.
(it?) The H
2
Evolution Reaction at Electrocatalytic Ni-Mo Alloys
Recently, much interest has centered o n the electro catalytic
behavio r of Ni-Mo allo yst (prepared electro lytically o r by thermal
reductio n of o xide o r mo lybdate mixtures) for catho dic H
2
evo lutio n
in alkaline-water electro lyzers o r as catho des in electro lytic Cl
2
cells. The h.e.r. at these electro de materials exhibits
46
remarkably
low Tafel slo pes, in the range 22-26 mV, at elevated temperatures,
~363 K. This is o ne of the reaso ns for their excellent behavio r as
electro catalysts for the h.e.r. Ho wever, the Tafel slo pes exhibited
by these materials depend o n temperature in a most unusual way,
decreasing with increasing temperature, as do some of the results
at Ni
2
(Fig. 4).
The rj vs. In [current-density] relatio ns (Fig. 6) exhibit two
linear regio ns (as with Ni under certain co nditio nssee Fig. 4),
each of which has a slo pe that decreases with T as shown in Fig.
7. This is no t seemingly due to so me change of mechanism as
temperature is increased since the decrease of the slo pes with T is
evidently (see Fig. 7) a co ntinuo us o ne for bo th regio ns of the In i
vs. rj relatio ns as is seen from Fig. 7.
This behavio r must co rrespo nd to variatio n of a with a po wer
of T > 1 in the relatio n b = RT/a(T)F in o rder for b to decrease
with increasing T, or b is of the form b = K' - cT for the particular
case where b decreases linearly with T as in some experiments.
$ There is some questio n whether these are true equilibrium metallic alloys (it is
unlikely) and also what is the state of Mois it metallic or in the form of MoO
in a Ni-metal host structure.
0.4
0.3
Q2
0.1
- 3
log i (mA cm
Figure 6. Tafel relatio ns for the h.e.r. at Ni-Mo electro plated electro catalysts at
several temperature curves (1-4), 341, 319, 298, and 278 K, co mpared with behavio r
of metallic nickel (curve 5) (Real apparent area factor for Ni-Mo coated electro de
450 x ); electro lyte is 1.0 M aqueo us KOH (from Ref. 46, see also Fig. 19).
(v) Redox Reactions at Electrodes Involving Werner Complex Ions
The behavio r of b as /(T) for io nic redo x reactio ns at elec-
tro des, especially tho se pro cesses that invo lve only o uter-sphere
changes of state, and bo th red and ox species which are no t
specifically adso rbed, is of great interest. From some of Weaver's
wo rk
107108
info rmatio n o n the dependence of b on T for such
reactio ns is available and some attempts have been made, e.g., by
Parso ns and Passero n,
7
to establish if the po tential-dependent facto r
in the electro chemical rate equatio n in fact includes a quadratic
term in rj as well as the usual linear o ne; ho wever, this is a different
questio n (cf. Ref. 8) related to the harmo nicity o r, o therwise, of
the fluctuatio ns involved in the activatio n pro cess.
14
Later in this article, we refer to Weaver's wo rk
107108
on the
evaluatio n of real entro pies of activatio n of some o ne-electro n redo x
reactio ns of complex metal io ns at Hg, and co rrespo nding data on
150
100
It!
3
u- 50
<
HIGH b REGION
NJ:Mo:Cd I
79 20: I I TAFEL SLOPES
I MNaOH
LOW b REGION
280
290 300
T/K
310 320 330
Figure 7. Decrease o f slo pe b fo r h. e. r. at Ni-Mo electro co ated catho des with
temperature: (O) upper c. d. regio n, and (x) lo wer c. d. regio n (fro m Ref. 46).
temperature variatio n of the transfer coefficient. These results are
of great interest.
The pro blem with redo x reactio ns of this type is that their rate
co nstants are usually to o large for regular steady-state techniques
to be reliably applied, a o r (3 then have to be determined thro ugh
the reactio n o rder o r by some metho d such as Faradaic rectificatio n.
Usually, such metho ds require evaluatio n of the do uble-layer
behavio r in o rder to make "do uble-layer co rrectio ns. " This is often
an unsatisfacto ry business, especially when co rrectio ns wo uld be
required over a range of temperatures. We co nclude that for this
impo rtant class of electro chemical reactio ns more data for
examinatio n of b(T) o r a(T) are required. However, for certain
io nic redo x reactio ns that are sufficiently slo w, Weaver
107
has been
able to evaluate a as /(T) from Tafel plo ts over a range of 0.3 ~
0.4 V: a is in fact found to be independent of T for these cases (see
p. 179), an impo rtant result.
The Tafel-slo pe behavio r as /(T) for so lvated electro n forma-
tio n
47
in, e.g., liquid NH
3
o r HMPA so lutio ns would be ano ther
interesting case for investigatio n.
126 B rian E . C on way
(vi) Anodic N
2
Evolution from N
3
-ion at Pt
Pro bably the earliest, well-do cumented case of unco nventio nal
behavio r of the Tafel slo pe with temperature was repo rted by Sto ut
48
for the ano dic evo lutio n of N
2
from discharge of azide io n at Pt in
aqueo us so lutio ns. The o verall reactio n is
2N3 -> 3N
2
+ 2e (20)
but detailed steps in the reactio n have no t been characterized;
presumably the N3 radical is an intermediate but whether its
deco mpo sitio n to N
2
is ho mo geneo us o r hetero geneo us is as yet
unkno wn and the questio n of reco mbinatio n to give an unstable
(and pro bably chemically unlikely) N
6
species is unreso lved.
Fo r the azide discharge reactio n at Pt, b in Eq. (5) is fo und
to be independent of T so that a itself is apparently linear in TI
This case can be regarded qualitatively as different from that for
the h.e.r. at Hg or limitingly as a special case of Eq. (14) where
K RT/ p'F. Theo retical aspects of this type of case will be treated
in Section IV.
Altho ugh very little is known abo ut the surface elec-
tro chemistry of the azide discharge reactio n, analo gies with the
situatio n in Cl~ o r R. COO"
36
discharge from aqueo us so lutio ns
wo uld suggest that N^ is discharged at Pt o n a surface covered o r
partially co vered by discharged OH o r O species (cf. Ref. 49) with
po ssible co adso rptio n of N^ io n (regarded as a pseudo halo gen).
Then the state of surface o xidatio n of the Pt and the temperature
dependence of the state of surface o xidatio n will determine, in part,
the temperature dependence of the Tafel slo pe of the N^ discharge
pro cess. That a pro cess o ccurring on a surface o xide is involved is
indicated by the unusually high Tafel slo pes of ART/F (as in
the Ko lbe reactio n
36
) characteristic (cf. Refs. 50 and 51) of charge
transfer acro ss a barrier-layer film. Co mpetitio n between specific
adso rptio n of N^ and electro depo sitio n of OH and O species
49
may
be expected in this reactio n. In this case, it is difficult to assign any
single reaso n for the independence of b o n temperature. Qualita-
tively, a tends to beco me smaller with increasing film thickness but
greater with increasing film co nductivity. The surface elec-
tro chemistry involved (cf. Ref. 49) is o bvio usly co mplex and little
is kno wn abo ut its temperature dependence except that surface
o xidatio n of Pt is facilitated, as may be expected, by elevatio n of
temperature ;
52
the charge transfer characteristics of the o xide film
are no t, ho wever, kno wn as a functio n of temperature, but co nduct-
ance measurements were made by Shibata and Sumino
53
at ro o m
temperature for thin and thick films in the absence of Cl" o r
pseudo halide io ns.
(vii) Anodic O
2
Evolution at Pt
In studies of the O
2
evo lutio n reactio n at Pt from aqueo us
H
2
SO
4
, it is fo und that the Tafel slo pes determined for the steady-
state kinetics of this reactio n at several temperatures do no t co rre-
spo nd to the co nventio nally expected behavio r acco rding to Eq.
(5), so that a is so mewhat temperature dependent as in the case
of Section III. 2, (ii). Ho wever, mo re wo rk o n this case is required,
taking into acco unt the temperature dependence of oxide-film
gro wth, etc.
(viii) Anodic Br
2
Evolution from Br~ in CH
3
CN Solution
In an experiment designed to determine if unco nventio nal
temperature dependence of Tafel slo pes (where a seems to be itself
linear in T) o riginates in some way o n acco unt of the temperature
dependence of the structure
54
'
55
of asso ciated so lvents such as H
2
O
and MeOH (cf. Ref. 2) in the electro de/so lutio n interphase or of
o rientatio n of so lvent dipo les of the structured so lvent, Co nway et
al
2
determined b for ano dic Br
2
evo lutio n at graphite from Br~ io n
in CH
3
CN over an 80 K temperature range: b was fo und to be
70 7 mV and independent of T o ver the who le temperature range
covered so that a is again, for this case, independent of T (Fig.
8a). Since CH
3
CN, altho ugh a stro ngly po lar so lvent, is generally
co nsidered to be "unstructured" in the sense that H
2
O o r MeOH
are, it can be co ncluded that it is unlikely that the temperature
dependence of a can be directly attributed to changes of structure
of the so lvent in the do uble layer o r of the structural facto r
55
in
the so lvatio n of the reactant io n. Recent results from this labo rato ry
on ano dic Cl
2
evo lutio n at Pt also show that b (=0. 04 V in this
case, prio r to a limiting current) is almo st independent of T. This
result is surprising since two co mplicating aspects of the electro de-
kinetic behavio r must be invo lved: temperature dependence of Cl~
128 B rian E . C oiway
O0O8
007
UJ
Q 0 06
00
1 0
z
0 9
J j
i t Q Q
Q_
< 07
GRAPHITE/(C
3
H
7
)
4
NBr-CH
3
CN
-
0
i 5
- 0
-
^ ~ "
0
^ - ^ ^ " D ^
- ^
t i l l
ft
0
0
0
0
0
1
0
' 0
0
1
230 250
270
T/K
290 310 330
Figure 8a. Independence of b on T and linear variatio n of a with 7 for ano dic
Br
2
evolution from (n-Pr)
4
NBr at pyrolytic graphite ano des (from Ref. 2).
io n adso rptio n that is also po tential dependent,
5
and temperature
and po tential dependence of surface o xide co verage.
Mo re recent work in this labo rato ry with Wilkinso n (to be
published) o n the Br
2
evo lutio n reactio n in CH
3
CN gave so mewhat
different results from tho se of Ref. 2 when glassy carbo n was used
as the ano de. Low Tafel slo pes (0.065 at 298 K) were again o bserved
but b was no t, in this case, found to be independent of T [Fig. 8b,
(i)]. In fact, the derived a values [Fig. 8b, (ii)] tend to beco me
co nstant with T for T < 267 K while they decrease with T abo ve
that temperature. This is the trend expected from Eq. (24) as /x7 < A
at sufficiently low T values, depending on the magnitude of fx.
The difference in behavio r of pyro lytic graphite, examined in
Ref. 2, and the glassy carbo n investigated in this mo re recent wo rk,
is pro bably do ne to the different electro catalytic surfaces that these
materials present. Thus, impedance measurements we have made
indicate little adso rptio n pseudo capacitance for adso rbed Br*
species at glassy carbo n whereas, at pyro lytic graphite, an adso rp-
tio n capacitance is measurable. The results depend on edge o r
basal-plane expo sure.
E le K hemical R eaction R ates and the T afel E quation 129
0 07
b/V
0.04
0 96
b AND 06 AS f ( T) FOR Br
2
EVOLUTION AT GLASSY
n)
220 320
Figure 8b. Tafel slo pe, b, and transfer co efficient, a, fo r
the Br
2
evo lutio n reactio n at glassy carbo n in CH
3
CN
fro m 0AM (n - C
3
H
7
)
4
NBr with 0.2 M Br
2
o ver a range
o f temperatures: (i) values o f b\ (ii) values o f a.
(ix) Cathodic O
2
Reduction in H
3
PO
4
at Pt over a Wide Range
of Temperature
Appleby
45a
and, later, Yeager et al
45h
have found interesting
cases of unco nventio nal temperature dependence of b for O
2
reduc-
tio n at Pt and Os in H
3
PO
4
over a 115 and 220 K range of 7,
respectively. The experimental behavio r for Pt
45b
is shown in Fig.
9. This case is impo rtant as it gives no t o nly ano ther example of
unco nventio nal temperature dependence of the Tafel slo pe (a oc
T), but also shows that this type of behavio r arises for a reductio n
reactio n as well as for o xidatio n reactio ns where the pro perties of
surface o xide films that can vary with temperature may co mplicate
the situatio n. Using this example of the independence of b o n 7,
Yeager has reemphasized
56
the impo rtance of the who le questio n
130 B rian E . C onwiy
1 Or
O
2
REDUCTION AT Pt in H
3
P0
4
a
0 5
INTERCEPT 0. 04*0 015
u
200 400 600
T/K
Figure 9. Behavio r o f the Tafel slo pe fo r O
2
reductio n in H
3
PO
4
as a functio n o f
temperature (fro m Yeager et al Ref. 45b).
of temperature dependence of a for the basic understanding of the
po tential-assisted activatio n pro cess in electro de kinetics.
(x) Reduction ofNitro Compounds
Recent unpublished work by Evans
102b
(see Ph. D. Thesis, 1982,
by R. A. Petersen, Chemistry Department, University of Wisco nsin,
Madiso n, Wisco nsin) has shown that for reductio n of C
2
H
5
NO
2
at
a hanging Hg dro p over a temperature range of ~40 K, a is sensibly
co nstant with a value of 0.45 0.03. This is evidently o ne of the
few cases where the co nventio nal form of the Tafel equatio n applies
with b linear in T. It wo uld be interesting to kno w if the Tafel slo pe
is co rrespo ndingly co nstant with po tential o r no t (cf. Ref. 8 for
reductio n of o ther nitro co mpo unds).
(xi) General Comment Regarding Independence ofb with T
When b is o bserved to be independent of temperature, b is
formally either equal co mpletely to the co nstant K in Eq. (14) or
a is linearly pro po rtio nal to T in the relatio n b = RT/a(T)F. Fo r
such cases, it is unpro ductive to try to evaluate I/a o r l/p by
taking the derivative of b with respect to T in the way that can
usefully be do ne for the h.e.r. behavio r at Hg
2
to which Eq. (14)
applies. Physically, the two situatio ns are no t necessarily identical
but canno t be experimentally distinguished except in a case where
say a (T) = a
0
+ yT rather than a (T) = yT. The latter form implies,
of co urse, that a - 0 as T -> 0; this is clo se to the behavio r actually
o bserved
2
for Br~ discharge at carbo n in aceto nitrile referred to in
Section II.
(XI I ) Phenomenological Conclusions from the Experimental Behavior
It is useful, at this po int, to summarize the pheno meno lo gical
co nclusio ns from the experimental data referred to abo ve.
1. The form of the Tafel-slo pe parameter b for the h.e.r. at
Hg is no t b = RT/pF with p a co nstant near 0.5 but is rather
b = RT/p'F + K or RT/(\ - fxT)F (cf. Eq. 24), so that the form
of the Tafel equatio n is no t that co mmo nly assumed. This co n-
clusio n is based on results of three different gro ups of wo rkers.
2. Fo r the H
2
evo lutio n reactio n at o ther metals, the deviatio n
from the co nventio nal form of b is even mo re striking, and a or p
may be/(T), usually linear.
3. Fo r o ther electro de reactio ns such as the ano dic N
2
and
O
2
evo lutio n pro cesses, and O
2
reductio n, b appro aches the form
b = RT/a(T)F, where a varies mo re o r less linearly with T making
b almo st independent of T.
4. Ano dic Br
2
evo lutio n at C from Br~ in CH
3
CN behaves
as in case 3.
5. Fo r the h.e.r. at special Ni-Mo electro des, a apparently
even decreases with increasing T, as is also fo und for o ne of the
h.e.r. pro cesses at Ni in MeOH.
6. Two types of cases can be limitingly distinguished where
(i) b = RT/p'F + K so that b is still linear with T, p' is a co nstant,
and K is a T-independent co mpo nent of b, and (ii) b = RT/a(T)F
and a is pro po rtio nal to T [a(T) = yT] so that b is independent
of T (cf. cases 1 and 3 abo ve).
7. A final and very impo rtant general pheno meno lo gical co n-
clusio n is that the co nventio nal form of the Tafel equatio n with
slo pe b = RT/aF with a co nstant is rarely o bserved at least for
tho se cases where adequate and reliable T- dependence studies of
the electro de kinetics have been made (cf. Yeager
56
). Simple io nic
redo x reactio ns seem, ho wever, to be an exceptio n.
86
8. The previo us co nclusio n means that existing co nventio nal
representatio ns of the activatio n pro cess acco rding to an
electro chemical Arrhenius type of equatio n involving the
Bo ltzmann facto r 1/kT are serio usly inadequate and fail to rep-
resent the real kinetic behavio r of most electro de reactio ns from
the impo rtant po int of view of temperature effecta central aspect
of most evaluatio ns of kinetics of chemical pro cesses.
9. Since b values for simple electro n-transfer-co ntro lled pro -
cesses are appro ximately of the co rrect magnitude at 298 K, taking
P 0.5, it is clear that the temperature facto r in the experimental
behavio r must be entering the electro chemical Arrhenius expressio n
in more o r less the co nventio nal way, i.e., as a (kT)~
l
term. Ho wever,
since b is often found to be independent of T, it is clear that there
must be ano ther co mpensating temperature-dependent effect,
namely an appro ximately linear dependence of a o r j3 on tem-
perature in the Tafel slo pe, b = RT/a(T)F. The experimental
results for a variety of reactio ns, summarized in Sectio n III, show
that this is a general effect. Reductio n of C
2
H
5
NO
2
is an exceptio n
while reductio n of o ther nitro co mpo unds takes place with substan-
tial po tential dependence of a.
8
IV. T H E O R E T I C A L DI S C US S I O N
I . Interpretation of the C ase W here a is P roportional to T
We have seen that this case arises for several reactio ns. Agar
82
was
the first to po int o ut that such behavio r co uld arise if the electro de
field mainly influenced the entropy of activation rather than the
energy, as was usually assumed. Co nway et al
2
in their paper in
1970 develo ped this explanatio n further and pro vided mo re experi-
mental examples of "unco nventio nal" variatio n of b with T, i. e. ,
where so me 7-dependent co mpo nent o f a was invo lved, as will be
sho wn belo w.
The electro chemical free energy o f activatio n is fo rmally
;* = AG* - a-qF = (AH;*
=0
" <*r)F) - TAS*. Ho wever, mo re
generally, the Tafel-slo pe facto r sho uld be regarded as o riginating
from the to tal derivative with respect to po tential of AG*. To
illustrate this, we write the electrical energy facto r which mo difies
the activatio n energy by changing the Fermi level as a fractio n A
(0.5) of r]F. Then, writing a fractio n A fo r /3 in Eq. (9) and for
o verpo tential 77,
- (d/d
V
)(\
V
F)
T(d/d7])(AS
ot
) - \F (21)
i. e. , AS* fo r the reactio n may be po tential dependent, a situatio n
that may well arise in structured so lvents
55
such as watert where
hydrated io ns are intimately asso ciated
57
with the co -plane of o rien-
ted water mo lecules in the inner regio n o f the do uble layer.
We write the two derivatives in Eq. (21) as \F (from the electric
po tential term in AG*) and /JLF (fro m the AS
0
* term). Then
^ = \F + fxTF (22)
In terms o f the usual empirical facto r a, d(AG*)/dr/ is written as
aF. Therefo re
(23)
Thus, in the general case, a is seen to have a T-independent
co mpo nent A (the term co rrespo nding to the co nventio nal behavio r)
and a seco nd co mpo nent, /JLT, giving rise to temperature depen-
dence. This result was also derived by Yeager et al
45b
Fro m Eq.
(23), intro ducing^ the Bo ltzmann facto r 1/RT [cf. Eq. (11)], the
t Thus many thermo dynamic and kinetic pro perties of aqueo us systems are "entro py
co ntro lled" as much as "energy co ntro lled," a fact first no ted by Butler
58
many
years ago .
t It may be no ted that there is also always a preexpo nential T term in kT/h that
appears in the transitio n-state equatio n for the rate co nstant. However, here we
neglect the influence of this factor on the temperature dependence of electro de
reactio n rates co nsidered here as is usual practice except over wide ranges of T.
134 B rian E . C onwty
Tafel slope is seen to be
RT/aF s RT/(\F +
M
TF)t (24)
If fiTF is sufficiently larger than AF as a limiting case, it is seen that
RT/IJLTF = K//xF (25)
o r, as written earlier, a(T) = yT = fiT. Thus, this case can
evidently arise, as was sho wn in Ref. 2, if under certain co nditio ns
the increase of electro de po tential has its principal effect o n AS*
rather than AH
0
* o r AE* (see fo o tno te t belo w).
2. General C ase
While the abo ve treatment (cf. Ref. 2) gives a basis for temperature-
independent Tafel slo pes, such as are o bserved, it must be reco gn-
ized that the special co nditio ns that are required for this case to
arise (/JLTF AF) are physically rather impro bable. Thus, in a
charge transfer pro cess, there will always be an electrical energy
change VF o r rjF of the initial o r final state due to the effect
of po tential o n the Fermi level acco rding to Eq. (10) given earlier,
and it is this effect that gives rise to the familiar /3VF term in the
electro chemical Arrhenius equatio n o r the AF term in Eq. (23).
Therefo re it is difficult, if no t impo ssible, to see ho w this facto r
co uld ever be negligible in co mpariso n with the effect of changing
po tential o r co rrespo nding interphase field o n AS
0
*, which leads
to the IJLTF term in Eq. (23). Hence the general form of b might
be [cf. Eq. (24)] RT/(\ + /JLT)F but hardly just R//xF, altho ugh
the latter form is what experiment requires for so me reactio ns.
It is seen that the general form for b derived abo ve, taking
into acco unt bo th A and the entro py derivative /xF, is no t either
identical with the experimental behavio r
2
at Hg where b =
RT/p'F + K. The general case abo ve is rather of the fo rm
R/{kF/ T + K') which is no t in any way reducible to , o r reco ncil-
able with, the experimental Eq. (14) for b for the h. e. r. at Hg.
The pro blem is further illustrated in the case of the h. e. r. at
Hg by writing the o bserved Tafel slo pe, b = RT/p'F+ K, as a
co rrespo nding "Lefat-slo pe" facto r (see p. 108) in the expo nential
t It is seen that this equatio n leads to the co nventio nal temperature dependence of
b at sufficiently low T, while at high T, b beco mes independent of T.
of the electro chemical Arrhenius equatio n: it is rj/(RT/p'F + K)
o r P'riF/(RT+ K/3'F); o r alternatively, (P'riF/RT)/(l +
Kp'F/RT). [Co mpare (A + ^T)riF/RT for the general case
treated abo ve thro ugh the AS
0
* facto r. ] The h.e.r. case [Eq. (14)]
do es no t seem to co rrespo nd to the situatio n where a linear depen-
dence of a o n T o riginates from a field effect o n AS*; the behavio rs
are mathematically different. Ho wever, a plo t of b~
l
vs. T~
l
also
seems to fit the same data.
At this po int in the discussio n, the very difficult pro blem and
impo rtant nature of the linear temperature dependence of a is
clearly perceived and its general significance for electro de kinetics
hardly requires reemphasis, altho ugh, as Yeager has no ted,
56
little
attentio n has been paid to this pro blem previo usly o r to the pub-
lished analysis of main aspects of it in Ref. 2.
3. A Question A bout the E lectrical E nergy Term
PVF in the R ate E quation
As referred to earlier, the usual representatio n of effects of electro de
po tential o n electro chemical reactio n rates is thro ugh a mo dulating
term pVF o perating o n AG* [Eq. (11)]. [Taking acco unt of do uble-
layer structure, this term is written as p{ V - ifj\)F, where i/^ is the
diffuse-layer po tential, but this is a trivial difference in the present
co ntext.] Change of po tential, V, modifies the Fermi level energy
by eV as in Eq. (10). In the usual transitio n-state treatment, this
quantity, modified by the facto r /3, appears in the Arrhenius-
Bo ltzmann expo nent [-(AG* - pVF)/RT\ It is from this
expo nent that the co nventio nal Tafel-slo pe quantity b arises, linear
in T.
Since the expo nential can be written identically as
exp(-AG*/jRT) exp(pVF/RT), this implies that the electrical
energy quantity is also Bo ltzmann distributed. Ho wever, it co uld
be argued that since it is electro ns in the metal at the Fermi
level that are invo lved, the term exp(/3VF/RT) sho uld in some
way be written as a Fermi-Dirac facto r rather than a Boltz-
mann facto r. The forms of such a term wo uld be P(E) =
1/{1 + exp[( - E
F
VF)/kT]}. Intro ductio n of such a pro babil-
ity facto r into the equatio n for electro n transfer rate is to be fo und
in Gerischer's treatment
88
(see belo w). The effect of this is a bro ad-
ening of the distributio n of electro n energies aro und E
F
to an extent
of the o rder of kT. No te that a co rrespo ndence with the Bo ltzmann
functio n o nly arises when E E
F
o r at very low T\ these co nditio ns
are no t always appro ached in mo st electro de-kinetic experiments.
In the o riginal treatment of Gurney,
15
the current was expressed
as the integral of the pro duct of electro lyte and electro n energy
distributio n functio ns but with the electro nic o ne written as a
Bo ltzmann facto r, exp(A//cT). The symmetry facto r was intro -
duced intuitively in terms of the shift of intersectio n po int of energy
pro files in relatio n to change of electro de po tential, i.e., of the
Fermi-level energy (cf. Butler
87
).
While Gurney
15
referred in his treatment of electro chemical
charge transfer to the Fermi distributio n functio n for electro nic
states in the metal, he did no t, ho wever, pursue the co nsequences
of using this functio n in preference to a Bo ltzmann distributio n.
In Gerischer's treatment
88
of redo x reactio ns, also referred to by
Schultze and Vetter
89
'
90
in their treatments of the ro le of electro n
tunneling in O
2
evo lutio n and o ther redo x pro cess at o xide-co vered
(Pt) electro des, the Fermi distributio n was explicitly used in the
current-po tential functio n which is written (cf. Gurney
15
and Geris-
cher
88
) as
r+o o
i=e\ D,
J -oo
>
M
(E)[f(E
F
- E)]D
El
(E)[f(E - E
F
)]v(E) dE (26)
where e is the electro nic charge, D
M
(E) and D
E1
() are the
distributio n functio ns (D) of the electro n states in the metal M
and the electro lyte redo x reagent EL, and v(E) is the electro nic,
tunnel-transfer, frequency facto r. The number of uno ccupied elec-
tro nic states in the metal is given by D
M
(E)[f(E
F
- E)] and in
the redo x system by D
E1
(E)[f(E - E
F
)], where, respectively, the
/ is the Fermi functio n
(27a)
o r
f(E - E
F
) = [1 + exp( - E
F
)/kTY
l
(27b)
As in the usual way, the current density i is po tential dependent
mainly o n acco unt of a shift of the Fermi level E
F
of the metal
relative to the effective "Fermi level" of the electro lyte redo x
system,
91
i. e. , as given by the shape o f the electro nic distributio n
functio n fo r the latter species. E
F
is po tential dependent acco rding
to E
F
= E
F
(<f)
M
= 0) e<f)
M
. In the abo ve kind of treatment, the
temperature dependence of the current is usually attributed to a
change of D
El
(E) with T, co rrespo nding to (classical) thermal
activatio n of surro unding io ns and mo lecules. The quantum-
mechanical electro n tunneling pro bability v(E) at co nstant energy
E is independent of T.
The significance of the so -called Fermi level for a so lutio n
redo x system is no t alto gether clear, but it has recently been critically
examined by Bo ckris and Khan
91
in relatio n to the vacuum energy
level of the electro n(s) invo lved.
Fro m the abo ve, it seems clear that a Fermi-type distributio n
for the electro nic energy levels in the metal sho uld certainly be
emplo yed in the representatio n of electro de reactio n rates as a
functio n of po tential and hence enters into ho w the Tafel slo pe o r
transfer coefficient is expressed, including its relatio n to T.
In relatio n to the abo ve, it is useful to no te here the well-kno wn
limiting cases of the Fermi functio n:
a. For EE
F
, f(E - E
F
) -> exp[-( - E
F
)/kT] (the
Bo ltzmann functio n).
b. Fo r E = E
F
J(E - E
F
) = \.
c. Fo r lo w eno ugh T,f(E - E
F
) -> exp[-( - E
F
)/kT] as in
(a), but for a different reaso n (T -> 0 rather than E E
F
).
Fro m the form of the Fermi functio n, it is seen that when it
is used fo r an electro de pro cess where E
F
is mo dulated acco rding
to E
F
= E
F
Ve, the Ve term do es no t simply facto rize from the
Fermi equatio n giving a no rmal Tafel relatio n even with an empiri-
cally included /3 facto r (cf. Gurney
15
), since
f(E - E
F
) = 1/{1 + exp[( -E
F
Ve)/kT]}
exp[( - E
F
)/kT] exp( Ve/kT)}
Facto rizatio n of a term in exp( Ve/kT) from such a functio n can
o nly be made when the exp term in the co mbined argument is 1.
So lo ng as the Ve term remains in the exp in the deno minato r of
the Fermi functio n, i. e. , so lo ng as co nditio ns o btain where such a
functio n applies, it is unclear ho w, in the general case, a /3 facto r
sho uld enter into this functio n, multiplying Vie, as it do es when the
co nventio nal Bo ltzmann form of the current equatio n is written.
The questio n of how the /3 facto r enters in relatio n to the
applicability of the Fermi-Dirac distributio n in electro n transfer
pro cesses appears to require further explo ratio n. The pro blem arises
from the way change of Fermi-level energy is assumed just to shift
the po tential energy surface up o r do wn by VF and hence cause a
change of (1 - /3) VF in the transitio n-state energy acco rding to the
Br0nsted principle.
4. T emperature-Dependent O rientation of S olvent Dipoles in the
Inner R egion of the Double Layer and the Entropy of A ctivation
A po ssible effect of the state of o rientatio n of so lvent dipo les in
the inner regio n of the do uble layer, as a functio n of po tential and
temperature, o n the temperature dependence of Tafel slo pes was
suggested in Ref. 2. Reacting io ns or mo lecules, especially in the
case of the h.e.r., are intimately invo lved
55
'
57
in so lvatio nal interac-
tio ns with the inner-regio n so lvent dipo les, so the temperature-
dependent state of the latter regio n co uld lead to effects o n the
Tafel slo pe. It wo uld be anticipated that these effects might also
be asso ciated with the entro py of activatio n (Sectio n IV. 1).
We have shown earlier (cf. Ref. 2) ho w, in a formal way, an
apparent temperature dependence of a o r a temperature-indepen-
dent co mpo nent of the Tafel slo pe co uld arise if the entro py of
activatio n rather than, o r as well as, the energy of activatio n is
affected in a linear way by electro de po tential [see Eqs. (21) and
(23) and Agar in Ref. 82]. This co uld arise by the electro de field
having an effect on the so lvent structure in the do uble layer, with
a co rrespo nding influence o n the entro pic co mpo nent of the free
energy of so lvent reo rganizatio n aro und the discharging reagent
io n o r mo lecule.
Several theo ries have been pro po sed in the past 20 years for
changing so lvent po larizatio n in the do uble layer with electro de
po tential. One of the most useful has been that of Mo tt and
Watts-To bin
59
and the develo pment of it by Bockris et al
60
The
mo del represents the inner regio n of the do uble layer in terms of
two -states of o rientatio n of so lvent dipo les, parallel and antiparallel,
|i , to the electro de field acro ss the interphase, analo go us to the
Ising mo del of paramagnetizatio n. Variants of this mo del, taking
acco unt of three states of dipo le o rientatio n, f -> |, or of clusters,
have been treated mo re recently.
61
'
62
Especially with electro -
chemical reactio ns invo lving a change of state of H bo nding, o r
co mplete eliminatio n or creatio n of a charge, may it be expected
that the po tential-dependent so lvent dipo le o rientatio n in the
do uble layer would have an influence o n entro py of activatio n of
the electro de pro cess and its respo nse to changes of temperature.
Co nway et al
2
examined this questio n in terms of the BDM
(Bo ckris-Devanathan-Miiller) two -state mo del
60
of so lvent dipo le
o rientatio n. The dipo le po larizatio n, expressed as a surface po ten-
tial co ntributio n, g
dip
, is given by
E Uc\
where Y is the o rientatio n distributio n expressed as (JVf - N)/ N
T
for JV
T
= 10
15
water dipo les cm"
2
; c is half the two -dimensio nal
effective co o rdinatio n number for the so lvent in the interphase, /JL
is the dipo le mo ment of water, e the electro nic plus ato mic dielectric
co nstant of water
60
(~6), and E the interphasial field. In BDM,
this is taken as 47rg
M
/6, with e = 6, for surface charge densities
q
M
on the electro de. g
dip
can be calculated as f(q
M
) for vario us
lateral interactio n energies U in Eq. (28). The results are sho wn in
Fig. 10.
It is interesting that while g
dip
decreases, as expected, with
increasing T for U = 0, it can increase with T if U is appreciable.
This is because g
dip
is always smaller with increasing U for a given
po larizing q
M
value, but the effect of U is diminished at higher T
so g
dip
can increase with T when U 0. Several examples are
shown in Fig. 11 for g
dip
as f(T) for vario us Uc/k values.
These results mean that the so lvent enviro nment of a discharg-
ing io n on the inner side of the o uter Helmho ltz plane can be quite
substantially modified to ward a state of o rientatio nal saturatio n
depending o n q
M
and T. The entro py of activatio n of a pro cess
involving change of charge number is clo sely asso ciated with chang-
ing state of so lvatio n in fo rmatio n of the transitio n state. Hence it
can be seen, at least qualitatively, how an influence of po tential on
so lvent dipo le o rientatio n in the inner layer co uld be transmitted
as a po tential o r field effect o n the entro py of activatio n. This
140
B rian E . C onway
2 885
o
<
o
<
o
o
Figure 10. (a) The o rientatio n distributio n function (N f -N J,)/N
T
for an o riented
two -state array of dipo les in the Mott and Watts-To bin/BDM model (Refs. 59 and
60) for vario us values of the interactio n parameter Uc/kT in Reference 60 [see Eq.
28]. (b) The configurational entro py s
c
and the libratio nal entro py S
L
for the
two-state model of solvent o rientatio n of electrodes as a function of q
M
(co rrespo nd-
ing to data in Fig. 10a). (From B. E. Conway and L. G. M. Go rdo n, J. Phys. Chem.
73 (1969) 3609.)
X
1 2
1 0
0 8
0 6
0 4
Uc/kT
,-
^ \
i . i , i ,
- 5 0
0 50
T/K
100 150
Figure 11. (a),(b), and (c) The surface
dipo le moment, as in Figure 10, as a
function of temperature for three
values of the interactio n parameter
Uc/kT. No te that x can increase with
T when U 0 (Fig. lie). (From Con-
way and Dhar, Croat. Chem. Ada 45
(1973) 109; based on BDM model
(Ref. 60) of solvent dipo le o rientatio n
in the inner regio n.)
1 2
1 0
0 8
>< 06
0 4
0 2
Uc/kT=5
-
-^
. r
16
b
12
8
4
*,
5 0
0 50
T/K
100 150
influence of po tential, as shown abo ve, will be temperature depen-
dent in a way determined by the magnitude of lateral interactio ns
between so lvent mo lecules in the do uble layer.
It may be anticipated that the effect of temperature on so lvent
dipo le o rientatio n at a given electro de charge o r po tential will have
a larger influence on the reo rganizatio n energy for large, weakly
so lvated io ns than for mo re stro ngly so lvated o nes having higher
charge density (larger charge/radius ratio
55
).
Expressed in ano ther way, the micro sco pic structure of the
profile of po tential difference A V between the metal electro de and
the so lutio n will be dependent on q
M
and g
dlp
, the latter being itself
determined by q
M
and Uc/kT; we assume here for co nvenience,
an absence of the diffuse layer p. d. , Ae/^, i.e., for an excess of
no nspecifically abso rbed electro lyte, so that AV A</>j, the p. d.
acro ss the co mpact layer to the o uter Helmho ltz plane, a regio n of
thickness d.
Acco rding to Mo tt and Watts-To bin's representatio n,
59
(29)
where K
o
is the vacuum (o r electro nic po larizability) capacitance
of the inner regio n, i.e., e/Aird. The field A</>/d can also be expressed
as
(30)
where g
dip
, the charge density asso ciated with the inner side of the
o riented array of so lvent dipo les, is given by the implicit equatio n
<7d.p = N
T
fi tanh[47r(g
M
- q
dip
)fi/kT] (31)
Physically, q
dip
is the reactive po larizatio n of the dipo le layer in
respo nse to the electro de charge density q
M
(co mpare the rep-
resentatio n in Ref. 60).
Fo r a given metal so lutio n p. d. , V A<$i = co nstant, the g
dipo le term will decrease with increasing T (U here taken as 0) so
that the p. d. co mpo nent due to net charge o n the electro de will
tend to decrease in o rder to maintain required co nstancy of A</>j
(the assumed co nstant po tential co nditio n). Fo r co nstant q
M
, o n
the o ther hand, a co rrespo nding increase of A^ wo uld have to
take place. Fo r finite and significant U, o ppo site trends wo uld
evidently arise. Thus, the co mpo nents of electrical po tential differ-
ence acro ss the inner regio n at a given q
M
will change with increas-
ing temperature. Qualitatively, it may be seen how this effect might
change /3 with temperature, no ting that o ne physical interpretatio n
of fi is that it represents
25
'
35
the fractio n of A V (A<^0 traversed
by the reactant io n as its co nfiguratio n attains that of the transitio n
state. t A fuller micro sco pic picture would have to take into acco unt:
(1) the lo catio n of the electric dipo le "within" the o riented layer
of so lvent mo lecules in relatio n to their van der Waals envelo pe
size; and (2) the finite size of the io ns, the lo ci of which co nstitute
the o uter Helmho ltz plane (see Fig. 12).
t The o rigin o f this represent at i o n was sho wn o n p. I l l (cf. Ref. 25).
Helmholtz L ayers
143
Diffuse-layer ionic
atmosphere
Double-Layer with Hydrated Ions and
Oriented Solvent Molecules
Figure 12. Diagram of inner regio n of the do uble layer
showing o uter Helmholtz (OHP) plane with o riented
solvent dipo les interacting with electro statically adso r-
bed solvated io ns [schematic; based on Stern-Grahame
model (Ref. 95); BDM model (Ref. 60) includes an extra
layer of solvent dipo les between the metal surface and
OHP of catio ns].
5. T afel S lopes and P roton T unneling
In electro chemical pro to n transfer, such as may o ccur as a primary
step in the hydro gen evo lutio n reactio n (h. e. r. ) or as a seco ndary,
fo llo wup step in o rganic electro de reactio ns o r O
2
reductio n, the
po ssibility exists that no nclassical transfer of the H particle may
o ccur by quantum-mechanical tunneling. In ho mo geneo us pro to n
transfer reactio ns, the co nsequences of this po ssibility were investi-
gated quantitatively by Bernal and Fo wler
63
and Bell,
26a
while Bawn
and Ogden
26b
examined the H/D kinetic iso to pe effect that wo uld
arise, albeit o n the basis of a primitive mo del, in electro chemical
pro to n discharge and transfer in the h.e.r.
Mo re detailed calculatio ns of these effects were given later by
Christo v
28
and Co nway,
27
who calculated pro to n tunneling pro b-
abilities thro ugh an Eckart barrier, the height of which was varied
with po tential. This gave a Tafel relatio n, as shown in Fig. 13, for
pro to n transfer at a catho de for the case of co mplete tunneling
co ntro l. In practice, bo th classical and no nclassical transfer o ccur
in parallel
64
to relative extents dependent on temperature.
The Tafel slo pe at low po tentials, for pure tunneling co ntro l,
has a higher value than for the classical case and the Tafel relatio n
is no nlinear. These calculatio ns
27
were based on Bell's metho d
26a
of integrating tunneling pro bability over the height of the barrier,
allo wing for a Bo ltzmann-distributed range of initial states from
which the H tunneling can o ccur. An appreciable D-iso to pe effect
is predicted
2613
'
27
for the Tafel slo pe for pure tunneling transfer of
H o r D altho ugh, in practice, D
+
discharge will tend to o ccur with
a relatively greater classical transfer pro bability
64
than that for H
+
,
again depending on temperature. Experimentally, appreciably
greater slo pes for D transfer than for H have no t been o bserved
42
'
65
in the h.e.r.
S
ui
O
5
1.0
0 5
0
-5 - 4 -3 -2 -1 0
LOG [INTEGRAL TUNNELING PROBABILITY ] (oc i )
Figure 13. Tafel relatio n arising from complete pro to n tunneling co ntro l in
the h.e.r. (from Co nway,
27
).
An impo rtant treatment of electro chemical pro to n discharge
and H transfer was given by Levich et al.
66
who co mbined the mo del
of hydratio n-shell reo rganizatio n
914
with quantum-mechanical
transfer of H from a so lvatio nally activated state (Fig. 14).t Krish-
talik
67
has described some co mparative experiments on H transfer
from H
2
O in a no naqueo us so lvent and from excess water, the aim
of which was to distinguish between the ro le of hydratio n-shell
reo rganizatio n and O-H bo nd breaking in the mechanism of the
activatio n pro cess in the step of discharge and ato m transfer in the
h.e.r. It was claimed that the results suppo rted the Levich mo del
which differs substantially in emphasis from some earlier treat-
ments.
11
'
12
'
21
The pro blems involved were examined
68
at a recent
Faraday Discussio n.
Inspectio n of the mo del and treatment by Levich et al.
66
shows
that it do es no t differ in principle from the earlier quantum-
mechanical treatments of rates of H transfer evaluated by Bell's
metho d;
263
there, an initial Bo ltzmann activatio n of the hydrated
pro to n to vario us levels (in his treatment, a co ntinuum of levels
was co nsidered but activatio n into a discrete quantized sequence
can easily be handled in a similar way to that given in Co nway and
Bo ckris's calculatio ns
69
on ho mo geneo us pro to n transfer in co n-
ductance) was assumed from each of which there was a pro bability
of quantum-mechanical H leakage thro ugh an energy barrier deter-
mined (see Refs. 11, 12, and 21) by the energetics of hydratio n of
the pro to n (including the main term for the interactio n: 1H
2
O +
Hg -> H
3
O
+
) o n the o ne hand and the adso rptive bo nding behavio r
of H to the metal (cf. Ref. 21) o n the o ther. It is evident that Levich's
mo del and calculatio n is a mo re generalized treatment of the earlier
calculatio ns
26
'
27
in which a co mbinatio n of classical activatio n and
t This treatment aro se from these autho rs' belief that because the quantum for OH
vibratio n (~40kJmo l~
1
) was kT, no activatio n of bo nd vibratio ns, that co uld
account for electrochemical pro to n discharge and transfer, was po ssible. Thus,
the activatio n energy sho uld co rrespo nd to fluctuatio ns in the hydratio n shell of
H
3
O
+
but the bo nd-breaking pro cess is a pro to n tunneling transitio n. Objectio ns
101
to this model are based on the fact that: (1) energy is always available, e.g., at a
value - bo H, Boltzmann distributed with a pro bability exp(-hv
OH
/kT), as in the
Arrhenius equatio n for the rate co nstant of any pro cess where the co nditio n
A* kT is often invo lved; and (2) in H-bo nded so lvents, OH vibratio ns are
coupled with libratio ns and intermo lecular modes giving a wide manifold of states
within which activatio n can arisecf. the kno wn
1023
heat-capacity behavio r of
H
+
(aq).
a) Model of Levich et at.
H.O"
H tunneling along
proton coordinate
Reorganization mode-
activation in multiple
coordinate space
b) Model of Bell
Reactant
Product
Figure 14. Po tential energy diagram for solvation-shell activa-
tio n of the hydrated pro to n co upled with quantum-mechanical
H
+
neutralizatio n and transfer a - b at an electro de: (a) after
Levich et al
66
and (b) co mpariso n with Bell's 2(a) appro ach
and o thers (Ref. 26b).
quantum-mechanical H transfer was envisaged but it was pro po sed,
and has been perceived apparently inco rrectly, as a new treatment.
Levich's mo del is illustrated in Fig. 14.
Unfo rtunately, the quantum-mechanical tunneling appro ach
do es no t lead to any better understanding of why a sho uld be
temperature dependent in many reactio ns, if only for the reaso n
that in mo st of the cases where such behavio r is o bserved, the
reactio ns invo lve heavy particles for which quantum effects are
negligible. O
2
reductio n, ho wever, co uld be quantally co ntro lled if
a pro to n transfer step were rate co ntro lling in the reactio n sequence
of reductio n to H
2
O, as investigated by Yeager.
In the h.e.r. case at Hg, where b is of the form RT/(3'F + K,
it was suggested
2
that the 7-independent co mpo nent, K, of b (the
intercept at T = 0 K of a plo t of b vs. T) might be co nnected with
a residual, no nclassical, H
+
transfer rate that was po tential depen-
dent at the abso lute zero . Ho wever, since the rate, expressed as i,
always invo lves a reciprocal form of b (the Lefat slo pe), namely,
i = i
o
exp(-iy/ft) = io exp[-i7j8'F/(KT +jS'FK)] (32)
it is unclear how K co uld characterize a T-independent rate due
to H tunneling (that wo uld have to be in parallel with the classical
transfer rate) since the expo nent of Eq. (32) canno t be expressed
as the sum of two terms.
6. B ehavior of a with T emperature on the B asis of E lectron
and P article T ransfer T reatment of Ulstrup
Ulstrup
70
has recently given a treatment of the po ssible variatio n
of a with temperature acco rding to theo ries of electro n transfer.
On this basis, a is expected to increase weakly with temperature
over a sufficiently wide range of T but the calculated effect is very
small. It o riginates from the fact that
70
the nature of the mo tio n of
the discrete mo lecular o r co ntinuum so lvent mo des is co nverted
from nuclear tunneling at low T to classical, thermally activated
mo tio n at elevated temperatures. The distributio n of so lvent mo des
which enters into the so lvent reo rganizatio n energy is replaced by
Ulstrup by the behavio r of a dielectric medium with an o ptical
dielectric co nstant e
0
and an effective static dielectric co nstant s
en
.
When the so lvent mo des are do minant, and as lo ng as po tential-
dependent work terms are disregarded, the T-effect on a arises
essentially from variatio n of e
eff
with temperature. If e
eff
is identified
with the bulk static dielectric co nstant of the so lvent, the effect is
deduced to be insignificant for co mmo n hydro xylic so lvents. On
the o ther hand, it is co ncluded that if e
eff
is determined by the
sho rt-range limiting "infrared" dielectric co nstant to a co nsiderable
extent, i.e., when spatial dispersio n effects are impo rtant, a may
exhibit a detectable T-dependence. In the range of T from 150 to
300 K, a varies only by 2-6%.
These effects, while of fundamental interest, are alto gether to o
small in relatio n to experiment where a typically varies by ~ 50%
over such a range of T (but no te that the lowest temperatures as
attained in the works of Conway et al. were ~ 173 K). Obvio usly,
an effect of a much mo re substantial and radical kind must be
o perative to keep b appro ximately co nstant and a linear in T over
a wide range of T in several impo rtant electro chemical reactio ns.
The effect is no t a subtle mino r o ne, altho ugh its o rigin is elusive,
as is apparent from the foregoing material.
7. N onlinear P otential Dependence of E lectrochemical
R eaction R ates
(i) Nature of the Effects
Co nstancy of /3 (o r a) over some appreciable range of po tential
is quite generally expected when po tential energy surfaces intersect
over the anharmo nic, linear regio n, as with Mo rse functio ns. When
o ne curve cro sses the o ther, o r bo th curves cross each o ther near
the zero -po int energy levels(s), which is usually in a harmo nic
regio n of small displacement alo ng the reactio n co o rdinate, then
P will beco me dependent on the electrical energy displacement,
A VF, asso ciated with change of energy of the electro ns at the Fermi
level. This situatio n was treated in the paper by Despic and Bo ckris
35
on metal-io n discharge. It is also the basis of the predicted quadratic
dependence of In [rates] of electro chemical pro cesses on po tential
acco rding to Marcus theo ry where the energy barrier is assumed
to be determined by po tential energy surfaces (profiles) in the
harmonic appro ximatio n which applies, ho wever, only to pro cesses
having small activatio n energies (cf. the harmo nic behavio rf of the
Morse functio n for small vibratio nal displacements).
The o rigin of po tential dependence of /3 was treated by Despic
and Bo ckris
35
in terms of the geometry of cro ssing of po tential
energy profile sectio ns of the po tential energy surface for io n
discharge. Using Mo rse functio ns to represent the co urse of energy
changes of the initial and final states of the reactio n alo ng a
t However, in Marcus's treatments, the harmo nic behavio r co rrespo nds usually to
fluctuatio ns in long-range dielectric po larizatio n and/o r solvation-shell interac-
tio ns.
unidimensio nal reactio n co o rdinate, these autho rs derived a rather
complex expressio n for /3 in terms of the equilibrium initial and
final energies of the system, the o verall energy change A
o
, (in the
reactio n step), the relative po sitio n of the transitio n state alo ng the
reactio n co o rdinate, and the anharmo nicity co nstants a of the
pseudo diato mic states invo lved. Their calculatio n was similar to
that of Co nway and Bo ckris
69
for the effect of changing heat of
adso rptio n in the H
2
evo lutio n reactio n.
The expressio n derived by Despic and Bockris gives a po tential
dependence of /3, especially when initial- and final-state profiles
cro ss asymmetrically (see Fig. 15), i.e., when A
o
is either a large
exo thermic o r endo thermic quantity, so that the transitio n state is,
respectively, either close in co nfiguratio n to the final state o r to the
initial state. The Tafel relatio n is co nsequently no nlinear; simulated
Tafel relatio ns were calculated
35
sho wing this behavio r.
From their representatio n of the o rigin of a po ssible po tential
dependence of /3, it is po ssible to perceive facto rs, e.g., tho se that
AH% 01 -
f \
\
\
A"
\
VV
/B
/
I
Ml
A
" /
\
A
\
10
Ar?r
o
Figure 15. Cro ssing o f po tential energy curves leading to po tential dependence o f
(3 (after Despic and Bo ckris,
35
).
150 B rian E . C oiway
determine the deso lvatio n po tential energy curve, that co uld also
give rise to a co rrepo nding temperature dependence of ft altho ugh
it is no t o bvio us how this wo uld be the linear o ne often indicated
experimentally.
This paper also identified how /3 co uld be represented in terms
of the co nfiguratio n of the transitio n state alo ng the reactio n co o r-
dinate in relatio n to that of the initial state; that is, j8 = r*/Ar
0
,
where r* is the "distance" of the transitio n-state co nfiguratio n alo ng
the reactio n co o rdinate and Ar
0
is the to tal "distance change" in
the reactio n (this basis of expressing /3 is to be fo und first in Ref.
11). As we mentio n elsewhere in this chapter, this definition of /3
is no t necessarily
25
identical with that made in terms of energy
changes asso ciated with changes of electrical po tential. Co in-
cidence, o r o therwise, of these representatio ns depends on the
geometry assumed for the po tential energy curves (surfaces), e.g.,
anharmo nic o r harmo nic, and the magnitude of A* relative to
AJ
0
- Also , of co urse, multidimensio nality of the function for the
energy of the system renders the representatio n of fi in terms of r*
and Ar
0
serio usly oversimplified as is now generally reco gnized for
an io nic redo x reactio n where no net ato m transfer pro cess, co upled
with electro n transfer, takes place.
Finally, we no te here that the representatio n of the po tential
dependence of /3 in the diagram in Despic and Bo ckris's paper
35
(their Fig. 14) implies ultimately that activatio nless discharge will
set in, as treated by Krishtalik.
83
Then, of co urse, the pro cess
beco mes entirely diffusion limited. Co rrespo ndingly, barrierless
discharge wo uld arise at the o ther extreme.
Two co nsequences of the energy barrier arising from harmo nic
po tential energy surfaces or profile sectio ns are: (1) that the activa-
tio n energy involves a term in \ of the so lvatio nal reo rganizatio n
energy asso ciated with charge transfer; and (2) that the electrical
energy facto r in rj o r V includes a seco nd-o rder term in 17
2
o r V
2
.
Since the effect of po tential on reactio n rates is intimately asso ciated
with the ro le of temperature (Sectio ns II and III), it will be
useful to show briefly how the quadratic term in po tential, that
use of harmo nic po tential energy curves predicts, arises
in the electro chemical Arrhenius equatio n: it is simply the
result of a co o rdinate-geo metry treatment of two intersecting
parabo las.
Acco rding to the Marcus theo ry, the electrochemical rate co n-
stant k
v
is written as
RT RT A AV-<ft
- ^
l n f c
v + l nZ
e l
- m/ >+ +
+ (AV-4>)
2
(33)
where k
v
is the po tential-dependent rate co nstant, Z
el
a
hetero geneo us co llisio n frequency, n the number of electro ns in
the charge transfer pro cess (usually 1), A the reo rganizatio n
energy,t (f> the po tential difference between the reactio n site and
the so lutio n (the ift
x
diffuse-layer po tential), and AV is the elec-
tro de po tential. The apparent transfer coefficient a =
- (RT/F) d In k
v
/d(&V) and is hence given by
d<f>
Saveant and Tessier
8
gave two ways of expressing the transfer
coefficient:
<t>) (35)
ZA
and
a = 0.5 H ( AV- 4>) (36)
so that
2a = 0.5 + a (37)
and
s =
{
a
-"iw)/{
1
-iw)
(38)
a
a
P
p is o btained, of co urse, from the experimental dependence of
In k
v
o r In [current density] on A V.
t For the convenience of readers who may not be familiar with the definitions given
in Marcus's papers, A, the reo rganizatio n energy, is the energy change that the
particle undergo ing electron transfer would experience if its change of state took
place from the initial-state energy surface to the final-state o ne, but in an unchanged
configuration on the reactio n co o rdinate. Then the so lvatio nal part of A* is A/4.
1S 2 B rian E . C onway
The po tential dependence of the predicted and experimental
transfer coefficients can be co mpared by means of
da FI d(fr \ da F ( d<b \ .
x
o r
TTT7 = T7 (1 ~ - TTTJ (
39
)
The "chemical" co mpo nent of the rate co nstant is expressed in the
usual way as k
c
= Z
eJ
exp(-\/4RT).
It will be no ted from the abo ve that no unco nventio nal tem-
perature dependence of a arises explicitly in this treatment;
ho wever (see belo w), a T-dependence of a co uld arise from the
A"
1
facto r in Eq. (34).
The experiments of Saveant and Tessier
8
aimed to establish
whether a was po tential dependent. k
v
was o btained as /(AV)
over a AV range of 0.5-1.0 V for reductio n of three nitro com-
po unds o n Hg in anhydro us aceto nitrile and dimethylfo rmamide.
Under tho se co nditio ns, the pro ducts of the electro n transfer pro cess
are anio n radicals. k
v
is co nvincingly po tential dependent and a
app
decreases with increasing negative po tential: da
app
/dAV
0.46 V"
1
. These results give the clearest evidence hitherto published
for a quadratic dependence of rates o n po tential but their interpreta-
tio n is no t witho ut ambiguity since the adso rptio n of the reactant
mo lecules and their o rientatio n, which will affect the A5*, are
po tential dependent if substitutio nal adso rptio n arises, as it pro b-
ably do es at the Hg/so lutio n interface.
60
Fo r the o rganic co mpo unds
used, nitro durene and nitro mesitylene, adso rptio n is almo st cer-
tainly significant since it is known that benzene is adso rbed at Hg,
e.g., from methano l as well as from water. In relatio n to Saveant's
results,
8
it is interesting that in work on reductio n of C
2
H
5
NO
2
at
Hg, Evans
102b
has sho wn that a is clearly constant over a tem-
perature range of ~ 60 K. The solvent in that work was aceto nitrile.
This is evidently o ne of the few cases where the co nventio nal form
of the Tafel equatio n, with b pro po rtio nal to T [cf. Eq. (5)], is
fo llo wed.
() Consequent Temperature Dependence of a
Fro m Eq. (34), it is seen that a
app
is a functio n of A in the
case where quadratic terms in the Tafel relatio n [Eq. (33)] are
significant. It is interesting that this situatio n co uld evidently give
rise to a temperature dependence of a since, in most liquids, the
reo rganizatio n energy will be temperature dependent, especially in
structured so lvents. If A is taken as a /ree-energy term, then it is
clear that |A| will decrease with increasing temperature since
entro pies of io nic so lvatio n are always negative (cf. the Born and
o ther treatments of the thermo dynamics of io nic so lvatio n
55
). In
Eq. (34), this means that the seco nd term 0.5 + (F/2A)(A V - </>)
will increase. This is the directio n required for co nsistency with
experiment. Ho wever, it is impo rtant to reco gnize that such an
effect wo uld arise only for pro cesses that exhibit a quadratic term
in the po tential dependence of In [rates]. Fo r some io nic redo x
reactio ns,
86
and especially for the h.e.r.,
10
'
11
the activatio n behavio r
is anharmonic, so an effect thro ugh the A"
1
term will no t arise [see
Eq. (33)]. Then reco urse must be had to o ther po tential-dependent
effects, that are also a functio n of temperature, to explain the
variatio n of a with T as was discussed in Sectio n IV.4 with regard
to e.g., so lvent dipo le o rientatio n in the electro de interphase.
Based o n careful work on Fe(III)(C
2
O
4
)3 reductio n, Sluyters
116
co nsiders that the potential dependence of a, o bserved with certain
electro de pro cesses, really arises from kinetic co mplicatio ns and
that the transfer coefficient for the elementary step of charge transfer
is co nstant at 0.5. Ho wever, the wo rk of Hupp and Weaver
86
o n
the Cr(OH
2
)l*
/3+
system demo nstrated a relatio n between the tem-
perature and po tential dependence of the rates, and showed that
at o verpo tentials of ca. 0.7 ~ 0.9 V the po tential dependence of rate
arises extensively from the entro pic facto r (p. 133). It was also
shown that the Marcus theo ry was able to predict a po tential
dependence of AS* co mparable to o r > that of A//* when the
system has a large entro pic asymmetry, i.e., a large net reactio n
entro py change.
(iii) Linear Relations between In i and Overpotentialthe
Common Behavior
While we have seen that experiments indicate that a or p are
functio ns of electro de po tential for o ne or two reactio ns,
7
'
8
the most
common kinetic behavio r over quite large ranges of po tential is a
linear relatio n between rj and In i, so that a o r f$ are usually co nstant
with varying po tential, e.g., as with the h.e.r. at Hg.
2
Qualitatively,
this has usually been attributed to variatio ns of the energy of the
transitio n state over a range where anharmo nicity of vibratio ns o r
o ther fluctuatio ns of energy o btains, as with Mo rse functio ns for
ato m transfer reactio ns
11
'
12
'
69
(cf. also Ref. 101 referred to belo w)
when Af/* is greater than ~20% of the disso ciatio n energy o r less
than - 60% of it.
In a recent interesting paper by Kuznetso v,
105
co nstancy of a
o r j8 over a wide range of rj has been attributed, thro ugh quantum-
mechanical calculatio ns, to the change of shape of the free-energy
surface as a functio n of the co o rdinates of the mo lecules of the
so lvent medium. This effect arises, it is suppo sed, on acco unt of
the partial charge o n the transferred H ato m, which beco mes adso r-
bed as a pro duct of the pro to n discharge pro cess, being dependent
o n these co o rdinates. The change of shape of the free-energy surface
is due physically to the change of the interactio n of the adso rbed
ato m with the medium po larizatio n in the pro cess of activatio n.
Calculatio ns were made of the variatio n of a with o verall free-
energy change AG
R
in the pro cess for two mo dels of the electro nic
state of the adso rbed H ato m at a metal electro de: (1) Anderso n's
mo del
106
for the electro nic energy of an ad-ato m in relatio n to
electro n energy levels in the metal; and (2) the LCAO (linear
co mbinatio n of ato mic o rbitals) appro ximatio n describing the elec-
tro nic energy of an adso rbed ato m in a two-level appro ximatio n.
It is co ncluded that a o r /3 actually vary little with AG
R
, tho ugh
small but significant changes do arise.
Since two of the facto rs involved in the relatio n between a o r
j8 and the free-energy charge in the reactio n, treated in this wo rk,
can be temperature dependent, qualitatively it follows that a vari-
atio n of a o r p with T co uld, to some extent, arise. However, a
satisfacto ry quantitative evaluatio n of the po ssible effect wo uld be
rather difficult to achieve ori the basis of Kuznetso v's treatment.
Co nsiderable attentio n has been given, e.g., in vario us works
of Lorenz and Schultze to the extent to which charge transfer is
co mplete in the electro so rptio n of vario us species at electro des,
e.g., ad-ato ms in UPD and with io ns that are specifically adso rbed.
If the extent of charge transfer in such pro cesses (the "electro so rp-
tio n valency") is temperature dependent, this wo uld pro vide
ano ther co ntributio n to the apparent variatio n of a with T in terms
of changing charge distributio n. However, almo st all existing data
on electro so rptio n valency are at o ne temperature o nly so the results
of such an effect must remain speculative.
(iv) Limiting Cases of the Activation Processes:
"Barrierless Discharge"
The situatio n where so -called "barrierless discharge" (the bar-
rier height then really co rrespo nds to an activatio n energy equal to
the endo thermicity of the reactio n) arises has been treated in some
detail in a number of papers by Krishtalik.
83
It is claimed that the
transitio n from a regular activated pro cess (/3 0.5) to the "barrier-
less" co nditio n (/3 = 1) can be o bserved in some pro cesses, e.g.,
the h.e.r. at Hg at very low current densities, altho ugh in Bowden
and Grew's
103
careful work such effects are no t apparent. There are
practical experimental pro blems that make o bservatio n of this effect
no t always unambiguo us, e.g., do uble-layer co rrectio ns and anio n
adso rptio n effects near the pzc (po tential of zero charge). Also , as
no ted by Krishtalik himself,
67
when the barrierless co nditio n is
established, the back-reactio n is activatio nless so it pro ceeds at its
maximum, diffusio n-limitedt rate which co mplicates the o bserva-
tio n of the desired, fo rward, barrierless pro cess.
The actual situatio n invo lving barrierless discharge is no t
alto gether clear when finite temperatures o btain, for then transitio ns
to some excited vibratio nal states in the pro duct species co uld be
barrierless, while transitio n to the gro und-state, zero -po int, energy
level may no t be.
8. E xpansion of the H elmholtz L ayer with Temperature
A further po ssible cause of a variatio n of /3 with temperature is
expansio n of the do uble layer with increasing T. If the po tential
energy surfaces cross symmetrically o ver a range of energies with
changing to tal length of the reactio n co o rdinate (asso ciated with
increasing do uble-layer thickness), then no expansio n effect on j8
will arise. This co rrespo nds to linear anharmo nic behavio r. On the
o ther hand, if the intersectio n regio n is o ne where the surfaces have
changing and unequal derivatives, then some variatio n of (3 with
t In certain cases, it is conceivable that the reactio n might still be limited by an
unfavorable entro py of activatio n.
do uble-layer thickness wo uld be anticipated, and hence with T.
This situatio n co rrespo nds to o ne po tential energy surface being
near either the zero -po int (harmo nic) limit o r the disso ciatio n limit
at the regio n of intersectio n; these are extreme cases, no t alto gether
pro bable in reality.
From the existing data, e.g., from Grahame's work in 1958,
for do uble-layer capacitance behavio r of the Hg/so lutio n interface
as a functio n of temperature, for a sufficiently negatively charged
Hg surface (absence of specific adso rptio n of anio ns), it seems that
the capacity C is virtually independent of temperature. Hence it is
unlikely that the o bserved unco nventio nal dependence of b on T
co uld arise in some way from a temperature-dependent change of
mean thickness d of the do uble layer expressed as d = E/ATTC. Of
co urse, the effective e of the inner regio n may also vary with
temperature at a given surface charge density, q
M
, o n the electro de
metal surface; generally, it will tend to decrease, except in the
saturatio n limit when q
M
is large.
Bockris and Parso ns,
11
ho wever, in an early discussio n of po ss-
ible effects on a of changing do uble-layer thickness with tem-
perature, co ncluded that such an effect co uld acco unt appro xi-
mately for the variatio n of a with T that was o bserved over a
certain temperature range in their wo rk. This questio n evidently
remains to be settled by further experiments.
9. E ffects of S pecific A dsorption of A nions
The presence of adso rbed anio ns in the do uble layer has at least
five distinguishable effects on the rate of an electro de pro cess:
1. The po tential profile acro ss the do uble layer is mo dified,
95
including the value of the diffuse-layer po tential, i/^, for a given
metal/so lutio n p. d. , A<.
2. The lo catio n of the transitio n state within the do uble layer
can be modified from that in the absence of specifically adso rbed
anio ns.
3. Co rrespo ndingly, the po tential </>* at this lo catio n is usually
modified.
4. The transitio n state suffers interactio ns with the adso rbed
anio ns that alters its activity coefficient (Parso ns
96
).
5. The interactio n of the transitio n state with o riented so lvent
mo lecules in the inner layer is dependent o n the charge density of
anio ns adso rbed thro ugh the co -sphere/so lvent co -plane o verlap
and resulting interactio n effect (Co nway
57
).
Especially, for an ano dic reactio n, the specific adso rptio n of
anio ns can be impo rtant, for then the anio n can be the primary
electro chemical reagent in tho se pro cesses that involve anio n dis-
charge, e.g., halo gen evo lutio n from Cl~, Br~, o r I" (usually stro ngly
adso rbed anio ns), carbo xylatio n (in the Ko lbe reactio n), o r N^ in
ano dic N
2
evo lutio n.
48
OH~ in oxygen evo lutio n is no t no rmally
regarded as stro ngly adso rbed altho ugh it may interact with o xide
films on ano des in aqueo us media o r be part of the surface structure
of an o xyhydro xide film, e.g., with NiO. OH.
Facto rs (1) to (5) abo ve are kno wn in o ne way o r ano ther to
affect the kinetics of an electro de reactio n including, in most cases,
the Tafel slo pe. Since the anio n adso rptio n is no rmally temperature
dependent owing to the usually finite enthalpy of adso rptio n (mo st
chemiso rptio ns are energy as well as entro py co ntro lled in their
thermo dynamics), it follows that anio n effects co uld give rise to
unco nventio nal temperature dependence of a.
We next co nsider a few cases individually.
(0 Hg
Altho ugh the h.e.r. has been studied extensively at Hg, a
relatively small amo unt of work has been do ne o n the temperature
dependence of the kinetics of this reactio n and previo us temperature
studies (with a few exceptio ns) were co ncerned mainly with o btain-
ing electro chemical activatio n energies and, co nsequently, a rela-
tively small temperature range was used. In the work of Co nway
et al,
2
Co nway and Salo mo n,
42
and Po st and Hiskey
41
in 0.1 N
aqueo us so lutio n, referred to earlier, b was fo und to vary with T
but no t acco rding to Eq. (5) (Fig. 3a). The work of Bockris and
Parso ns
39
o n the h.e.r. at Hg in so lutio ns of aqueo us 0.1 N HC1,
0.1 N HC1 + MeOH, and 0.1 N HC1 + H
2
O + MeOH mixtures over
the temperature range 0 to 40C gave b values that were, ho wever,
independent of temperature over a sho rt range of T but also
dependent o n T over a different range of T.
In aqueo us medium at the high rj values involved in most
steady-state studies at Hg, specific adso rptio n of Cl~ io ns in dilute
HC1 is no t indicated by electro capillary and capacitance studies
92
"
95
no r in the wo rk of Po st and Hiskey.
41
Similarly, in alco ho lic so l-
utio ns o f HC1, specific adso rptio n of Cl~ do es no t appear to be
significant at the po tentials used in that wo rk,
2
'
42
altho ugh nearer
the pzc specific adso rptio n of Cl~ is greater
92
than it is in aqueo us
HC1 at the same co ncentratio ns. Hence the dependence of b o n T
sho wn in Figure 3 for Hg and represented by Eq. (17) with /3 =0. 71
and K = 0.04 is unlikely to be the result of specific adso rptio n of
Cl~ and an explanatio n of the fo rms of Eq. (17) o r b = RT/a(T)F
must therefo re be so ught in o ther terms.
At high acid co ncentratio ns, ho wever, the kinetic results are
undo ubtedly co mplicated by anio n adso rptio n,
93
'
94
particularly fo r
halides; interpretatio n of the kinetics (b and lo g i
0
) in terms of H
tunneling
26
~
28
o r o ther facto rs is then difficult and special mo dels
must be intro duced. Fo r example, anio n effects o n the lo catio n of
the H
+
io n in the initial state and anio n interactio ns with the
transitio n state
96
have been co nsidered.
Fro m a treatment of Parso ns,
96
it is po ssible to sho w appro xi-
mately ho w a temperature-dependent apparent co ntributio n to p
can arise fo r specific adso rptio n. If adso rbed anio ns affect the
activity coefficient of the activated co mplex, then the relative change
of rate co nstant k with co verage 6 by the anio ns is given by
ln(k/k
o
) = 2B0 (40)
where k
0
is the rate co nstant in the absence of adso rptio n of anio ns
and resulting interactio ns with the activated co mplex and B is the
seco nd virial coefficient in the equatio n of state for the ad-species.
If 6 is appro ximately linear in electro de po tential </> (co nstant
inner-layer capacity co ntributio n C), then
96
\n(k/k
o
) = 2BC(f> (41)
The o verall rate expressio n will then invo lve an expo nential facto r
in (f> of the fo rm exp(-p<t>R/RT) exp(-2C<), i. e. ,
exp(-<f>F/RT)(p + 2BCTR/F) s exp(-/3'F/RT). The apparent
symmetry facto r fi
r
is hence co mpo sed of the no rmal /3 plus a
temperature-dependent term invo lving the interactio n parameter B
and a capacity term C characterizing the po tential dependence of
co verage o f the adso rbed anio ns. This is of the co rrect fo rm required
to explain cases where b varies ano malo usly with T fo r anio n
adso rptio n.
( i i ) Ni
The results in Fig. 4 for Ni in alco ho lic HC1 are co nsidered
to gether with tho se of Bockris and Po tter
97
in dilute aqueo us acid
and alkaline so lutio ns. The Tafel lines for Ni in the alco ho lic
so lutio ns co nsistently show two linear regio ns bo th for the pro tium
and deuterium so lvents (CH
3
OD, C
2
H
5
OD + DC1). Changes of
slo pe were no t, ho wever, o bserved in a similar study carried o ut
in methano l + HC1O
4
so lutio ns. This pro ves that the anio n of the
electro lyte can have a qualitative effect o n the po tential dependence
of the electro de reactio n rate as well as o n its i
0
value. Ho wever,
in this wo rk, the methano lic HC10
4
co ntained a small quantity of
H
2
O from the 70% HC1O
4
(aq) used to make up the CH
3
OH
so lutio ns.
Reaso nably linear Tafel relatio ns were o bserved at all tem-
peratures (do wn to low T) and the b values co rrespo nded closely
to tho se o btained for the high c.d. regio n at Ni in the alco ho l + HC1
so lutio ns. The (fc, T) plo t (Fig. 5) shows that b decreases linearly
with T do wn to the lowest temperature attained i.e., -89C). This
behavio r is to be co ntrasted with that sho wn in Fig. 4 for the chlo ride
so lutio ns.
On the basis of these results, it may be argued that the lo wer
Tafel lines at Ni in aqueo us HC1 represent the kinetics of the h.e.r.
at a Ni surface with specifically adso rbed Cl" (cf. Ref. 92), while
the upper line (which has b similar to that for the HC1O
4
so lutio n
at Ni) represents the kinetics in the absence of specific adso rptio n.
That the Cl~ io n may have mo re of a kinetic effect than it do es at
Hg pro bably arises since: (1) o verpo tentials at Ni are nearer the
pzc than they are at Hg for c.d. > KT
6
AcnT
2
; and (2) H is
appreciably adso rbed at the Ni electro de surface and its co verage
and binding energy may hence be sensitive to co adso rptio n of Cl~
(cf. the results of Breiter
98
at Pt). Similar co nclusio ns apply to Pt.
The results of Bockris and Po tter
97
o ver a small temperature range
in aqueo us HC1 indicate that b is almo st independent of T. Since
this result was o bserved in 0.001 and 0.01 N HC1, and in dilute
KOH, it seems justified to regard it as also applying to the h.e.r.
in the absence of specific adso rptio n of anio ns.
The lo wer Tafel regio n at Ni and the who le behavio r at Pt thus
seem co nsistent with anio n adso rptio n effects since: (1) the Tafel
slo pe (at Ni) beco mes changed at higher po tentials and then varies
more no rmally with T; and (2) for ascending changes of T at Pt,
it is fo und that b remains almo st co nstant with T as low T
2
but
suddenly changes at ~270 K, whereas for descending changes of
T, 6, bo th for the h.e.r. and d.e.r. co ntinuo usly increases with
decreasing T. Similarly, in the Br
2
e.r. (Fig. 8), b is independent of
T and, since this is an ano dic reactio n, Br~ adso rptio n may be
expected.
(iii) Lead and Cadmium
Mo re co mplex relatio nships between hydro gen o verpo tentials
and specific anio n adso rptio n are o bserved for these metals" and
slow anio n adso rptio n is indicated;
100
e.g., rj is lowered in HC1
and HBr so lutio ns as the co ncentratio n is increased.
We co nclude that changing anio n adso rptio n at electro des with
temperature can, in some cases, lead to unco nventio nal behavio r
of Tafel's b coefficient; but this is no t the only reaso n for such
ano malies, especially in catho dic reactio ns where po tential ranges
for appreciable currents are negative to the pzc of the electro de
material co ncerned.
Co nclusio ns abo ut an intrinsic variatio n of a o r fi with T, o r
the applicability of Eq. (17), must be based o n experiments where
temperature-dependent anio n adso rptio n effects are minimized o r
absent, as ensured by appro priate cho ice of chemistry of the system
o r of the electro chemical co nditio ns. A favo rable cho ice is no t
always easy to achieve; suitable systems are limited.
10. Tafel S lopes for Reactions Proceeding in M ultistep Pathways
It is well kno wn
313
'
25
'
32
'
34
that when an electro chemical reactio n
pro ceeds in a multistep pathway with the steps in series, the Tafel
slo pe o bserved for the log i vs. rj relatio n depends o n the partial
reactio n sequence, and the state and po tential dependence of
adso rptio n of intermediates [see Eqs. (12) and (13)]. Various
values of b for the reactio n, < RT/0.5 F
9
can arise depending o n:
(1) which step determines the rate of the o verall reactio n; and (2)
the co nditio ns of coverage of the electro active intermediate (H in
the h.e.r.) in the reactio n and the po tential dependence of that
co verage. Values >RT/0.5F (/3 = 0.5) so metimes arise with reac-
tio ns pro ceeding at barrier-layer films which exhibit no n-Ohmic
charge transfer thro ugh them.
50
'
51
When steps o ther than simple electro n transfer are rate co ntro ll-
ing, the forms of the o verall rate equatio n that then can be deduced
are assumed to arise on acco unt of po tential dependence of co verage
by a reactio n intermediate (X) in the main reactio n sequence given
K
X
C
R
^(VF/RT)
l + K
x
C
R
exp(VF/RT)
K }
where R is the reactant fro m which adso rbed X is discharged.
6
X
o r 1 - 6
X
terms which appear in the kinetic equatio n fo r
the rate-co ntro lling step then have limitingly the respective
fo rms: K
X
C
R
exp( VF/RT) o r [1 + K
X
C
R
exp( VF/RT)]-
1
=
(K
x
C
R
)~
l
exp(-VF/RT) when V is large. Thus VF/RT terms
arise limitingly as co mpo nents in the rate-equatio n expressio ns
giving the Tafel slo pes having the forms written in Eqs. (12) o r
(13). The T facto r thus appears in a no rmal way.
In the case when discharge is no t rate co ntro lling, so that, for
example, in the h.e.r., ato m-io n deso rptio n step characterizes the
mechanism, we have
d In i pF dlnO pF J_^0
drj " RT
+
d
v
~ RT
+
6 dV
dO/ dV = 1/ qi multiplied by the capacitance, C
H
due to the adso r-
bed electro active H species in the h.e.r., where q
x
is the charge for
mo no layer co verage of tho se H species (no t necessarily the stro ngly
bo und H that is o bserved in underpo tential depo sitio n (u. p. d. )
experiments at Pt). We see that the Lefat slo pe is, in general,
co mpo sed of two co mpo nent terms, o ne from the charge transfer
facto r and the o ther from the po tential dependence of co verage;
each gives rise to an inverse dependence of b~
l
o n T o r a mo re
co mplex functio n of T (see belo w). Fo r the Langmuir case we find
d
v
RT RT 1 + K
X
C
X
exp(VF'/RT)
This relatio n gives the regular Tafel slo pe for this mechanism of
b = RT/(\ + p )F only when K
X
C
X
exp(VF/RT) 1. Under o ther
co nditio ns it is seen that b - (drj/d In i) will no t be simply pro po r-
162 B rian E . C on way
tio nal to T so that a will be apparently T-dependent. The range
of po tentials o ver which this co nclusio n will be valid is, ho wever,
strictly limited. A wider range will apply when the g facto r in the
Temkin-type iso therm [see Eq. (45)] is appreciable (gRT = 5 ~
10 RT in energy). Such co nditio ns are treated as fo llo ws.
Fo r the so -called "Temkin" case, the adso rptio n iso therm
equatio n fo r 0
X
is written with an exp(g0
x
) term in it,
71
'
72
i. e. , for
the co nditio n where K is 0-dependent [K = X
o
exp(-g0
x
)],
(0
x
/l - 0
X
) exp(g0
x
) = K
0
C
R
exp(VF/RT) (45)
The rate equatio n must then be written co rrespo ndingly with similar
exp(g0
x
) o r exp(/3g0
x
) terms, where g is an interactio n o r
hetero geneity parameter (as specifically in Temkin's o riginal treat-
ment) characterizing the variatio n of energy of adso rptio n of X
with co verage. Then, for example, for the ato m-io n deso rptio n
mechanism in the h. e. r. , the Tafel slo pe is given by
dV RT
which, fo r 0 = 0, beco mes the usual value RT/{\ + p)F. Fo r H
adso rbing metals, b can be reaso nably co nstant with 17 o r V if
g 0 but varies less with T than is usually assumed.
It sho uld be remarked here that except perhaps for OH and
O species o n no ble metals, the adso rptio n energy of an intermediate
is rarely distributed in a linear way with co verage; thus for sub-
mo no layer chemiso rptio n, states with discretely different adso rptio n
energies are the rule rather than the exceptio n, so that a co ntinuo us
expo nential functio n in
4
g0' is usually less than realistic as a basis
for writing an electro chemical adso rptio n iso therm equatio n. When
terms such as exp(g0) are included, this intro duces a further implicit
T-dependent quantity since really exp(g0) = exp(r0/RT), i.e., g is
a/XT"
1
).
Vario us limiting cases have been wo rked o ut in the literature
for several well-kno wn electro de pro cesses: the H
2
,0
2
, Cl
2
evo lutio n
reactio ns and the Ko lbe reactio n, as well as O
2
reductio n and so me
electro o rganic o xidatio n pro cesses with simple mo lecules. The gen-
eral co nclusio ns can be summarized as fo llo ws:
1. When the rate-co ntro lling step invo lves an electro n
transfer, b has the form b = RT(n + p)F [Eq. (12)].
2. When the rate-co ntro lling step invo lves a "chemical" pro -
cess, b has the form b = RT/nF [Eq. (13)] (o r oo for a
chemically co ntro lled limiting current as in mo lecule dis-
so ciatio n or H reco mbinatio n as 0
H
* 1), where n is an
integer characterizing the number of quasiequilibrium
charge transfer steps that precede the rate-co ntro lling step.
It will be no ted that pro perties of the barrier-to -electro n
transfer do not enter into the determinatio n of b for "chemically
co ntro lled" rate-determining steps pro vided the quasiequilibrium
hypo thesis applies adequately to the steps prio r to the rate-
co ntro lling o ne, which may no t always be the case. This means
practically that the exchange rate in the pre-rate-determining steps
must be at least 10 times the net velo city of the rate-co ntro lling
step at all o verpo tentials.
In practice, judging by the numerical variety of Tafel-slo pe
values that are o bserved but do no t acco rd exactly with theo retically
predicted limiting cases, it is generally no t adequate to assume that
the co nditio ns required for the limiting values to arise acco rding
to Eqs. (12) o r (13) are met. Then, of co urse, rather arbitrary
dependences of b o r a o n T can arise and do no t have any special
fundamental significance.
Gileadi has po inted o ut in a private co mmunicatio n
73
that the
b values for chemically co ntro lled pro cesses, e.g., the value RT/2F
for ad-ato m reco mbinatio n in the h.e.r. o r for Cl
2
evo lutio n under
certain co nditio ns,
5
must follow the no rmally expected T-depen-
dence, i.e., b is linear in T and a is then independent of T. This
is because no e-barrier pro perties are invo lved in determining b for
such cases. This is an impo rtant po int but difficult to exemplify
unambiguo usly from experimental data since b = RT/2F for the
h.e.r. is o nly o bserved at Pt and its significance for that case, with
respect to reco mbinatio n co ntro l, has been questio ned
4
'
6
(diffusion
of H
2
from the electro de can give the same behavio r). Fo r Cl
2
evo lutio n, where reco mbinatio n co ntro l is indicated under same
co nditio ns,
5
'
49
the behavio r is co mplicated by T-dependent Cl~
adso rptio n and surface o xidatio n of the ano de metal, e.g., Pt. In
fact, this is pro bably a co mplicatio n in all ano dic reactio ns in
aqueo us media, including the discharge of N^ at Pt,
48
which pro -
vided the first example of a being temperature dependent. It is
surprising that in o ur recent studies of ano dic Cl
2
evo lutio n at Pt,
164 B rian . C onway
where the Tafel slo pe at lo wer current densities is 38 mV, i.e.
~2.3RT/(1 + 0.5)F, the slo pes are again independent of T yet
this slo pe wo uld be expected to be of the form RT/(l + j8)Ft so
that even if /3 were linear in T, b wo uld still be T-dependent.
11. T afel S lopes in R elation to E xchange C urrent Densities i
0
It is often fo und that electro chemical pro cesses that take place in
a multistep sequence (see Section IV.7) exhibit Tafel slo pes that
have relatively high values (~120 mV) when the i
0
values are large.
This behavio r is impo rtant in evaluatio ns of trends of elec-
tro catalytic activity for a given electro chemical pro cess at a series
of electro de materials.
46
Practically, it is evident that a reactio n
pro ceeding by a rate-co ntro lling pathway with a low Tafel slo pe,
e.g., 29 o r 42 mV (23RT/2F o r 23RT/3F at T = 298 K say), may
well have a better o perating po larizatio n perfo rmance
46
in terms
of r) at say 200 mA cm"
2
than ano ther pro cess with a higher i
0
but
also a greater b value, say 120 mV. This is illustrated qualitatively
in Fig. 16.
It is quite clear from general principles of electro de kinetics
that, for a reactio n which pro ceeds by two o r mo re steps in series,
there will arise a sequence of Tafel-line segments in the relatio n
shown in Fig. 17. Thus, the step "furthest do wn" the reactio n step
sequence tends to be rate co ntro lling at the lowest current densities.
This will also be the step with the smallest Tafel slo pe as can be
shown by treating the kinetics of the sequence by the quasiequili-
brium emtho d or the steady-state metho d, taking into acco unt
po tential dependence of surface co ncentratio ns of the (adso rbed)
intermediates (cf. Refs. 13, 25, 32, and 34). Thus, in the three-step
sequence illustrated in Fig. 17, there is a pro gressive increase of
the In i
0
values of the segments and an asso ciated increase in b
values. In the example schematically given, it is clear that had step
III remained rate co ntro lling up to high current densities, better
electro de perfo rmance wo uld have been realized at practical, ele-
vated current densities, despite the lower i
0
value. In practice, of
t Yo ko yama and Enyo
74
have recently argued that Cl
2
evo lutio n at Pt is co ntro lled
by the kinetics o f discharge o f Cl~ but this is no t suppo rted by the Tafel-slo pe
behavio r o r the reactio n o rder (cf. 76) when adso rptio n effects invo lving Cl~ io n
are taken into co nsideratio n.
75
165
o
LU
s
1 V
0,I
ni
o, n
n i
Figure 16. Illustrating relative po larizatio n performance of two
processes at an electro de having two po ssible In i
0
and co rrespo nd-
ing b values, I and II. Process I gives better po larizatio n perform-
ance at high c.d. despite its lower i
0
value.
O
En i
Figure 17. Sequence of Tafel regions for a hypo thetical three-
stage series electro de process as o verpo tential r\ is increased at
co nstant temperature (schematic).
166 B rian E . C onwty
i
/

o
r

7
]
I
T
I
A
L

\
P
O
T

E
N
=Î
I ,
Increasing temperature
Ti \ T
3
/ / /
7/A
Figure 18. Sequence o f Tafel regio ns o f a three-stage series electro de
pro cess, as in Figure 17, with increasing temperature, T
x
-> T
2
- T
3
, assum-
ing the steps have different activatio n energies (schematic).
co urse, vario us cases can arise, depending o n the kinetic behavio r
of the sequential steps of the reactio n.
Temperature is an impo rtant aspect of the abo ve type of
behavio r since the steps in a multistep sequence are usually asso ci-
ated with different activatio n energies. Then the step with the lower
activatio n energy tends to co ntro l the kinetics at the higher tem-
perature in a series reactio n sequence (see Fig. 18).
An interesting example of this behavio r has recently been
o bserved in o ur own work on the kinetic behavio r of the h.e.r. at
high activity Ni-Mo -Cd catho de materials.
104
These electro des give
remarkably low o verpo tentials (<100mV) for catho dic H
2
evol-
utio n at a practical c.d. of ~200mAcm~
2
but only at an elevated
temperature of 80-90C. The reaso n is clear as is seen from the
graph of the actual Tafel lines for o ne of these electro de materials
in aqueo us NaOH at vario us temperatures (Fig. 6). The Tafel
relatio ns show two , or so metimes three, segments but the low c.d.
regio n (II) has a low Tafel slo pe in the range 23-29 mV. It is
superceded by a regio n (I) of greater slo pe (~120mV) at higher
c.d.'s which, ho wever, is asso ciated with a larger (apparent) heat
of activatio n. Hence this regio n moves relatively more to higher
c.d.'s at elevated temperatures, leaving the lo w-slo pe regio n (advan-
tageo us for go o d electro de perfo rmance) to characterize the kinetics
under the latter co nditio ns. Hence relative perfo rmance is much
enhanced at elevated temperature. No te that the slo pe of the upper
regio n line I do es no t change very much with T, thus pro viding
ano ther example of a being temperature dependent. The two
regio ns are asso ciated with measurably different
77
behavio rs of the
H intermediate; po ssibly so rbed H as an hydride is invo lved
46
as
well as two -dimensio nally adso rbed H.
12. E lectrode A rea and T afel S lopes
Recent work o n the h.e.r. at high-area electro de materials, e.g.,
Raney-Ni type preparatio ns by Tilak,
78
seems to indicate that low
Tafel slo pes are exhibited at such materials in co mpariso n with the
behavio r of the same metal in bulk fo rm. This is no t just a matter
that arises o n acco unt of the lo wer real c.d.'s that can be achieved
at high-area po ro us materials since at co rrespo nding low current
densities at the bulk metal, e.g., Ni, there is not an indicatio n of a
change of Tafel slo pe from the usually o bserved value of 100 mV
(298 K) to a lower value within -100 mWfro m the reversible H
2
/H
+
o r H
2
/H
2
O, OH~ reversible po tentials. An example is sho wn in
Fig. 19 from the work of Tilak.
78
Current Density/A cm'
Figure 19. Co mpariso n of Tafel relatio ns for the h.e.r. at vario us Ni electro de
preparatio ns, and Fe, having varying real to apparent area ratio s; T = 343 K (from
Tilak
78
).
The behavio r at high area, po ro us catho de materials is, in fact,
the o ppo site of that no rmally predicted for a po ro us electro de,
namely that the Tafel slo pe, for a given pro cess, will be twice the
value at the co rrespo nding bulk metal plane surface. Hence the
o bserved behavio r must be due to some intrinsic difference in the
adso rptio n behavio r of H and/o r the kinetics of the h.e.r. under
such co nditio ns.
Bearing in mind that low Tafel slo pes for the h.e.r. are usually
asso ciated with a mechanistic step involving a po tential-dependent
state (H co verage o r degree of H so rptio n) of the H [see Eq. (43)
o r (44)], it is tempting to suggest that the interesting behavio r of
the h.e.r. at high-area active metal catho de materials is asso ciated
with a special state of the H intermediate
46
which is pro mo ted by
the diso rdered state of the metal in Raney-type materials or elec-
tro depo sited co mpo sites such as Ni-Mo -Cd. Here it is useful to
recall that special catalytic effects are o bserved with metal-ato m
cluster materials as recently investigated, e.g., by Ozin and Po wer
79
and Messmer and Salahuf.
80
This is an area of much practical impo rtance for research and
develo pment in electro lyzer techno lo gy; mo re work is currently
required for elucidatio n of the behavio r of high-area po ro us and
co mpo site electro de materials with regard especially to the values
of Tafel slo pe and co nditio ns under which low b values can be
achieved for H
2
, O
2
, and Cl
2
evo lutio n reactio ns, thus minimizing
activatio n o verpo tential energy losses in high current-density
o peratio ns.
V. P R O B L E M S W I T H E VA L UA T I O N O F H E A T S O F
A C T I VA T I O N W H E N a I S T E M P E R A T UR E DE P E N DE N T
1. Derivation of the A pparent H eat of A ctivation at the
R eversible P otential
No rmally, as may be seen from Eq. (11), evaluatio n of A//* can
be made from plo ts of In k vs. \jT o r, taking acco unt of any do uble-
layer effects, from In i
o
vs. I/T. This gives the apparent heat of
activatio n at the reversible po tential. The real but experimentally
undeterminable AH* at rj = 0 differs from the apparent value by
a AH, where AH is the heat change in the single electro de reactio n
invo lved. This pro blem was first treated by Temkin
81
(see Sectio n
V.2).
As is well kno wn, the apparent heat of activatio n evaluated
experimentally is dependent o n 77, as fo llo ws from Eq. (11). Fo llo w-
ing the form of that equatio n, the exchange current density i
0
can
be written in an abbreviated practical fo rm as
i
o
= k
o
exp(-&H?/RT) (47)
where AH* represents the (apparent-see belo w) heat of activatio n
at 7] = 0 (reversible co nditio n V). At o ther current densities, i
v
,
for 17 > 0, is
i
v
= fco exp(-Atf ; */ *r ) = k
0
exp[-(AH* - a
V
F)/RT] (48)
where a may o r may no t be a functio n of T in the abo ve equatio ns,
k
0
is written to include a temperature-independent mo lal reactant
co ncentratio n but this is a trivial po int. Fo r simplicity here, it is
assumed in Eq. (48) that 17 do es no t affect AS
0
* in k
0
(see p. 131).
Fo r pro cesses that o bey the co nventio nal form of the Tafel
equatio n with b = RT/aF, the AH* evaluated at vario us 17 is
simply given by
A//;* = AH?* - a
V
F (49)
for the case where no quadratic term in rj is invo lved. Ho wever,
when a is/( T) in Eq. (48), it is clear that this must be taken acco unt
of when AH^* for vario us 77's is evaluated from d In i
v
/d{l/T).
Co nway and MacKinno n
82
first examined this pro blem in relatio n
to their paper o n b(T) with Tilak.
2
It is useful to sho w the results of their illustrative calculatio ns
of the co nsequences of b no t being simply RT/aF, with a co nstant,
by evaluating AH* for vario us cases co rrespo nding to the several
fo rms of b as /(T) enco untered experimentally. Fo r this purpo se,
AH* is taken arbitrarily as 41. 8k. Jmo r
1
and co rrespo nding i
0
values can be calculated for vario us temperatures. Co rrespo nding
1 values at vario us rj and for vario us temperatures can be evaluated
from the Tafel equatio n in the form lo g 1 = lo g i
0
+ rj/2.3b
9
where
b is taken as o ne of the fo ur po ssible fo rms enco untered experi-
mentally:
170 B rian . C onway
Case 1:b = RT/pF with p = co nstant = 0.5 - the classical
expressio n for b with co nventio nal T-dependence. (Fo r this case,
AH* sho uld be reco vered witho ut co mplicatio ns. This is just a
reference example).
Case 2:b = RT/p'F + X, where K = 0.04 V and p = 0.71 as
for Hg
2
(this co rrespo nds to b = 0.116 V at 298 K).
Case 3:b = RT/a(T)F = R/yF = const, independent of T,
as o bserved for a number of electro de pro cesses exemplified in
Section III.
Case 4:b = K
f
- RT/pF or b = RT/a(T)F with a = yT
m
,
where m > 1 so that b decreases as T increases.
Fo r each of the cases listed abo ve, AH* and AH* can be
reco vered
82
from the calculated In i
v
vs.l/T taking acco unt of the
form of b as f(T). The following metho ds may be used:
1. AHf is reco vered from d In ijd{\/ T) = -AHf/R. This
is the usual and most co nvenient way of o btaining the heat
of activatio n at 77 = 0.
2. A//* is reco vered at vario us 77 from dlni^/d(l/T) =
-(&Hf-a
V
F)/R.
3. From (drf/dT), = -AH^/aFT.
4. From (d
V
/d In T)
t
= -AH\/aF.
The latter two derivatives give, of co urse, Af/* values for respective
77 values co rrespo nding to the i
v
values at which the derivatives
are evaluated.
The results of the illustrative calculatio ns, made in these vario us
ways, may be co mpared as shown in Fig. 20 for plo ts of the
log i
v
vs. i/T type. Fig. 21-22 show 77, vs. log T plo ts (metho d 4)
for cases 1-3.
In Case 1, treated by the co nventio nal metho d (1), linear
electro chemical Arrhenius plo ts result with slo pes that decrease in
the expected way with increasing 77. Case 2 gives curvature in such
plo ts as do es case 4 (but with the curvature in the o ppo site direc-
tio n). Case 3, with a linear in T, as often fo und, gives log /,, vs. 1/ T
plo ts that are parallel for vario us 77 values so that the AH* values
that are reco vered are apparently independent of 77. This is an
interesting and significant case. The behavio r of Case 3 follows
o bvio usly from Eq. (48) when a = yT since then the expo nent in
Eq. (48) o nly involves the term AH*/ RT as a T-dependent quantity
so that a co mmo n A//* is reco vered for all 77 values. Fo r Case 4,
U b
05
04
0 3
0 2
01
1) Smooth Pt
_ 2) Thermally formed Pt
3) Teflon bonded Pt on Pt screen
-
yT
2
3
- i '
- 4 - 3 - 2 -1 0
Current Densi t y/A cm"
2
Figure 20. Co mpariso n of Tafel relatio ns for the h.e.r. at three types of Pt: smooth
Pt and two high-area materials (from Tilak
78
).
AH* evidently increases (!) with increasing rj when b decreases
linearly with T; this is also a case so metimes enco untered experi-
mentally.
It is interesting to no te that when co nditio ns co rrespo nding to
case 3 apply, as shown in Fig. 21c, no co nditio n of activatio nless
discharge (cf. Krishtalik
83
) wo uld be reached acco rding to experi-
mental evaluatio ns of ln^ as/(I/ T) for vario us increasing rj values.
Ho wever, at a given co nstant 7, such a co nditio n sho uld still
(theo retically) be attainable when r)F beco mes sufficiently large.
In case 1, activatio nless discharge does fo rmally arise as is seen in
Fig. 21a when \ogi
v
beco mes parallel to the 1/ T axis. This co nditio n
arises, of co urse, at an o verpo tential 77* determined by the limit
AH?* - arj*F = 0. The line for -rj = 1.0 V in Fig. 21a is physically
fictitio us.
Results for o ther cases are to be fo und in Reference 82.
Fo r the co nventio nal case where AG* is modified by an elec-
trical energy -arjF with increasing po tential and a # / ( T) ,
increase of T In i
0
to an extent dependent o n AH* =
0
[cf. Eq. (48)].
Ho wever, b also increases in pro po rtio n to T so a series of Tafel
lines arises for increasing temperatures as sho wn schematically in
-4 0 -
E
o
-8 0
-12 0 -
-160
30
4-x1O
3
(K'
1
)
-150-
Figure 21 (a)-(d) Results o f illustrative calculatio ns fo r evaluatio n o f heat o f activatio n o f an electro de pro cess fro m plo ts o f lo g i
v
vs \/T fo r cases 1-4
174
B rian E . C onway
Figure 22. (a) Tafel relatio ns for a process with a finite heat
of activatio n (log i
0
dependent on T) and a b value linear in
T (co nventio nal case, schematic) and (b) as in part a but for
a pro po rtio nal to T (b independent of T) (schematic).
Fig. 22af; these lines evidently cro ss at some po tential TJ* so that
i
v
* is then independent of T, i.e., AH** = 0. This evidently co rre-
spo nds to the co nditio n of activatio nless discharge co nsidered by
Krishtalik
83
and referred to above for the case of increase of rj (at
a given T) to a limit co rrespo nding to AH* = 0, i.e., when arjF =
A/f *
=0
, assuming a is no t/(i7); actually it pro bably always is, over
t We are indebted to Mr. D. Wilkinson in our labo rato ry for useful discussions on
this po int.
a sufficient range of 77, as shown by Despic and Bo ckris
35
(but
co ntrast the h.e.r. case).
Fo r the case where the co nventio nal form of the Lefat slo pe
applies b~
x
= aF/RT with a independent of T, it is easy to show
that a family of Tafel relatio ns o btained (Fig. 22a) at vario us
temperatures intersect at a common o verpo tential 77* given by
since log (io
tTl
/io,T
2
) is determined by the quantity (-AH*/2. 3#)
(I/Ti l/T
2
), it is clear that 77* will be a co mmo n intersectio n
po int for all temperatures. Thus, at this po tential, the apparent
AH* is zero . These co nclusio ns depend, of co urse, on the usual
assumptio n that AH* itself is appro ximately independent of T if
the T range is no t to o large.
Fro m the fo rego ing, it also follows that when b~
l
is of the
form (yT + c)F/RT (cf. p. 133) there will be no common 77* po int
since the term b~
T
\-b~
T
\ is then (F/R)(yT
x
+ c)/ T
x
-
(yT
2
+ c)/T
2
], which will no t cancel with the term \/T
x
- l/T
2
from the difference of lo g/
0
values at any two temperatures.
In the limiting case of a(T) = yT, Tafel lines will remain
parallel with increasing T so that no cro ssing po int as in Fig. 22a
will ever be reached; this is indicated in Fig. 22b. di
v
/d(l/T) will
then be finite (hence AH* > 0) at all po tentials but, for a given T,
increase of 77 will decrease AH* from its zero-17 value in the usual
way, eventually leading to activatio nless discharge.
Care must therefo re be taken in interpreting apparent activa-
tio n energies as f(rj) from electro chemical Arrhenius plo ts when
a = yT, i.e., when b is independent of T.
2. a and the R elation between R eal and A pparent H eats of A ctivation
In any practical electro chemical experiment the abso lute, but
unkno wn, metal/so lutio n p. d. at the reference electro de must no r-
mally vary with temperature on acco unt of the single interface
reactio n entro py change. This leads to the now well-known situatio n
that measurements of i
v
o r i
0
as a functio n of temperature can
never give the true or "real" heat of activatio n for the electro de
pro cess. This was first po inted o ut by Temkin
81
who showed that
o nly an apparent^ heat o f activatio n (which we have called AH*
o r A//* abo ve) can be derived fro m electro chemical Arrhenius
plo ts. Similar limitatio ns apply to the evaluatio n o f vo lumes o f
activatio n, AV*.
30
The relatio n between Temkin's energy o f activatio n quantity,
W
ot
, i. e. , at zero metal-so lutio n p. d. (V), and the apparent o ne
AH* (referred to by Temkin as the "real" heat o f activatio n) that
is bo th experimentally measured and practically significant, i. e. , as
o btained fro m the recipro cal temperature co efficient o f ln/
0
,
d l ni
o
/ d( l / T) , is co nveniently derived (cf. Refs. 25, 81) as fo llo ws.
Ln i
0
is written as
In I'O = In k
0
- (A W* - aV
r
F)/RT (50)
where V
r
is the value o f V when the reactio n is at equilibrium
(i = 0; 7] = 0) and a is the transfer co efficient, taken fo r this case
to be independent o f T. No ting that the reversible po tential V
r
is
expressible fo r say a l e pro cess as AG
r
= -FV
r
where AG
r
is the
free-energy change in the single electro de interface reactio n under
study and AG
r
= A//
r
- TAS
n
ln i
0
can be written further as
- ^ ) ] / / ? T (51)
Hence, o btaining the heat o f activatio n in the usual way fro m
d ln i
o
/ d( l / T), it is fo und that*
d ln i
o
/d(l/T) = -(AW
0
* - aAH
r
)/R (52)
t Sometimes this quantity is referred to , somewhat misleadingly, as the "real" heat
of activatio n as it is the quantity that is accessible experimentally. However, it is
obviously no t the "true" heat of activation of the pro cess that would be measurable
if a co nstant electro de/so lutio n p.d. could actually be maintained as temperature
is varied in the experiment to evaluate the heat of activatio n. In this respect, it is
seen that the apparent, experimentally measureable, heat of activation of an
electro de pro cess does not have the same significance as the AH* quantity for a
simple ho mo geneo us chemical reactio n.
The pro blem of the variatio n of reference-electrode po tential can, of co urse,
be avoided if the reference electro de is kept at co nstant T while the temperature
of the working electro de is varied. However, then a thermal diffusion junctio n
p.d. is intro duced that depends on the temperature difference, as is well known.
$In deriving the result in Eq. (52) from Eq. (50), it is usually assumed that over
relatively small ranges of T
y
A//
r
itself does not vary with T, i.e., AC
p r
is small.
This is no t always the case, however, for reactio ns involving change of charge in
hydro xylic, structured solvents (see Ref. 55).
or
AHf = AW
oX
-aAH
r
(53)
A//
r
is the enthalpy change in the single interface reactio n under
study in the ln/
0
vs. T experiment but canno t directly be determined
in a thermo dynamically rigo ro us manner. Ho wever, with so me
extrathermo dynamic assumptio n abo ut evaluatio n of individual
heats of io nic so lvatio n,
55
'
84
estimates of AH
r
can be made but they
are never very satisfacto ry. Uncertainties are 20-35 kJmo r
1
.
Ho wever, no n-iso thermal cell measurements offer an appro ximate
way of o btaining A W
0
*.
When a o r (3 is a functio n of temperature, o r b is given by
Eq. (17), the simple additive relatio n between A W
ot
and AH
n
given
in Eq. (53) do es no t arise. The case where a is linear in T, namely
a(T) yT, as fo und fo r a number of pro cesses experimentally, is
of special interest with regard to evaluatio n of the true heat of
activatio n, A W
ot
.
In this case we intro duce a (T) as yT in Eq. (51) which beco mes
A W
ot
In i
0
= In /c
0
- - j ^ r - (yTAH
r
- yT
2
AS
r
)/RT (54)
giving
d In i
o
/d(l/T) = - 4 r * / R - yT
2
AS
r
= -AH?/R (55)
assuming, as previo usly, that A//
r
is no t a functio n of T. Thus the
experimentally accessible apparent activatio n energy A//* is no w
A W
ot
+ yT
2
AS
r
(no te that y has the units T~
l
and is experimentally
measurable). This quantity is of interest since the AS fo r the single
interface reactio n is much mo re reliably determinable
55
'
84
than the
co rrespo nding A/f
r
. Thus, AS? will no rmally invo lve, amo ng o ther
accurately kno wn thermo dynamic quantities: (1) the abso lute stan-
dard partial mo lar entro py of a single type of io n; and (2) the
entro py of electro ns in the electro de metal. Single-io n entro pies
required in (1) are no w kno wn by at least o ne mo re-o r-less reliable
extrathermo dynamic metho d
84
to within 1 e.u. (1. 2 kJ mo l"
1
fo r
7A5 at 298 K) and the entro py of electro ns is usually justifiably
assumed to be 0 <1 e.u. due to the lo w heat capacity
85
of the
degenerate "electro n gas" in metals. Hence AW
ot
can be derived
for this case with a reliability of -1. 5 kJ mo P
1
which is very much
better than wo uld be the case where AH
r
was required, as in Eq.
(53). Fo r that case, the uncertainty is at least 28 kJ mo l"
1
based
on the much larger uncertainty of abso lute io nic heats of
hydratio n.
84
Reliable evaluatio n of A W* wo uld also then lead to an esti-
mate of abso lute entro pies of activatio n for tho se electro de
pro cesses that are characterized by temperature-independent Tafel
slo pes, e.g., for ano dic Br
2
evo lutio n at C,
2
O
2
reductio n at pt
s
45a
-
45b
and N
2
evo lutio n from the NJ at Pt.
48
3. E xperimental E vidence for P otential Dependence of the Entropy
of A ctivation, AS*
(i) A S * for Ionic Redox Reactions
We have referred earlier to the requirement
211
'
82
that the
entro py of activatio n of an electro de pro cess be po tential dependent
if fi is fo und to be dependent on temperature.
In recent impo rtant papers, Weaver
107
"
108
and Weaver et al
109
have made interpretatio ns of the free energy of activatio n of some
io nic-co mplex redo x reactio ns in terms of their entro pic as well as
enthalpic co mpo nents. His appro ach has been to co mbine regular
kinetic measurements over a range of temperatures which give, in
the usual way, the apparent heat of activatio n, with no niso thermal
emf (electro mo tive force) measurements o n thermo cellst invo lving
the po tential of the reference electro de at different temperatures.
Within the limitatio ns that (1) the entro py of transfer of electro ns,
A5
e
, invo lved in the cell reactio n at the two temperatures is small
eno ugh to give a negligible TA5
e
over the range of T involved in
the measurements and (2) that the thermal diffusion po tential at
the bo undary of the two so lutio ns at different temperatures in the
thermo cell is small, o r can be co rrected for, this appro ach enables
the "real" heat of activatio n (i.e., the AH* free from an incidental
effect of variatio n of electro de po tential with T) to be distinguished
fairly reliably from the apparent value in a mo re o r less quantitative
t A treatment of the thermo dynamic backgro und of thermo cell measurements may
be found in the present autho r's (2) in Vol. 1 of this series, 1954, which refers to
the earlier o riginal work of Eastman, Crockford, and Hall, and Tyrell and Hollis
on this to pic.
way. Then, from the o bserved free energies of activatio n, the 7AS*
co mpo nent o r the co rrespo nding frequency facto r can be evaluated
and related to the so lvatio nal, steric, and o ther pro perties of the
co njugate redo x pair, and examined for any dependence o n
po tential.
In this wo rk, AS* values, co rrected for co ulo mbic do uble-layer
effects,
110
"
113
were fo und
107
to be bo th large and sensitive to the
ligand structure aro und the metal io n [Cr(III), Co (III) co mplexes,
and Eu(H
2
O)
3
1
+
, and V(H
2
O)6
+
] in o uter-sphere redo x reactio ns at
Hg. Ammine, anio nic, aquo , and o ther simple ligands were invo l-
ved.
107
"
109
These o bservatio ns of specificity in the kinetic para-
meters, to ligand structure, must be co nsidered in relatio n to the
expectatio ns of lo ng-range po larizatio n activatio n theo ry ("po laro n
theo ry") but the behavio r o bserved is, in fact, what may be expected
on the basis of mo re "mo lecular" pictures of the activatio n pro cess
and the ro le of sho rt-range effects and so lvent structure, taking into
acco unt ligand-specific effects that determine the "thermo dynamic
part" of the barrier.
Of special interest for the to pic of the present chapter is the
o bservatio n of Weaver
107
that while the "do uble-layer-co rrected"
AS* quantities are ligand sensitive, they are fo und to be independent
of po tential. This is no t the case for the ato m and electro n transfer
pro cess invo lved in the hydro gen evo lutio n reactio n at Hg studied
by Co nway, et al,
114
where an appreciable po tential dependence
of AS* is o bserved, co rrespo nding to "co nventio nally ano malo us"
variatio n of the Tafel slo pe with temperature. Unfo rtunately, in the
work with the io nic redo x reactio ns, as studied by Weaver, it is
o nly po ssible to evaluate the variatio n of the transfer coefficient o r
symmetry facto r with temperature with a limited variety of redo x
pairs since Tafel slo pes, co rrespo nding to any appreciable lo garith-
mic range of current densities, are no t always easily measurable.
Alternatively, evaluatio n of a o r @ from reactio n-o rder deter-
minatio n requires detailed do uble-layer studies over a range of
temperatures.
It is interesting also that the AS* quantities are appro ximately
o ne-half of the co rrespo nding o verall reactio n entro pies as was
found for the co rrespo nding A V* and A V quantities in the work
of Co nway and Currie
115
on kinetic studies at high hydraulic
pressures.
(11) A S * for the Hydrogen Evolution Reaction
In wo rk on the hydro gen evo lutio n reactio n at Hg from
CF
3
SO^H
3
O
+
(where the pro to n is present only as the unhydrated
H
3
O
+
io n) and from CF
3
SO
3
H in excess water (where the pro to n
is present as the fully hydrated ion H9O4), Co nway et al
114
directly
derived the real entro pies of activatio n for pro to n discharge at Hg
by means of kinetic measurements at vario us temperatures employ-
ing a no niso thermal cell, i.e., with a reference H
2
/H
+
electro de at
co nstant, ambient temperature. These measurements give, within a
good appro ximatio n (see Ref. 107), the true heat of activatio n free
from effects of incidental variatio ns of the reference electro de
po tential (cf. Temkin
81
), so that the entro py of activatio n o r the
co rrespo nding frequency facto r can be evaluated.
By applying this appro ach to rates measured at a series of
o verpo tentials, the po tential dependence of what we have referred
to abo ve as the "true" heat of activatio n and the entro py of activa-
tio n, ASj, at co nstant po tential, <, was evaluated for pro to n dis-
charge from the abo ve two media. The impo rtant co nclusio n that
was reached from the results is that ASj, (o r equivalently AS* (since
these A5* functio ns differ only by a co nstant quantity) is dependent
on po tential for the h.e.r. at Hg, as shown in Fig. 23.
From these results, we have evaluated,
114
using Eq. (23), the
values of A and /iTas follows for the h.e.r.: in 1M aq. CF
3
SO
3
H,
A = 0.22, /ULT = 0.28 with the o verall a = p = 0.5 while in the
mo no hydrate melt, A = 0.77, /nT = -0. 07, with the o verall p = 0.77.
No te that JJL has the units T~\
It is of co nsiderable interest that the h.e.r., which involves bo th
ato m and electro n transfer, shows this effect quite clearly (Fig. 23),
while for io nic redo x reactio ns involving suppo sedly only o uter-
shell reo rganizatio n in the activatio n pro cess, Weaver's results
107
show that there is little or no dependence of ASj, on po tential. This
difference implies that there is a qualitative difference between the
activatio n pro cesses in an atom transfer pro cess such as the h.e.r.
and in io nic redo x pro cesses where a state of hydratio n- or ligand-
shell interactio n is maintained in the electro n transfer pro cess while,
in atom transfer pro cesses, the state of hydratio n and io nic charge
is eliminated in the electro de reactio n. These results lend some
suppo rt to the view we have expressed elsewhere
68
that the activa-
181
8 -
0.1 M aq HCI
1 M aq CF3SO3H
0
0.4 0.8 1.2
-97/V
Figure 23. Evaluatio n of dependence of Arrhenius frequency factor
or entro py of activatio n on electro de po tential for the h.e.r.from H
3
O
+
in CF3SO JH
3
O
+
melt and from aqueo us H
+
in 1 M aqueo us CF
3
SO
3
H
[from Conway et al. (to be published)]; see D. F. Tessier, Ph.D Thesis,
University of Ottawa, 1985.
tio n pro cess in the discharge step of the h.e.r. is no t that of o uter
hydratio n-shell reo rganizatio n (as in an io nic redo x reactio n) as
has been pro po sed by Levich et al
66
but rather a mo re intimate
neutralizatio n and transfer, closely co upled with the deso lvatio n
pro cess as treated in earlier papers
39
'
69
o n this questio n.
Since the effect of po tential o n AS* for the h.e.r. is evidently
quite substantial, it seems reaso nable to suggest that it arises from
po tential dependence of the so lvent-structure enviro nment (e.g.,
H bo nding and po tential dependence of io n co ncentratio ns in the
do uble layer
57
) of the transitio n state in the interphase rather than,
e.g., from changes in anharmo nicity o r OH-bo nd frequency with
po tential, which co uld lead only to small changes of AS*.
It is curio us that the striking deviatio ns of electro chemical
kinetic behavio r from that expected co nventio nally, which are the
subject of this review, have no t been reco gnized o r treated in the
recent quantum-mechanical appro aches, e.g., of Levich et al. (e.g.,
see Refs. 66 and 105) to the interpretatio n of electro de reactio n
rates. The reaso ns for this may be traced to the emphasis which is
placed in such treatments on (1) quantal effects in the energy of
the system and (2) co ntinuum mo deling of the so lutio n with co n-
sequent neglect of the specific so lvatio nal- and so lvent-structure
aspects that can lead, in aqueo us media, to the impo rtant entropic
factor in the kinetics and in o ther interactio ns in water so lutio ns.
55
Ho wever, the work of Hupp and Weaver,
86
referred to on p. 153,
showed that the results co uld be interpreted in terms of Marcus
theo ry, with regard to po tential dependence of AS*, when there
was a substantial net reactio n entro py change in the pro cess.
VI C O N C LUS IO N S A N D FIN A L REMARK S
1. Review of the experimental literature shows that the Tafel
equatio n written in the co nventio nal form In i =
In i
0
+ ar)F/ RT = In i
0
4- 77/fc, with a co nstant, is rarely
o beyed in the sense that b is no t linearly dependent o n
T, so that a is apparently temperature dependent; the
latter dependence is usually quite large, e.g., 25% over
a 150 K range of T.
2. Appro ximate independence of the Tafel slo pe b on T is
the "rule rather than the exceptio n" in electro de kinetics
of a variety of pro cesses.
3. The situatio n summarized in remarks 1 and 2 implies that
quite fundamental aspects of electro n transfer asso ciated
with thermal activatio n and so lvatio n changes in
electro chemical charge transfer reactio ns are no t yet well
understo o d. Indeed, the pro blem suggests that the
fo undatio ns of electro de kinetics, co mmo nly regarded as
well understo o d, are, in fact, no t yet adequately formu-
lated.
4. Fo r the h.e.r. at Hg, several series of experimental results
show that it is no t because /3 is dependent o n T that b
is no t equal to RT//3F but rather that b =
RT//3'F + co nst, in certain cases.
5. Fo r some pro cesses, b may even decrease with T.
6. If the entro py of activatio n, AS*, as well as the
electro chemical energy of activatio n, is po tential o r field
dependent, it can be shown that the Lefat slo pe b~
x
will
co ntain a temperature-independent co mpo nent, so that
a o r {$ is apparently linear in T. In the general case, b~
l
will co ntain bo th temperature-dependent and tem-
perature-independent co mpo nents. The case where b is
entirely co nstant with T requires, fo rmally, that it is o nly
the entropy of activatio n that is po tential dependenta
situatio n that is difficult to understand on the basis of
current and established ideas o n the ro le of electro de
po tential in influencing rates of hetero geneo us charge
transfer reactio ns thro ugh changes of the Fermi level.
7. It is po ssible to understand how a po tential o r field effect
o n AS
t
co uld o riginate from the influence of the kno wn
field-dependent so lvent o rientatio n in the inner regio n of
the do uble layer on the so lvatio n-shell reo rganizatio n in
the activatio n pro cess thro ugh so lvatio n co -sphere/so l-
vent co -plane interactio n. Quantitative fo rmulatio n of this
effect has no t yet been made.
8. Specific adso rptio n of anio ns can give rise to unco nven-
tio nal temperature dependence of Tafel slo pes on acco unt
of the temperature dependence of the io n adso rptio n and
co nsequent changes of the structure and electric po tential
profile acro ss the do uble layer where the transitio n state
is established.
9. Co mplex reactio n sequences can also give rise to unco n-
ventio nal temperature dependence of a since then a
invo lves po tential dependence of surface coverages of
adso rbed intermediates.
10. When a i s/(T), co mplicatio ns arise in electro chemical
Arrhenius plo ts for evaluatio n of the apparent A//*; then
AH* is found to depend on po tential in an unco nventio nal
manner.
11. Fo r the case of reactio ns for which a is linear in T, the
abso lute heat of activatio n of the electro de pro cess can
be quite reliably derived from the experimental variatio n
of In i
0
with I/T. This is no t the case when the co nven-
tio nal behavio ur o btains (b = RT/aF; a = co nst.).
12. Fluctuatio n theo ry can only acco unt for a very small
variatio n of a o r /3 with T. The experimental variatio n
is much larger, indicating the impo rtance of o ther effects,
such as the influence of the field effect on entro py of
activatio n.
13. The relatively large influence of temperature on a o r /3
suggests that temperature dependence of so lvent structure
is an impo rtant facto r in the effect, especially in asso ciated
so lvenb such as H
2
O, H
3
PO
4
, etc.
14. Further measurements need to be made on the tem-
perature and po tential dependence of the rates of simple
ionic redox reactions at electro des with pro per co rrectio ns
for do uble-layer effects at vario us temperatures, so that
the temperature dependence of /3 for an elementary elec-
tro n transfer reactio n, witho ut chemiso rptio n and
co upled ato m transfer, wo uld beco me better kno wn. This
is an essential requirement for pro gress in understanding
the true significance of the temperature effects on elec-
tro de-kinetic behavio r; reliable experiments will no t,
ho wever, be easy to acco mplish and will require parallel
do uble-layer studies over a range of temperatures.
15. Fo r certain io nic redo x reactio ns, it appears that co nven-
tio nal behavio ur does arise, i.e., /3 is independent of T.
The case of 7-dependence of /3 pro bably arises when
there is some stro ng co upling in the reactio n with the
electro de surface either when ato m transfer o ccurs o r a
reactant ion so lvatio n o r ligand shell is shared with the
so lvatio n co -plane of the electro de surface, the co nditio n
of which is po tential or surface-charge dependent.
16. In a pro per representatio n of electro n transfer rates (cf.
Gerischer
88
) the Fermi-Dirac distributio n must be used
to express the o ccupancy of electro n energy states in the
metal as a functio n of T, relative to the Fermi level. This
intro duces a no nclassical temperature effect, i.e., differing
from that given by the Bo ltzmann functio n, except under
the limiting co nditio ns for which the Fermi- Dirac distri-
butio n goes over to the Bo ltzmann distributio n.
A C K N O W L E DGM E N T S
Ackno wledgement is made to the Natural Sciences and Engineering
Research Co uncil of Canada for suppo rt of theo retical work on
the pro blem of variatio n of a with T which is, in part, repo rted in
this chapter. The autho r is also grateful to pro fesso rs J. O'M.
Bo ckris, E. Gileadi and M. Weaver, and Dr. J. Appleby, to whom
this chapter was circulated prio r to publicatio n, for their co mments.
Thanks are due also to Pro fesso r E. B. Yeager for pro visio n of data
on O
2
reductio n in pho spho ric acid and for material related to Eq.
(24) in this chapter; to Dr. R. P. Bell, F.R.S., for helpful discussio n
in co rrespo ndence on the questio n of temperature dependence of
Br0nsted coefficients; to Pro fesso r D. F. Evans for pro visio n of
unpublished data on nitro -co mpo und reductio n; and to Messrs. D.
F. Tessier and D. Wilkinso n in o ur labo rato ry for helpful discussio n
on vario us po ints.
The autho r also gratefully ackno wledges award of the Killam
Senio r Research Fello wship of the Canada Co uncil for 1983-1985
during the tenure of which this wo rk was carried o ut.
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E lectrochemistry of S emiconductors:
N ew P roblems and P rospects
Yu. V. Plesko v and Yu. Ya. Gurevich
A. N. Frumkin Institute of Electrochemistry, Academy of Sciences of the USSR,
Moscow, USSR
I. INTRODUCTION
Electro chemistry of semico nducto rs is now in a state of o utliving
its "seco nd yo uth. " This directio n of electro chemical physics, which
emerged mo re than a quarter of the century ago , develo ped
especially intensively at the beginning of the 1960s when its scientific
fo undatio ns were laid do wn and metho ds of surface treatment of
semico nducto r materials were designed, which fo und applicatio n
in the techno lo gy of semico nducto r devices.
1
Electro chemistry of
semico nducto rs did no t retire into itself; o n the co ntrary, the results
o btained in this field made it po ssible to lo o k in a new way at such
co ncepts, co mmo n for electro chemistry as a who le, as the zero -
charge po tential, exchange current, the transfer coefficient of an
electro chemical reactio n, etc. Later, ho wever, interest in the pro b-
lems of electro chemistry of semico nducto rs dro pped significantly,
mainly because practical applicatio ns pro ved to be mo re difficult
than was expected.
A new surge of activities in this field (which is being co ntinued
no w) aro se after the beginning of the 1970s when the po ssibility
had been fo und of emplo ying semico nducto r electro des for so lar
energy co nversio n via pho to electro lysis of water with hydro gen
pro ductio n. At present, when, on the o ne hand, the danger of the
depletio n of natural reso urces beco mes mo re and mo re acute and,
o n the o ther, gro wth of enviro nmental po llutio n increases, wide
189
190 Y u. V. P leskov and Y u. Y a. Gurevich
attentio n
2
has been drawn to po tentially impo rtant "liquid junctio n
so lar cells" which are eco lo gically pure and utilize renewable
energy. Research and develo pment effort in the "so lar-semico n-
ducto r" field has led to co nsiderable develo pment in elec-
tro chemistry of semico nducto rs. At the same time, pro gress made
in electro chemistry of semico nducto rs has pro ved to be rather useful
for electro chemistry as a who le. Fo r example, the study of semico n-
ducto r electro des has resulted in co mprehensive develo pment of
such general pro blems as the co ncept of the electro chemical po ten-
tial of electro ns in the so lutio n, the relatio nship between the "phy-
sical" energy scale and the "electro chemical" scale of electro de
po tentials, etc. These pro blems co nstitute the co ntent of first
sectio ns of this review.
In the following sectio ns we co nsider new pro blems in elec-
tro chemistry and pho to electro chemistry of semico nducto rs pro per,
such as "Fermi-level pinning" at the surface of a semico nducto r
electro de (as an alternative to the more co mmo n "band-edge pin-
ning"), the quasithermo dynamic descriptio n of electro de reac-
tio nsin particular the co ncept of quasi-Fermi level and the limits
of its applicabilityand so o n. In these sectio ns we also co nsider
briefly the principles of certain of the most up-to -date practical
applicatio ns of electro chemistry of semico nducto rs.
Info rmatio n co ncerning the physics of semico nducto rs and
their surfaces can be fo und, for example, in References 3 and 4;
general pro blems of electro chemistry of semico nducto rs are dis-
cussed in References 1, 5, and 6. Finally, all these pro blems are
co nsidered in greater detail in a mo no graph of the autho rs.
7
No tatio ns used in this review are in acco rd with the IUPAC
electro chemical no menclature, but only with the exceptio n that the
electro de po tential is deno ted by <p instead of E, because, in semi-
co nducto r physics, the symbol E co nventio nally deno tes the energy
characteristics (such as, for example, the band-edge energies E
c
and E
v
, and the band gap E
g
).
I I . C H A R A C T E R I S T I C E N E R GY L E VE L S I N T H E
E L E C T R O DE /E L E C T R O L Y T E S O L UT I O N S Y S T E M
The thermo dynamically co rrect descriptio n of energy characteristics
of electro ns in electro chemical systems is a rather impo rtant pro b-
E lectrochemistry of S emiconductors: N ew P roblems and P rospects 191
lem bo th in purely metho do lo gical and practical respects. In par-
ticular, the co ncept of the electro chemical po tential of electro ns in
a so lutio n which co ntains a redo x co uple, is essential for the
understanding of the laws go verning electro chemical and pho to -
electro chemical pro cesses. Next, the reo rganizatio n energy of a
so lvent affects significantly the kinetics of reactio ns which invo lve
charge transfer. Finally, the electro n energy levels, which are
directly related to the o xidized and reduced co mpo nents of the
co uple, determine the quantitative characteristics of the co rre-
spo nding electro n currents.
1. T he E lectrochemical P otential of E lectrons in the S olution
C ontaining a R edox C ouple
Co nsider an electro de immersed in a so lutio n, which co ntains a
redo x co uple taking part in a reversible electro n exchange reactio n
ox + ne~^ r e d (1)
Here ox and red deno te the o xidized and reduced forms of the
substance (e.g., Fe
3+
and Fe
2+
) in the so lvated state, and n is the
number of electro ns transferred in the electro de reactio n. Under
thermo dynamic equilibrium, the following relatio n ho lds:
/Z
ox
4- n/I
e
= /I
red
(2)
where /I
o x
and /Z
red
are the electro chemical po tentials of the redo x
co uple co mpo nents in the so lutio n (per mo le), and {x
e
is the
electro chemical po tential of electro ns in the electro de. The quan-
tities /I
O
x,red can be represented in the form
Mox,red = RT I n C
ox
,
red
+ Z
OXfTed
^(f) + Mox,red ( 3)
Here R is the universal gas co nstant, T the abso lute temperature,
c
O
x,red are the co ncentratio ns (the activities in a mo re general case)
of the ox and red reactants in the so lutio n, z
o x red
are their charge
numbers, 8F is the Faraday co nstant, <f> is the electric po tential, and
Mox,red
ar
e co nstants independent of c
ox red
and </>.
Taking into acco unt Eqs. (2) and (3), we can calculate the
equilibrium electro de po tential <p, which co rrespo nds to reactio n
(1) o ccurring on an electro de:
where <p
0
is the standard electro de po tential in a given so lutio n;
<Po depends o n the difference /x
ox
- /ji
ed
and, thereby, on the nature
of the electro de reactio n and also on the cho ice of the reference
electro de.
It is rather impo rtant that if thermo dynamic equilibrium is
established, in acco rdance with Eq. (1), we can intro duce the
co ncept of the electro chemical po tential of electro ns in the elec-
tro lyte so lutio n, /I*
1
, which is in no way related to the presence of
the electro de itself. The fact is that within the framework of ther-
mo dynamics, a specific mechanism, thro ugh which an equilibrium
is established, do es no t play any ro le, so o ne may assume, in
particular, that electro n exchange between ox and red pro ceeds
witho ut any electro de invo lved. In this case, /If for reactio n (1) is
given by
^ = ~ (/Ired - Mox) (5)
Ti
where /2
red
and /I
o x
are taken at the po tential <f>
el
'
b
of the bulk
electro lyte so lutio n. Since the quantities /I
re
d,ox depend only on the
pro perties of the ox and red reactants and the so lvent, /If is in no
way related to the nature of the electro de and do es no t depend on
its interface structure. Mo reo ver, it is the quantity /If which deter-
mines the electro chemical po tentials of electro ns in a given electro de
under equilibrium co nditio ns. In particular, this electro chemical
po tential has the same value for any electro de which is in equili-
brium with a given redo x co uple.
The abo ve co nsideratio ns show how impo rtant it is to find a
relatio nship between jxf and the characteristic parameters of a
redo x co uple. To this end, we shall co nsider a so lutio n co ntaining
o ne red particle. Deno ting the most pro bable thermo dynamic
energy of the electro n level of the red particle by E
ed
and that of
the ox particle by E
ox
, we shall analyze, following papers,
8
'
9
the
thermo dynamic cycle (a-d) shown in Fig. 1 [in Eq. (1), n = 1 is
assumed for simplicity):
a. An electro n is instantly transferred from a so lvated red
particle (from the level E
cd
) to the level E
vac
. Here
vac
is the po tential energy of an electro n in vacuum, mo re
precisely, in the vapo r phase in a close pro ximity of the
electro lyte surface, yet beyo nd the actio n limits of purely
surface fo rces.
vac
L
ox
L
red
Figure 1. Determinatio n of the po sitio n of energy
levels of an electro n in the so lutio n co ntaining a
redox co uple. E is the internal energy and G is
the free energy.
b. The state of the so lvent near the red particle, which has
now beco me the ox particle, changes, co rrespo nding to
the thermo dynamic equilibrium of the ox particle in the
so lutio n.
c. The electro n from the level
vac
is instantly transferred to
the ox particle formed (to the level
ox
) witho ut any change
in the state of the so lvent.
d. A certain rearrangement of the so lvent o ccurs aro und the
red particle fo rmed; as a result, the who le system returns
to the initial equilibrium state.
In this cycle, the changes in the internal energy of the system
taking place at stages a and c characterize the depths of the levels
ed and E
ox
with respect to
vac
; these changes are also equal to
the io nizatio n energy of the red particle and the electro n affinity
of the ox particle in the so lutio n. The energy characteristics co rre-
spo nding to stages b and d represent reo rganizatio n energies of the
so lvent, R,
red
and E
Rox
, related to the red and ox particles.
Fo r the pro cess co nsidered here, the quantities E
Kredox
> 0 are
the abso lute value of energies (free energies to be exact), which
are necessary to alter the state of the medium (so lvent) from the
initial to the final equilibrium state when the charge of the particle
changes by unity.
10
"
12
194 Y u. V. P leskov and Y u. Y a. Gurevk*
T hus, by virtue o f the abo ve analysis,
red + E
Rr e d
~ E
ox
+ E^
ox
= 0 (6)
T he quantity F
o
is defined by the relatio n
F
0
=
E%d + ^R,red = ^ ox ~ ER,OX 0)
which fo llo ws fro m Eq. (6) and characterizes the change in the free
energy o f the system co nsidered when an electro n is transferred,
in an equilibrium manner, fro m the red particle in the so lutio n into
vacuum (o r when an electro n is transferred, again in an equilibrium
manner, fro m vacuum to the o x particle). Co mbining Eqs. (6) and
(7), we o btain
(8)
where
AE
R
=
R
,
r ed
- E
Kox
and E
ox
- E
Ted
= E^
ox
+
R
,
r ed
(9)
We no te that relatio n (9) can also be derived if we co nsider
the equilibrium transfer o f an electro n directly fro m the red particle
to the o x particle within the so lutio n.
In po lar liquids, in particular in water, o ne may assume E
Kox
=
/?,red ER, especially fo r the so -called o uter-sphere reactio ns.
13
In
this case, the main co ntributio n to the change in state o f the medium
is due to repo larizatio n o f the so lvent caused by lo ng-range electro -
static interactio ns.
We have then fro m Eqs. (8) and (9),
Fo = Kô x + red), E
ox
~E
red
= 2E
R
(10)
It can be seen fro m Eq. (10) that, in the simplest case co nsidered
here, the characteristic level F
o
lies midway between E
ox
and E
ed
,
and the difference between E
ox
and E
ed
is twice the value o f E
R
.
Thus, using Eqs. (3) and (5) and taking into acco unt that F
o
is calculated per particle, we finally o btain fo r the electro chemical
po tential, /I*
1
,
8
- RTIn (11)
where N
A
is the Avo gadro number.
Since relatio n (11) is of fundamental impo rtance, we shall give
ano ther, independent derivatio n of this relatio n by the metho ds of
statistical mechanics,
7
'
9
witho ut using Eq. (5).
Co nsider a system which is a set of cells who se average number
per unit vo lume is N. These cells co ntain at most o ne electro n per
cell, so that the average number of electro ns per unit vo lume is
n < N. In this case, the free energy of the system with only o ne
electro n is F
o
. The free energy of a unit vo lume of such a system
co ntaining n electro ns, G, is given by the relatio n (see, e.g., Ref. 14)
G = F
o
n- TS (12)
the 5 is the so -called co nfiguratio nal entro py, equal to
AM
S = -k\nC
n
N
= -k\n - (13)
(N - n)\n\
where k is the Bo ltzmann co nstant (k = R/ N
A
) and C
n
N
is the
number of ways acco rding to which n particles may be placed in
N cells. The electro chemical (chemical) po tential of electro ns jx
e
per mole of the substance is {x
e
= N
A
dG/dn. Taking into acco unt
Eq. (13) and the fo rmula a (In q\)/aq In q (q 1), we o btain
for /I
e
:
fl
e
= Jf
A
F
0
-RT In ^ - ^ (14)
n
We no te that the mo del system co nsidered here is, in fact, a
redo x co uple in the so lutio n. Indeed, electro ns in this system, who se
number is, o bvio usly, c
red
, are distributed o ver (c
o x
+ c
red
) po sitio ns.
Thus, substituting N = c
ox
+ c
red
and n = c
red
into Eq. (14), we
o btain an expressio n which co incides with Eq. (11).
Hence, the electro chemical po tential of electro ns in the so lu-
tio n can be intro duced quite rigo ro usly and co nsistently within the
framework of bo th the thermo dynamic and statistical-mechanical
appro ach.
In analo gy with the Fermi level of electro ns in so lids (calculated
per electro n), we intro duce the quantity F
redo x
, which is denned by
the relatio n F
redo x
= {*.*!N
A
and represents the electro chemical
po tential of electro ns in the so lutio n, per particle. The quantity
^Vedox is frequently called "the Fermi level of electro ns in so lutio n. "
We no te that this term (and mo re so the term "Fermi level of
so lutio n") sho uld be co nsidered as no t quite adequate and often
leading to co nfusio n. It sho uld be stressed that the po sitio n of F
redo x
in the so lutio n is in no way related to the co ncentratio n of "free"
electro ns in it, but is determined by the presence in the so lutio n of
a redo x co uple, which co ntains only "bo und" electro ns. The quan-
tity F
redo x
do es no t characterize the energy of any particle because
no electro ns with the energy F
red
ox are present in the so lutio n
(unlike, e.g., the case of metals where the Fermi level F
met
co incides
with the energy E
F
of electro ns at the Fermi surface). Thus, in the
co urse of electro de reactio ns, electro ns can pass neither from the
level F
red
ox to the electro de, no r from the electro de to this level;
transitio ns o ccur with the levels E
ed
and F
x
invo lved. At the same
time, it is the po sitio n of the level F
redo x
, which determines the
thermo dynamic pro perties of a redo x co uple and the interface
between the electro de and so lutio n co ntaining this co uple. Fo r
example, pro ceeding from the co nditio n of thermo dynamic
equilibrium in the semico nducto r/so lutio n system,
F=Fre6ox (15)
(F is the Fermi level of the semico nducto r), the co nditio n for an
electro chemical reactio n to o ccur can be written in the form
F > F
redox
(catho dic reactio n) (16a)
and
F < F
redo x
(ano dic reactio n) (16b)
Similar expressio ns can be used in co nsidering pho to elec-
tro chemical reactio ns (see Section IV.2).
The electro chemical po tentials of redo x co uples in so lutio n
are calculated in a kno wn manner from the thermo dynamic charac-
teristics of the substances invo lved. Fo r certain reactio ns, which
pro ceed with the participatio n of the semico nducto r electro de
material, in particular ano dic or catho dic deco mpo sitio n reactio ns,
the values of F
redo x
are as repo rted in References 15-18.
2. R elationship between the Energy S cale and the S cale
of E lectrode P otentials
The po sitio n o f the energy levels E
ox
and F
ed
and the level o f the
electro chemical po tential F
redo x
with respect to the level F
vac
can
be determined by establishing a quantitative relatio nship between
the "physical" energy scale, in which the energy
vac
is taken as
the zero reference po int, and the electro chemical scale of electro de
po tentials, which is recko ned from the po tential of a certain
arbitrarily cho sen reference electro de. The relatio nship between
these scales is, in general, of the form
F
red
ox = - V+ c o n s t (17)
Here e > 0 is the abso lute value of the electro n charge.
Let us co nsider such an o x/red co uple, for which the equili-
brium po tential <p is co nditio nally taken as zero ; the junctio n
between the so lutio n of this co uple and an inert co nducto r [i. e. ,
o ne which do es no t take part in reactio n (1)] is, by definitio n, the
reference electro de. The co nstant in Eq. (17) co incides then with
^Vedox, thereby representing the change in the free energy in the
co urse of the reactio n
ox + e~
ac
= red (18)
In o ther wo rds, this co nstant is the change in the free energy in
the transfer of an electro n from a po int in vacuum near the so lutio n
surface to the Fermi level of the reference-electro de metal, this
change being equal to F
o
for c
ox
= c
red
. The quantity F
o
/ e is so me-
times called the "abso lute po tential" of an electro de.
19
An attempt at determining this quantity was first made in
Reference 19 and then in Reference 20. By analyzing a rather
co mplicated thermo dynamic cycle,t the autho r of Reference 20
fo und that the change in the free energy of the reactio n
H:
q
+e
v
-
ac
*!H
2
(19)
which is equal to the value of the co nstant in Eq. (17) for the
no rmal hydro gen electro de (NHE), amo unted to -4. 5 eV.
The results of Reference 20 have been extensively used in the
literature (in particular, in co nsidering the pho to electro chemical
metho d of so lar energy co nversio n) for determining the
electro chemical po tential level of vario us redo x co uples.
t This cycle was based on the known value of the standard po tential of a silver
electro de in a so lutio n of Ag
+
io ns relative to the NHE and comprised the following
stages: sublimatio n of metallic silver, io nizatio n of silver atoms thus formed, and
hydratio n of the io ns.
It sho uld be no ted, ho wever, that the metho d cho sen in Refer-
ence 20, as well as in certain subsequent papers (see, e.g., Reference
21) for determining AG appears to be unjustifiably co mplicated
and gives lo wer accuracy. Indeed, in tho se calculatio ns the values
of, for example, sublimatio n energy and io nizatio n energy were
taken into acco unt twice, and with o ppo site signs, so they cancel
o ut in the final result.
A simple and accurate metho d of co mparing the scales of
energies and electro de po tentials follows from Reference 22 and
lies in the calculatio n of the work functio n of a metal, which is in
the electro lyte so lutio n at the reference-electro de po tential. This is
illustrated in Fig. 2, which shows a metal in equilibrium with an
o x/red co uple in the so lutio n (so that their electro chemical po tential
levels co incide: F
redo x
= F
met
). The change in the free energy of
reactio n (16) is the sum of the energies of stages c and d of the
cycle sho wn in Fig. 1, that is the quantity F
redo x
(which co incides,
as was already no ted, with F
o
for c
ox
= c
red
).
It can be seen from the cycle of Fig. 2 that
= w
(20)
Here w is the work functio n of the uncharged metal in vacuum,
and At/us the Vo lta-po tential difference in the metal/so lutio n system
which arises as a result of mutual charging of "free" surfaces of
the metal and so lutio n when they are bro ught into co ntact.
Fo r a particular case, for example, for the no rmal hydro gen
electro de, it is co nvenient to perform calculatio ns using data for
the Vo lta-po tential difference in the mercury-aqueo us so lutio n sys-
tem
23
: A</f = -0. 07 eV at zero po tential against NHE. Assuming
that the work functio n of mercury in vacuum is
24
w = 4.50 0.03 eV,
P -
redox
w
F
met
Figure 2. Diagram illustrating
the relatio nship between the
"physical" and "electro chemical"
scales.
we o btain from Eq. (18)
- F
redo x
(NHE) = 4.50 - 0.07 = 4.43 - 4.4 eV.
Thus, the level of the electro chemical po tential of the no rmal
hydro gen electro de, F
redo x
(NHE), lies 4.4 eV belo w the energy level
^vac-
Let us recall in this co nnectio n that the thermo dynamic work
functio n is equal to w = x + \F - E
c
\. Here x is the electro n affinity
of the semico nducto r, and the po sitio n of F relative to the co nduc-
tio n-band bo tto m, E
c
, in the semico nducto r bulk is given by the
following relatio ns:
F-E
c
= -E
g
/2 + kT\n(N
v
/N
c
)
1/2
9
n
o
= p
o
(/-type) (21a)
F- E
c
= -kTln(N
c
/n
0
)
9
n
0
p
0
(n-type) (21b)
F - E
c
= -E
g
+ kT ln(N
v
/p
0
), Po o (p-type) (21c)
where E
g
is the band gap, N
c
and N
v
are the effective densities of
states in the co nductio n and valence bands, and n
0
and p
0
are
thermo dynamic equilibrium co ncentratio ns of electro ns and ho les
in the semico nducto r bulk.
3. Determination of the R eorganization E nergy of a S olvent
Using the results presented abo ve, o ne can suggest a metho d of
determining the reo rganizatio n energy from data on pho to emissio n
of electro ns from so lutio ns into the vapo r phase (see review
25
).
Illuminatio n of a so lutio n co ntaining red particles with light
of quantum energy exceeding the electro n work functio n leads to
pho to emissio n of electro ns into the vapo r phase. Since pho to io niz-
atio n is a fairly rapid pro cess, an electro n passes into the vapo r
phase from the level E
ed
, so that the "pho to electric" work functio n
appears to be equal to E
ed9
if we take
vac
= 0. It follows from
Eq. (11) that for c
ox
= c
red
it differs from the "equilibrium" (ther-
mo dynamic) work functio n, equal to -F
r e do x
= - F
o
, by the reo r-
ganizatio n energy E^
Ted
(see Fig. 1). Thus, the latter can be fo und
as the difference between the pho to electric work functio n, w
ph
=
-E
cd
, and -F
r e do x
(a similar metho d for determining R,
red
was
emplo yed previo usly
26
for the case where so lvated electro ns served
as "emitters" in the so lutio n).
The quantity w
ph
can be fo und from the dependence of the
pho to emissio n current on the light quantum energy by extrapo lating
it to the zero current. Reference 27 repo rts the work functio n as
5.95 eV for pho to emissio n from aqueo us so lutio ns of Fe(CN)
6
4
~.
Using the standard po tential of the system Fe(CN)
6
4
"/Fe(CN)
6
3
~
as +0.36 V (relative to the no rmal hydro gen electro de), we o btain
for the reo rganizatio n energy of water aro und ferro cyanide/fer-
ricyanide io ns: 5.95 4.4 0.36 1.2 eV. Fo r the system co n-
sidered, the electro n transfer reactio n is an o uter-sphere o ne, so
o ne can take E^
ox
= E
Kred
= E
R
.
We no te in this co nnectio n that reliable experimental data o n
the values of E
R
are rather scanty.
10
Acco rding to Reference 28, in
aqueo us so lutio ns at ro o m temperatures E
R
amo unts to abo ut
0.5-2 eV. The pro blems co ncerning mo del calculatio ns of E
R
are
co nsidered in detail in the review.
13
Mo reo ver, we have to bear in
mind that the "ho mo geneo us" values of E
R
(which can be deter-
mined, in particular, using electro n pho to emissio n from so lutio ns)
are, apparently, much higher than the "hetero geneo us" values
(which can be fo und, for example, by pro cessing experimental data
on tunnel currents flowing from semico nducto r electro des into
so lutio ns
28
). Physical reaso ns for this discrepancy are mainly related
to the fact that in hetero geneo us charge transfer pro cesses only the
half-space o ccupied by the solvent is rearranged, and, to a lesser
extent, to the co ntributio n of image forces near the surface to the
reo rganizatio n energy, and also to the effect of specific adso rptio n,
structurizatio n of the so lvent near the interface, defo rmatio n of
so lvatio n shells of reacting particles near the electro de, etc. In the
simplest mo del, the "ho mo geneo us" reo rganizatio n energy exceeds
appro ximately twice the "hetero geneo us" reo rganizatio n
energy.
10
'
13
It is of interest that Reference 28 repo rts for the system
Fe(CN)
6
4
~/Fe(CN)
6
3
~ the "ho mo geneo us" value 1.24 eV o btained
by mo del calculatio n, which agrees well with the value presented
abo ve. As for the "hetero geneo us" reo rganizatio n energy, the same
paper repo rts, as it might be expected, a much lower value (0.4 eV)
o btained from tunnel currents measured o n heavily do ped SnO
2
electro des.
III. S PEC IFIC FEA TURES O F THE STRUC TURE O F THE
S EMIC O N DUC TO R/ELEC TRO LY TE IN TERFA C E
An electrical do uble layer arises at the semico nducto r elec-
tro de/electro lyte so lutio n interface, as in the case of the metal/ so l-
utio n interface. The do uble layer co nsists of the "plates" carrying
charges of o ppo site sign, each "plate" being lo cated in o ne of the
phases in co ntact. In the near-surface regio n of the semico nducto r
the charge is formed as a result of redistributio n of electro ns and
ho les, while in the so lutio n it is formed as a result of io n redistribu-
tio n. Under equilibrium co nditio ns, the abso lute values of these
charges are the same.
1. The Electrical Double-Layer Model
The facto rs which lead to the fo rmatio n of an electrical do uble
layer are rather general. First, charges flo w acro ss the interface
when a thermo dynamic equilibrium is established between the
phases in co ntact; seco nd, it is charging pro cesses, which are no t
generally related to charge transfer acro ss the interfacefor
example, charging of surface states (see belo w), certain types of
adso rptio n, etc.
Acco rding to the co nventio nal mo del,
1
'
29
'
30
three regio ns can
be distinguished within the electrical do uble layer: the space-charge
regio n in the so lutio n, the intermediate regio n, called the Helmho ltz
layer, and the space-charge regio n in the semico nducto r.
Helmholtz
layer
Space charge
(
layer \
Electrolyte Semiconductor'
Figure 3. Co mpo nents of po tential dro p at the semi-
co nducto r/electro lyte interface.
Figure 3 sho ws schematically (no t to scale) the spatial distribu-
tio n o f the interphase po tential dro p (the Galvani po tential) A^<
at the semico nducto r/electro lyte interface.
The semico nducto r o ccupies the regio n to the right o f the
vertical so lid line representing the interface (x = 0). To the left o f
it, there is the Helmho ltz layer fo rmed by io ns attracted to the
electro de surface, and also by so lvent mo lecules; its thickness, L
H
,
is the o rder o f the size o f an io n. The space-charge regio n in the
so lutio n (the Go uy-Chapman layer) is adjacent to the Helmho ltz
layer fro m the electro lyte side.
Let us deno te the electric po tential in the electro lyte so lutio n
bulk (fo r x - -o o ) by <f>
el>b
and in the semico nducto r bulk (x -> oo)
by <f>
sc
'
b
. The to tal po tential dro p acro ss the interface A si* b</> =
<f>
sc
>
b
- <t>
eKb
i s t h e n
A U = A
e
2
ub
< + tf<t> + Mt:l<l> (22)
Here &f'
b
<f> = <f>
{2)
- </>
elb
is the po tential dro p in the space-charge
regio n in the so lutio n, i. e. , between the so lutio n bulk and the o uter
("2") Helmho ltz plane; this quantity is usually deno ted by \fj'
("psi-prime" po tential). The seco nd term A
2
s
<f> = <f>
sc
'
s
- </>
(2)
is the
po tential dro p acro ss the Helmho ltz layer. Finally, the third term
Kl\b<f>
=
<t>
sc
'
b
~<
sc
'
5 i s
the po tential dro p in the space-charge
regio n in the semico nducto r. Belo w we shall o mit, fo r the sake o f
brevity, the index "sc" and use the no tatio n A^ ; ^ = A<.
We sho uld no te here the fo llo wing circumstance, impo rtant in
metho do lo gical respects. In electro chemistry, the po sitive directio n
o f the electro de po tential is co nventio nally the o ne fo r which
po sitive electro de charge gro ws. On the co ntrary, in the physics o f
semico nducto r surfaces the po sitive surface po tential, which is
usually recko ned fro m </>
scb
, is characterized by the accumulatio n
o f electro ns in the space-charge regio n, i. e. , the fo rmatio n o f a
negative space charge. All this directly fo llo ws fro m the Bo ltzmann
distributio n determining the co ncentratio n o f electro ns n
s
and ho les
p
s
near the surface:
n
s
= n
o
exp[e(</>
sc
'
s
-</>
sc
'
b
)//cr],
Equatio n (23) sho ws that if </>
sc
'
5
> </>
sc
'
fc
, then n
s
> n
0
and p
s
< p
0
.
Thus, the directio n o f the po tential axis accepted in electro chemistry
is o ppo site to that accepted in semico nducto r physics! This is
reflected in the fact that the sign of po tential dro p in the semico nduc-
to r, (f>
sc
'
s
- <t>
sc
-
b
(which is equal to -AJ0) recko ned from the
po tential in the bulk </>
sc
'\ is o ppo site to the sign of the last term
in expressio n (22) for the Galvani po tential. This sho uld always be
taken into acco unt in o rder to avoid co nfusio n in co mparing results
co ncerned with the physics of semico nducto r surfaces and
electro chemistry.
It is to be no ted that the po sitive directio n of the po tential axis
in the semico nducto r is in co nfo rmity with the directio n cho sen as
po sitive in the "physical" scale of energy (see Sectio n 2.2). Indeed,
in fo rmula (17), the terms characterizing the po sitio n of the Fermi
level and electro de po tential have o ppo site signs.
When an electro de is po larized, i.e., the electro de po tential is
varied by A<p, the Galvani po tential changes by A(AsJ$<) = A0. 1 M), which are, as a rule, used
in electro chemical experiments, the quantity Al
hb
(/> = \jj' (and hence
its change) is negligibly small. Precisely this case is co nsidered
belo w. Thus
A<p = A(A^) + A(A
s
6
0) (24)
Besides charge carriers, dipo les at the interface also co ntribute
to the fo rmatio n of the do uble layer. Here we mean first of all the
dipo le mo ments, which arise in the fo rmatio n of po lar bo nds
between the semico nducto r surface and ato ms adso rbed from the
so lutio n, and also o riented adso rbed so lvent mo lecules.
The distributio n of the dipo les do es no t co ntribute to the net
electro de charge, but gives rise to a certain additio nal po tential
dro p included into the quantity k
2
s
(j>. Experiment shows that this
dipo le dro p A
dip
</> may vary relatively little when the electro de
po tential changes, but it is usually rather sensitive to preliminary
treatment of the electro de surface and to the co mpo sitio n of the
surro unding medium.
Variatio n of the po tential <f){x) with the co o rdinate in the
semico nducto r is equivalent, within the framework of the band
mo del, to energy-band bending. The bands are bent do wnwards if
AJ0 < 0 and upwards if A
s
b
4> > 0. In the latter case, which co rre-
spo nds to depletio n of the near-surface regio n with electro ns, a
depletio n layer (the Mo tt-Scho ttky layer) is formed in n-type
semico nducto rs if the following inequality is satisfied:
kT
kT/e < M<f> <\n(n
o
/p
o
) (25a)
e
The space charge in this layer is mainly pro duced by io nized do no r
impurities of co ncentratio n N
D
n
0
. Similarly, in p-type semico n-
ducto rs, the charge of the depletio n layer, which arises in do wnward
band bending in the po tential range
kT kT
- \n(p
o
/n
o
) < M</> < (25b)
e e
is mainly pro duced by an accepto r impurity (that captured an
electro n) of co ncentratio n N
A
p
0
.
The case where a depletio n layer is formed is of most impo rt-
ance in practical respects, since in wide-gap do ped semico nducto rs,
which are used very extensively in mo dern electro chemistry of
semico nducto rs, the po tential range given by Eqs. (25a) and (25b)
is rather large.
If Ab</> = 0, the bands remain unbent ("flat") up to the inter-
face, and the space charge in the semico nducto r is zero . Under this
co nditio n, the po tential <p of a semico nducto r electro de, measured
against a certain reference electro de, is called as the flat-band
po tential, <p = (p^. The flat-band po tential in the electro chemistry
of semico nducto rs is equivalent to the zero -charge po tential (the
po tential of the zero free charge, to be exact
31
) in the elec-
tro chemistry of metals and plays an impo rtant ro le in the kinetics
of electro chemical pro cesses o ccurring o n semico nducto r
electro des.
It sho uld be no ted that at = 0, the quantity
A
2
s
<f> is no nzero , in particular, due to specific adso rptio n of io ns
from so lutio n. Fo r example, in the case of o xide semico nducto rs
(TiO
2
, ZnO, etc.) and also semico nducto rs who se surface is o xidized
in aqueo us so lutio ns (say, Ge), the co ncentratio ns of OH~ and H
+
io ns chemiso rbed on the surface are no t equal to each o ther, which
necessarily gives rise to a co ntributio n to A$. AS follows from the
co nditio ns of thermo dynamic equilibrium between io ns adso rbed
on the surface and present in the so lutio n bulk, the abo ve co ntribu-
tio n to A
2
b
<f> must be a linear functio n of so lutio n pH. Fo r a certain
pH value, dependent on the nature of a semico nducto r electro de,
the to tal charge of adso rbed io ns appears to be equal to zero . This
pH value (o r a similar quantity in the case of adso rptio n of io ns
of ano ther kind) is characterized by the "po int of zero zeta po ten-
tial" (PZZP, which is so metimes called the iso electric po int) o r,
acco rding to termino lo gy accepted in Reference 31, by the "po ten-
tial of zero to tal charge. " At the same time, even at PZZP, A
2
^
may, in general, be different from zero because of adso rptio n of
so lvent dipo le mo lecules at the interface and also (in the case of
o xide semico nducto rs) because of the dipo le character of the bo nd
between a semico nducto r ato m and o xygen.
In the study of specific features of the semico nducto r/elec-
tro lyte interface we have to co nsider surface electro n states. (In
this case it wo uld be mo re co rrect to speak abo ut interface states,
rather than surface states; in what fo llo ws, the co nventio nal term
"surface states" is used to mean "interface states". ) These states
can be rather impo rtant just in semico nducto r electro des, unlike
metal o nes where they are of no significance because of the
eno rmo us number of "free" electro ns.
Surface electro n states, which exist o n ato mically pure (ideal)
crystal surfaces, are usually called intrinsic. In recent years,
co nsiderable pro gress has been made bo th in theo retical and
experimental metho ds of studying intrinsic surface states (see, e.g.,
Refs. 32-34).
Under o rdinary co nditio ns, in particular when the electro de
material is in co ntact with an electro lyte so lutio n, adso rbed ato ms
o r even layers are present o n the surface; mo reo ver, real surfaces
may co ntain structural defects. They all can exchange electro ns
with the semico nducto r bulk to give rise to surface electro n states
of kinds and pro perties o ther than tho se inherent to intrinsic surface
states. The former play an impo rtant ro le in adso rptio n and catalysis
pro cesses.
Thus, a real semico nducto r surface co ntains vario us types of
surface electro n levels, which are characterized by a co mplicated
energy spectrum and may be bo th do no r and accepto r in functio n.
Their co ncentratio n depends on the way the surface is treated and
may reach values of 10
14
-10
15
cm"
2
, which appro ximately co incides
with the number of lattice sites per unit surface area of a so lid.
No nstatio nary metho ds of investigatio n reveal bo th "fast"
and "slo w" surface states and enable their characteristic relaxatio n
times to be estimated. In mo st cases, a set of states with different
characteristic relaxatio n times exists o n the surface.
The existence of surface energy levels leads to two very impo r-
tant effects. First, electro ns and ho les can be trapped at the surface
to form a surface electric charge layer and thereby induce an
o ppo site charge in the bulk. In particular, the influence of the
surface o n equilibrium pro perties of semico nducto rs is related
precisely to this effect. Seco nd, surface energy levels can change
significantly the kinetics of pro cesses with electro ns and ho les
invo lved: o n the o ne hand, they pro duce additio nal centers of
reco mbinatio n and generatio n of charge carriers; o n the o ther hand,
they can act as intermediate energy levels in pro cesses of charge
transfer acro ss the interface.
It is the existence of surface states that can lead to a co nsider-
able change in vario us electro chemical pro perties of semico nduc-
to rs in the co urse of treatment of their surfaces.
Finally, surface states of a special type arise under co nditio ns
of stro ng band bending. If, fo r example, A< < 0, so that the bands
are bent do wnwards, a po tential well for electro ns is fo rmed at the
surface. If this well is sufficiently deep, bo und states can arise in
it, and electro ns in these states are lo calized near the surface. The
o ccurrence of such states is o ne of the manifestatio ns of the surface
quantizatio n effect.
All that has been said abo ve is, o bvio usly, valid fo r ho les, with
the o nly exceptio n that in this case a po tential well is fo rmed when
the bands are bent upwards.
2. P otential Distribution: "P inning" of B and E dges and/or
the Fermi Level at the S urface
Co nsider no w ho w the to tal po tential dro p A si;
b
b<t> at the interface
is distributed between its co mpo nents A
2
s
</> and A$. Acco rding to
the well-kno wn electro static co nditio ns, the fo llo wing relatio n
e
H
%
H
= 4TTQ
S S
- s
sc
%
sc
(26)
must ho ld at the interface. Here %
H
and g
sc
are the values of electric
field strength near the interface from the side of the Helmho ltz
layer and semico nducto r, respectively; e
H
and e
sc
are the static
dielectric permittivities, and Q
ss
is the charge density at surface
levels which depends o nAJ</>; the sign "minus" in the seco nd term
o f Eq. (26) acco unts fo r the difference in the directio ns o f po tential
axes mentio ned abo ve. Fo r estimates, we can assume that \%
H
\~
\&
2
b
(t>\/L
H
and |
s c
| - |A*</>|/L
SC
, where L
H
and L
sc
are the thick-
nesses o f the Helmho ltz layer and the space-charge regio n in the
semico nducto r, respectively. They are related to the co rrespo nding
capacities by C
H
= 4rre
H
/ L
H
and C
sc
= 4ire
s
J L
sc
, and depend, in
general, o n A</> and A*<. If the charge asso ciated with surface
states is no t to o large, then, acco rding to Eq. (26), |A^ | |A
fo
0|,
pro vided
e
ac
L
H
/f
H
L
ac
1 (27)
It is a simple matter to verify that co nditio n (27) is satisfied
fo r reaso nable values o f the parameters e
sc
and s
H
. At the same
time, fo r heavily do ped semico nducto rs when the co ncentratio n n
0
(o r po) is sufficiently high, and also fo r large |A
b
</>|, the quantity
L
sc
may beco me so small that inequality (27) will no t ho ld true.
In o rder to estimate the effect o f surface states o n the po tential
distributio n, we have to calculate their capacity C
ss
= dQ
ss
/d(A
s
b
<f>).
This calculatio n appears to be rather simple in the mo no energy
mo del where all surface electro n levels are assumed to have the
same energy E
ss
. It can easily be demo nstrated (see, e. g. , Ref. 7)
that if
N
ss
> e
H
kT/7re
2
L
H
(28)
where N
ss
is the number o f surface levels per unit area o f the
interface, then |A( A^) | > |A(A
b
</>)|. In o ther wo rds, if co nditio n
(28) is satisfied, the variatio n o f the electro de po tential gives rise
to a po tential change in the Helmho ltz layer, which is larger than
the co rrespo nding po tential change in the space-charge layer. The
critical value o f N
ss
(to an o rder o f magnitude), at which inequality
(27) beco mes equality, is 10
13
-10
14
cm~
2
.
Thus, since usually L
H
L
sc
, then |A</>| |A</>|, and there-
fo re in electro lyte so lutio ns o f no t very lo w co ncentratio n, A
b
</>
co nstitutes, as a rule, the main po rtio n o f the interphase po tential
dro p Asc,b<. If we take into acco unt the abo ve co nsideratio ns,
ho wever, we see that this statement do es no t ho ld true in the
following cases:
1. Fo r very stro ng charging of an electro de when the Fermi
level at the surface is in close pro ximity to the edge of the
co nductio n o r valence band ("metalizatio n" of the
surface).
2. Fo r high co ncentratio n of surface states: the change in the
degree of their o ccupatio n (charging) leads to a co nsider-
able charge and po tential redistributio n, and can increase
no ticeably the co ntributio n of the co mpo nent A
2
s
<t> for a
fixed value of A^</>.
3. Fo r heavily do ped semico nducto rs, for which the Fermi
level in the bulk lies near the majo rity-carrier band edge
(o r, as in metals, even lies inside this band).
All that has been said is valid for po tential distributio n acro ss
the interface bo th under equilibrium co nditio ns and under electro de
po larizatio n with the aid of an external vo ltage so urce.
Co nsider now two impo rtant extreme cases
35
"
37
:.
1. Suppo se that |A(AJ<)| |A(A^)| when the electro de
po tential varies. This inequality means that the po tential dro p acro ss
the Helmho ltz layer remains practically unchanged (A
under electro de po larizatio n. Therefo re, the po sitio ns of all energy
levels at the surface and, in particular, of band edges E
CtS
and E
VjS
,
remain the same with respect to the po sitio n of energy levels in the
electro lyte so lutio n and reference electro de (Figs. 4a and 4b). In
this case, the band edges are said to be "pinned" at the surface.
Band-edge pinning is eventually related to the fact that, as was
already no ted, the po tential dro p acro ss the Helmho ltz layer, A*</>,
is solely determined by the chemical interactio n between the semi-
co nducto r and so lutio n, and do es no t depend, to any significant
extent, o n such external facto rs as po larizatio n and illuminatio n.
Therefo re, the band edges E
cs
and E
VtS
have the same po sitio n at
the surface for all samples of a given semico nducting material,
which are in co ntact with a given redo x co uple, irrespective of the
type and value of co nductivity because the chemical nature of the
material remains practically unchanged thro ugh do ping. Experi-
mental determinatio n of E
cs
and E
vs
for several semico nducting
materials (see, e.g., Ref. 38) confirms this co nclusio n.
2. Suppo se, on the co ntrary, that in electro de po larizatio n
)| |A(A0)| for o ne reaso n or ano ther (mentio ned abo ve),
E lectrochemistry of S emiconductors: N ew P roblems and P rospects
El
209
Reference
*
electrode
Electrolyte Semiconductor
(a) (b) (c)
Figure 4. Energy diagram of the interface with an external voltage applied illustrat-
ing the band-edge pinning (transitio n from a to b) or the Fermi-level pinning
(transitio n from a to c) at the surface of a semico nducto r electro de. The flatband
case is chosen as the initial state.
i.e., it is the po tential dro p acro ss the Helmho ltz layer which mainly
changes. Under these co nditio ns (see Figs. 4a and 4c) the energy
levels at the surface shift relative to tho se in the so lutio n by A) but relative to the Fermi level in the semico nducto r, the
band edges E
cs
and E
VtS
retain the po sitio ns they had prio r to the
change in the electro de po tential since the quantity A</> do es no t
vary. In o rder to stress the difference between this case and the
preceding o ne, it is said that the bands are "unpinned" from the
surface (this effect is so metimes called, tho ugh no t quite adequately,
pinning of the Fermi level with respect to band edges).
Fermi-level pinning leads to the situatio n that the level F can
reach the level F
redo x
even for systems characterized by a rather
po sitive o r negative value of the equilibrium po tential when the
level F
redo x
is beyo nd the semico nducto r band gap. Thus, in the
case of Fermi-level pinning, co nditio ns (16a) and (16b) are satisfied,
which permit electro chemical reactio ns to pro ceed at a semico n-
ducto r electro de, while in the case of band-edge pinning these
co nditio ns are "unattainable. "
In real systems, an intermediate case often arises, namely, bo th
po tential dro ps A</> and L
2
h
<f> change in the co urse of electro de
po larizatio n, so that neither the band edges no r the Fermi level are
actually pinned.
Experimental investigatio n of po tential distributio n acro ss the
do uble layer o n semico nducto r electro des is most frequently perfo r-
med by differential capacity (see the next sectio n) and pho to current
measurement techniques. A survey of experimental results o btained
in this field is beyo nd the sco pe of the present review. Certain data
illustrating the pinning and mo re detailed discussio n of its o rigins
will be presented in Section IV.2.
3. Determination of the Flat-B and Potential
The flat-band po tential, as was already po inted o ut, is o ne of the
most impo rtant physico chemical characteristics of a semico nducto r
electro de. In the electro chemistry of semico nducto rs this co ncept
has beco me even mo re impo rtant than the co ncept of the zero -
charge po tential in the electro chemistry of metal electro des. The
quantity cp^, appears to be quite essential in the quantitative descrip-
tio n of the do uble-layer structure and the kinetics of electro chemical
reactio ns at semico nducto r electro des. This is especially true for
the pho to electro chemistry of semico nducto rs because co nsiderable
pho to currents can only be o btained under efficient separatio n of
light-generated electro ns and ho les in the space-charge regio n (for
details, see Section IV.2). This separatio n o ccurs reliably only for
electro de po tentials that are mo re po sitive (in the case of n-type
pho to electro des) or mo re negative (in the case of p-type pho to elee-
tro des) than the flat-band po tential cpn, of a semico nducto r (tho ugh
this co nditio n of charge separatio n, as such, is no t sufficient for
the o ccurrence of pho to current).
The capacity of the space-charge regio n in a semico nducto r
C
sc
, under the fo rmatio n of a depletio n layer, is related to the
po tential dro p in this regio n A</> by
1
C;
c
2
= -^ (M<t> - kT/e) (29)
eN
D
e
sc
(we co nsider, for specificity, an n-type semico nducto r). Relatio n
(29) implies that a plo t of C~
c
2
vs. A
s
h
(f> sho uld beco me a straight
line (the so -called Mo tt-Scho ttky plotsee Fig. 5). If we assume
that only the co mpo nent A</> varies with the changing electro de
E lectrochemistry of S emiconductors: N ew P roblems and Pro spects 211
Figure 5. The Mo tt-Scho ttky plo t for a zinc o xide
electro de (co nductivity = 0.59 ft"
1
cm"
1
) in
1 N KC1 (pH = 8.5).
39
The dashed line is calculated
by Eq. (29).
-0,5 0 0.5
po tential cp and the semico nducto r/electro lyte junctio n capacity C
co incides with C
sc
, the slo pe of the Mo tt-Scho ttky plo t gives the
co ncentratio n of io nized do no rs and its intercept with the po tential
axisthe flat-band po tential (p^.
This metho d has widely been used in electro chemical measure-
ments. It sho uld be stressed, ho wever, that direct applicatio n of
Eq. (29) to experimental determinatio n of <p^ is based on several
assumptio ns (often accepted witho ut pro o f) co ncerning the pro per-
ties of the semico nducto r/electro lyte junctio n. These assumptio ns
have been analyzed, for example, in Reference 38). Here we
fo rmulate the most impo rtant of these assumptio ns:
1. It is assumed that the capacity measured, C, is no t disto rted
due to the leakage effect at the interface, a finite value of the o hmic
resistance of the electro de and electro lyte, etc. A co rrect allo wance
for these o bstacles is an individual pro blem, which is usually solved
by using an equivalent electrical circuit of an electro de where the
quantity in questio n, C
sc
, appears explicitly. Several measurement
techniques and metho ds of pro cessing experimental data have been
suggested to find the equivalent circuit and its elements (see, e.g.,
Ref. 40).
2. It is assumed that do no rs (accepto rs) in the semico nducto r
are, first, co mpletely io nized at the temperature of measurements
and, seco nd, uniformly distributed in the sample, at least within
the space-charge regio n. (A no n-unifo rmity whose scale is large in
co mpariso n with the space-charge regio n thickness can be deter-
mined by a special metho d; see Sectio n V.4). If the co ncentratio ns
N
D
and N
A
depend o n the co o rdinate, mo re co mplicated relatio ns
for the dependence of C
sc
on A</> are o btained instead of Eq. (29)
(see, e.g., Ref. 41). Deviatio ns from Eq. (29) are also o bserved in
the presence of deep do no rs (accepto rs), which are no t io nized in
the semico nducto r bulk at the temperature of measurements, but
beco me io nized in the space-charge electric field, thereby co ntribut-
ing to the capacity.
42
3. The capacity measured is assumed to represent only the
capacity of the space-charge regio n in the semico nducto r and no t
to include, for example, the capacity of surface states, adso rptio n
capacity, etc. In certain cases, this co nditio n is satisfied, for example,
on a zinc o xide electro de
39
; but mo re frequent is the situatio n where
the co ntributio n of the capacity of surface states is co nsiderable.
4. It is assumed that the electro de capacity measured, C, is
no t affected by the Helmho ltz-layer capacity, C
H
. If the dependence
of the measured capacity C on the electro de po tential (p beco mes
a straight line in the co o rdinates C
2
- <p
9
this fact is frequently
interpreted, in acco rdance with Eq. (29) and the relatio n C"
1
=
C^
1
+ C^
1
, as a pro o f that the following co nditio ns are satisfied:
C
SC
C
H
; |A(A
S
6
<)| |A(A^)| (30)
In o ther wo rds, it is suppo sed that: (1) the electro de capacity
measured is entirely determined by the capacity of the space-charge
regio n in the semico nducto r; and (2) a change in the electro de
po tential leads only to a change in the po tential dro p in the semico n-
ducto r, while the po tential dro p acro ss the Helmho ltz layer remains
co nstant.
A mo re detailed co nsideratio n
43
sho ws, ho wever, that the effect
of C
H
is a rather subtle pro blem which requires tho ro ugh analysis.
If the change in the po tential dro p acro ss the Helmho ltz layer
A(Ab<) in the co urse of electro de po larizatio n is no t neglected and
no r is the co ntributio n of the capacity C
H
to C, we o btain, with
due acco unt of Eq. (29), the following relatio n between C and <p:
C~
2
= C
H
2
+ - ^ - (p - ?fb - kT/e) (31)
eN
D
e
sc
This expressio n shows that C'
2
depends linearly on <p, i.e., in
the same manner as [acco rding to Eq. (29)] C~
2
depends on A<
[o r C~c o n <p, under the assumptio n that Ab# = co nst and A)]. Mo reo ver, it fo llo ws from Eq. (31) that the slo pe of the
co rrespo nding straight line in the co o rdinates (C~
2
, <p) is the same
as for the straight line (C~
c
2
, A$) [o r the straight line (C~
2
, <p)
pro vided A
2
,^ is co nstant].
But no w the straight line intersects the <p-axis at the po tential
<p' = v* + kT/e - ee
sc
N
D
/S7rC
2
H
(32)
With respect to the po tential determined from Eq. (29), (i. e. ,
when the co ntributio n due to the Helmho ltz layer is neglected) this
value is shifted by -eN
D
e
sc
/$7rC
2
H
. This shift, especially for heavily
do ped semico nducto rs, is by no means small; for example, for TiO
2
it amo unts to abo ut -0. 12 V at No = 10
19
cnT
3
and C
H
=
10"
6
Fcm"
2
.
Thus, the linear dependence of C~
2
o n <p, o bserved experi-
mentally, do es no t necessarily imply that the effect of the Helmho ltz
layer o n the experimental value of cpn, is insignificant, i.e., the
inequalities (30) do ho ld true. And vice versa, the abo ve co nsider-
atio ns sho w that deviatio ns of the dependence of C
2
o n <p from
a straight line, as such, canno t pro ve the fact that the inequalities
(30) are no t valid, i. e. , that it is the Helmho ltz layer C which is
respo nsible fo r the deviatio ns.
Finally, it sho uld be no ted that in many cases where (p^ is
determined by the capacity metho d uncertainty arises, which is
related to the frequency dependence of Mo tt-Scho ttky plo ts. (In
particular, the frequency of the measuring current is increased in
o rder to reduce the co ntributio n of surface states to the capacity
measured. ) As the frequency varies, these plo ts, as well as the plo ts
of the squared "leakage resistance" R vs. the po tential (in the
electro de equivalent circuit, R and C are co nnected in parallel),
are defo rmed in either of two ways (see Figs. 6a and 6b). In mo st
of the cases, o nly the slo pes of these plo ts change but their intercepts
o n the po tential axis remain unchanged and are the same for
capacity and resistance plo ts (Fig. 6b). So metimes, ho wever, no t
o nly do es the slo pe vary but the straight line shifts, as a who le,
with respect to the po tential axis, so that the intercept o n this axis
depends upo n the frequency (Fig. 6a).
No co mprehensive explanatio n of the dependences o bserved
has been suggested so far. A mo del
44
has been pro po sed for the
case sho wn in Fig. 6b; acco rding to this mo del, the semico nducto r
Figure 6. The effect o f the measuring
current frequency o n the Mo tt-Scho ttky
plo t.
44
C and R are the capacity and
resistance in the "parallel" equivalent
circuit o f the electro de; R^ is the value
o f R extrapo lated to infinite frequency,
(a) CdSe (N
D
- 10
15
cm"
3
) in
0.25 M K
2
SO
4
+ 0.25 M CH
3
COOH +
0.05 M CH
3
COONa; frequency: 1-320,
2-2440, 3-7080 Hz and (b) TiO
2
(N
D
=*
10
18
cm"
3
) in 0.25 M K
2
SO
4
+ 0.1 M
Na
2
B
4
O
7
; frequency: 1-320, 2-980, and
3-2440 Hz. All the po tentials are given
against the no rmal hydro gen electro de.
dielectric permittivity in the space-charge regio n depends on
frequency. It sho uld be no ted, ho wever, that this physical explana-
tio n seems to be no t sufficiently well substantiated and is no t the
only o ne po ssible.
Nevertheless, plo ts of the type of Fig. 6b are, in fact, used
to estimate the flat-band po tential by extrapo lating them to
intersectio n with the po tential axis; apparently, in this case,
N
D
(N
A
) canno t be fo und from the slo pes of these plo ts, and plo ts
of the type of Fig. 6a are co nsidered to be inapplicable even for
determining cp^.
Besides direct measurements, a metho d
45
has been suggested
to estimate the flat-band po tential cp^ using the pro perties of the
semico nducto r and so lutio n.
It follows from Eqs. (21) and (22) that under thermo dynamic
equilibrium and for sufficiently high electro lyte co ncentratio ns, the
following relatio n ho lds:
+ A
s
b
</>) = F - F
r
edox(ref)
= -x + F - E
c
- F
r
edo x(ref)
(33)
where F - E
c
< 0 is the difference between the level F and the
majo rity-carrier band edge E
c
, and F
redo x(ref)
co rrespo nds to the
reference electro de. The electro n affinity of the semico nducto r
appearing in Eq. (33) can be found by semiempirical fo rmulas
relating \ to the first io nizatio n po tential l
x
and electro n affinity
A
f
of the chemical co mpo nents that form the semico nducto r, and
also to the band gap; for example, in the simplest case of a binary
semico nducto r MX we have x
=
K^V + h + Eg)- Acco rding to Eq.
(21), the difference F - E
c
can be calculated if the charge-carrier
co ncentratio ns n
0
and p
0
, the band gap E
g
, and the densities of
states in the bands N
c
and N
v
are kno wn. The value of i
7
redo x(ref)
is also kno wn (see Section 2.2). Finally, if we assume that at the
po int of zero zeta po tential (PZZP) &l(f) is zero , Eq. (33) yields the
band bending eA</>, whence the flat-band po tential can be fo und.
The quantity (pH)
PZZP
co rrespo nding to PZZP can be calcu-
lated if the standard electro chemical po tentials of reactio ns with
adso rbed io ns involved (OH~ and H
+
in aqueo us so lutio ns) are
kno wn, o r it can be determined experimentally by po tentio metric
titratio n of a suspensio n co nsisting of micro particles of a given
semico nducto r in the so lutio n of a kno wn io nic strength (for details,
see Ref. 45). This permits Eq. (33) to be verified experimentally,
at least in part. It was fo und that for a large number of o xide
semico nducto rs there exists an appro ximately linear relatio nship
between (pH)
PZZP
and x> A linear relatio nship was also empirically
fo und between calculated values of x
a n
d measured values of cp^
(see Fig. 7). Using the straight line thus o btained we can calculate,
for a given o xide semico nducto r, the value of x
an(
* find
appro ximately its flat-band po tential.
It is to be no ted in co nclusio n that the existence of a linear
dependence between x
a n
d <Pn, discussed here is quite analo go us
to the well-kno wn relatio nship between the electro n work functio n
w and the zero -charge po tential in the electro chemistry of metals.
31
This analo gy beco mes especially clear if we take into acco unt that
for do ped wide-gap semico nducto rs E
c
- F is usually rather small
(^0. 1 eV), so that # w. In the case of metals, certain experimental
Figure 7. Relatio nship between the calcu-
lated electro n affinity and measured flat-
band po tential (against the saturated
calomel electro de) for several semicon-
ducto rs at their iso electric po ints.
45
(Reprinted by permission of the publisher,
The Electrochemical Society, Inc.)
XeV
*
5.0
ZrO
2
.
-
\ BaTiO
3
ZnO
T i O K
S nO 2
Fe
2
0
FeTiO j
' . CdO
3
\. wo
3
deviatio ns from this linear dependence can be attributed to a
difference in the dipo le po tential dro ps, which arise due to so lvent
adso rptio n o n vario us metals.
31
A similar effect (tho ugh, pro bably,
no t well pro no unced for semico nducto r electro des of the same
nature) sho uld also be o bserved in the electro chemistry of semi-
co nducto rs.
IV. QUA S I T H E R M O DY N A M I C A P P R O A C H T O T H E
DE S C R I P T I O N O F P H O T O E L E C T R O C H E M I C A L
P R O C E S S E S
In this sectio n, we shall co nsider several pho to electro chemical
pheno mena which o ccur in a semico nducto r/electro lyte system
under illuminatio n. The study of such pheno mena is very impo rtant,
no t only from the purely scientific po int of view, but also in view
of practical applicatio ns of electro chemical systems with semico n-
ducto r electro des. Electro de pro cesses are most stro ngly affected
by light of frequencies that are higher than the thresho ld of the
intrinsic (fundamental) abso rptio n of a semico nducto r, when the
energy of a light quantum abso rbed is sufficient for pho to generatio n
of electro n-ho le pairs. Redistributio n of charge carriers in the
semico nducto r near the interface with the so lutio n, caused by such
pho to generatio n, can change radically no t only the rate but also
the character of electro chemical pro cesses taking place at the
interface.
1. Quasi-Fermi L evels
At present, several metho ds have been develo ped to describe pho to -
electro chemical pheno mena. Fo r example, the kinetics of pho to -
electro chemical pro cesses can be studied theo retically by solving
transpo rt equatio ns (with allo wance for charge-carrier pho to gener-
atio n) which are supplemented by certain bo undary co nditio ns
acco unting for the specific features of electro de reactio ns with
electro ns and ho les invo lved.
46
"
50
In the simplest cases, this
appro ach enables o ne to o btain an exact so lutio n of the pro blem
but, with rather co mplicated bo undary co nditio ns, it appears to be
so mewhat difficult, and the expressio ns o btained are cumberso me.
At the same time, ano ther appro ach is quite efficient for qualitative
understanding and so metimes for quantitative interpretatio n; this
appro ach is quasithermo dynamic rather than kinetic and is based
on the co ncept of "quasi-Fermi levels. "
We recall that the co ncept of quasi-Fermi levels, first suggested
by Sho ckley,
51
can be intro duced in the following way. Suppo se
that, in additio n to thermal generatio n, charge carriers in a semico n-
ducto r are also generated because of certain external facto rs, say,
illuminatio n. In the steady-state regime, a dynamic equilibrium
arises between generatio n and reco mbinatio n of electro n-ho le pairs.
As a result, certain steady-state (but no t equilibrium) co ncentratio ns
n* and /?* are established in the semico nducto r under illuminatio n.
Suppo se, further, that the lifetimes of excited states are rather large.
Then, interactio n with lattice vibratio ns (pho no ns) gives rise to
equilibrium distributio ns with the temperature of the lattice (the
pho no n system) separately in electro n and ho le gases co ntaining
the pho to generated particles. Ho wever, the electro n and ho le gases
may no t, in general, be in equilibrium with respect to each o ther.
Under such co nditio ns, each distributio n (electro n and ho le) is
characterized by its own chemical and electro chemical po tentials.
Fo r electro n and ho le systems, the latter will be deno ted by F
n
and
F
p
, respectively. Unlike the case of co mplete thermo dynamic equili-
brium where F
n
= F
p
= F, the quantities F
n
and F
p
, called the
quasi-Fermi levels and co rrespo nding to a partial equilibrium, are
no t equal to each o ther (Fig. 8).
Thus, in the quasi-thermo dynamic appro ximatio n co nsidered
here the o ccurrence of no nequilibrium electro ns and ho les in the
bands can be described as the "splitting" of the initial Fermi level
F into two quasi-levels F
n
and F
p
.
///////////////////
-F
V/////////////////
F
P
(a) (b)
Figure 8. Diagram illustrating the splitting of the Fermi level
into quasilevels of electro ns and ho les (a) in the dark (b)
under illuminatio n of the semico nducto r.
The quasi-equilibrium co ncentratio ns /i* and p* are given by
w J = n
0
+ An, pt = p
0
+ Ap (34)
and o utside the space-charge regio n An = A/? because carrier pho to -
generatio n o ccurs in pairs.
Substitutio n of n* and p* into Eqs. (21a)-(21c) yields the
quasi-Fermi levels F
n
and F
p
. Fo r example, in the case of an n-type
semico nducto r, Eq. (21b) gives F
n
~ F, if the co nditio n An n
0
is
satisfied. At the same time, since p
0
n
0
, the co nditio n A/? p
0
can be satisfied simultaneo usly; for F - F
p
we find then from
Eq. (21c):
F-F
p
~kT\n^
9
App
0
(35)
Po
Similar relatio ns ho ld for a p-type semico nducto r.
Thus, Eq. (35) implies that a no ticeable shift of the
electro chemical po tential level under pho to generatio n can only take
place for mino rity carriers. Fo r mo derate illuminatio n intensity, the
shifts of the quasi-levels, F
nj
are pro po rtio nal to the lo garithm of
the intensity; as it increases, further gro wth of the shifts slows do wn
due to enhancement of reco mbinatio n pro cesses. The ultimate shift
of F
np
with increasing illuminatio n intensity, so lo ng as Eq. (35)
(and a similar fo rmula for a p-type semico nducto r) is valid, is the
edge of the co rrespo nding band.
2. Description of the M ost Important T ypes of
P hotoelectrochemical R eactions
Let us now turn, using the co ncept of quasi-Fermi levels, to the
descriptio n of qualitative peculiarities in the o ccurrence of pho to -
electro chemical reactio ns at an illuminated semico nducto r/elec-
tro lyte interface.
15
'
52
The quasithermo dynamic appro ach emplo yed below relies
upo n the assumptio n that an electro de reactio n is accelerated under
illuminatio n due to the fo rmatio n of quasi-levels F
n
and F
p
, which
are shifted relative to the equilibrium po sitio n F. Co nditio ns (16a)
and (16b) sho uld now be modified. Namely, for an ano dic pro cess
to o ccur with ho les being invo lved, the following inequality sho uld
E lectrochemistry of S emicoajuctors: N ew P roblems and P rospect! 219
be satisfied:
F
P
< f w (36a)
and a catho dic pro cess, with co nductio n-band electrons, requires
analo go usly the fulfillment of the inequality:
F
n
> F
redo x
(36b)
Let us first co nsider a semico nducto r electro de under o pen-circuit
co nditio ns, an individual particle of a semico nducto r suspensio n
in a co nducting liquid being an example. Suppo se that in a certain
po tential range, electro n transitio ns acro ss the interface between
the semico nducto r and so lutio n do no t take place in darkness, i.e.,
the semico nducto r behaves as an ideally po larizable electro de. This
po tential range has an upper and a lo wer limit, namely, the po tential
of so lvent deco mpo sitio n and/o r the po tential of semico nducto r
deco mpo sitio n (co rro sio n). The statio nary electro de po tential in
the regio n of ideal po larizability is determined by chemiso rptio n
pro cesses (in aqueo us so lutio ns, it is mo st o ften chemiso rptio n of
o xygen) o r, which is the same in the language of the physics of
semico nducto r surfaces, by charging of slo w surface states. It is
these pro cesses which determine steady-state band bending.
Figure 9 sho ws the energy diagram of a semico nducto r, rc-type
as the example, in co ntact with the so lutio n. Besides the energy
levels in the semico nducto r, the bo tto m of the co nductio n band E
C9
and the to p of the valence band E
V9
the figure depicts the
electro chemical po tential levels fo r reactio ns of ano dic disso lutio n
of the semico nducto r, F
dec p
, and catho dic evo lutio n of hydro gen,
FH
2
/H
2
O (We co nsider the case where semico nducto r deco mpo si-
tio n with invo lvement of ho les, and water-to -hydro gen reductio n,
with invo lvement of co nductio n-band electro ns, are the mo st pro b-
able ano dic and catho dic reactio ns, respectively).
Figure 9 co rrespo nds to the case where a depletio n layer is
fo rmed in the near-surface regio n of the semico nducto r. Light-
generated electro ns and ho les mo ve in o ppo site directio ns in the
depletio n-layer electric field: ho les to ward the interface and elec-
tro ns into the semico nducto r bulk. The electric field, which arises
as a result of such charge separatio n, co mpensates, in part, for the
initial field. This is manifested in the decrease in band bending
ek
s
b
<f) under illuminatio n, i. e. , the bands unbend. Band unbending
r
H
2
/H
2
0
'decj
Figure 9. E nergy diagram of the semiconductor/electrolyte junction: (a) in darkness
and (b) under illumination.
leads in turn to the change in the mutual po sitio n of o ther energy
levels in the system. Indeed, suppo se for simplicity that the po tential
dro p acro ss the Helmho ltz layer do es no t change under illuminatio n
(As</> = co nst), so that the po sitio n of the band edges at the surface,
E
cs
and E
VtS9
is fixed with respect to the reference electro de and,
therefo re, to energy levels in the so lutio n (band-edge pinning at
the surface; see Section III. 2). At the same time, the po sitio n of
the electro chemical po tential level of the semico nducto r F (the
Fermi level) relative to band edges is strictly determined in the
semico nducto r bulk. Thus, the bands unbend under illuminatio n
and "pull" the Fermi level, so that it shifts with respect to its
po sitio n in the no nilluminated electro de, as is shown in Fig. 9. The
shift of the level F under illuminatio n can be measured by a
reference electro de. It is this shift, AF, which is o bserved as the
pho to po tential <p
ph
= AF/e.
Let us co nsider the effects related to the fo rmatio n of quasi-
Fermi levels of electro ns and ho les. Fo r majority carriers (electro ns),
the shift of F
n
with respect to F is very small, as was no ted abo ve,
and it is usually neglected; on the co ntrary, for mino rity carriers
(ho les) the quasilevel F
p
can shift quite significantly with respect
to R
Fo r a certain illuminatio n intensity, the ho le quasilevel F
p
at
the semico nducto r surface can reach the level of an ano dic reactio n
(reactio n of semico nducto r deco mpo sitio n in Fig. 9). In turn, the
electro n quasilevel F
n
can reach, due to a shift of the Fermi level,
the level of a catho dic reactio n (reactio n of hydro gen evo lutio n
from water in Fig. 9). Thus, bo th these reactio ns pro ceed simul-
taneo usly, which leads eventually to pho to co rro sio n. Hence, no n-
equilibrium electro ns and ho les generated in a co rro ding semico n-
ducto r under its illuminatio n are co nsumed in this case to accelerate
the co rrespo nding partial reactio ns.
Simultaneo us co nsumptio n of no nequilibrium electro ns and
ho les at the semico nducto r surface in the co urse of pho to co rro sio n
formally resembles surface reco mbinatio n. Therefo re, pro cesses of
this type are referred to as "electro chemical reco mbinatio n. "
53
In principle, ano ther ano dic reactio n can take place instead
of semico nducto r deco mpo sitio n (disso lutio n), for example, o xida-
tio n of disso lved substance o r oxygen evo lutio n from water.
Apparently, in the latter case, the illuminatio n of semico nducto r
leads to pho to electro lysis of water with the fo rmatio n of hydro gen
and o xygen, that is, co nversio n of the energy of light into chemical
energy of the pho to electro lysis pro ducts.
If the who le semico nducto r/electro lyte interface is illuminated
unifo rmly, bo th co njugate reactio ns pro ceed at the same rate over
the same areas on the interface. The statio nary po tential of an
illuminated semico nducto r is thus a mixed po tential. If the surface
of a semico nducto r, ho mo geneo us in its co mpo sitio n and pro per-
ties, is illuminated no nunifo rmly, in the illuminated and no nillumi-
nated areas co nditio ns will no t be identical for electro chemical
reactio ns. Here the co njugate reactio ns appear to be spatially separ-
ated, so that we can speak abo ut lo cal ano des and catho des. This
situatio n is deliberately created, for example, for selective light-
sensitive etching of semico nducto rs (see Sectio n V.2).
There is ano ther way of spatially separating ano dic and
catho dic reactio ns on an illuminated semico nducto r, namely by
pro viding certain regio ns of the semico nducto r surface with differ-
ent electro chemical (in particular, electro catalytic) pro perties. Such
regio ns act as lo cal electro des, and the entire system as a galvanic
co uple. A suspensio n of platinized stro ntium titanate in an aqueo us
so lutio n may serve as an example of such micro hetero geneo us
systems. When it is illuminated, light-generated electro ns and ho les
are separated in the electric field of a depletio n layer near the
surface (Fig. 10), the ho les moving to ward the semico nducto r
surface and the electro ns into the bulk where they are transferred
acro ss the semico nducto r/metal interface. Therefo re, hydro gen is
evolved o n the surface of the metal (platinum in this case) and
oxygen o n the stro ntium titanate surface. Such micro hetero geneo us
systems have been widely used in recent years in view of their
applicatio ns for so lar energy co nversio n.
54
"
56
Finally, a natural extensio n of this appro ach would be the
creatio n of a "macro hetero geneo us" system: for example, an
electro chemical sho rt-circuited cell with a semico nducto r pho to -
electro de and light-insensitive, say, metal, auxiliary electro de (Fig.
11). If a stro ntium titanate electro de in an aqueo us so lutio n is used,
illuminatio n of such a cell leads to pho to electro lysis of water, with
the gaseo us pro ducts, hydro gen and o xygen, being evolved o n
different electro des of the cell. Reliable and co nvenient separatio n
of pho to reactio n pro ducts, which is a direct co nsequence of the
separatio n of primary pho to generated charges, electro ns and
Electrolyte
Figure 10. Scheme of water pho to electro lysis on a particle of
semico nducto r (platinized SrTiO
3
) suspension in an aqueo us
so lutio n.
0 Electrical circuit -*0
223
0
t
Metal
Diaphragm
Hz | 0
2
E
4
u
U3eV
i
f
H
2
0/0
2
Electrolyte
>\
1
1
i
- - c
/
/
Semiconductor
6F
Figure 11. Energy diagram of an illuminated pho to cell with an
n-type semico nducto r pho to ano de for water splitting.
ho lesdue to the space-charge field, is the most impo rtant advan-
tage of semico nducto r pho to electro chemical devices for co nverting
the energy of light into chemical energy.
The advantage of spatial separatio n of ano dic and catho dic
partial reactio ns of the o verall pro cess, stimulated by the illumina-
tio n of the semico nducto r/electro lyte interface, is two fo ld. First,
no nequilibrium electro ns and ho les tend to reco mbine and the
energy of light sto red in these particles is transfo rmed into heat
and canno t be utilized again. By directing the carriers of o ppo site
sign, immediately after their fo rmatio n, into different areas on the
surface where they participate in the co rrespo nding reactio ns
(instead of offering them a po ssibility to react in the same area, as
is the case with unifo rm illuminatio n of a ho mo geneo us semico n-
ducto r; see previo us text), we can radically reduce energy lo sses
due to reco mbinatio n, thereby increasing the pho to current quantum
yield and co nversio n efficiency. Seco nd, the efficiency of pho to elec-
tro lysis is increased co nsiderably if o ne of the two co njugate reac-
tio ns, namely that pro ceeding with majority carriers invo lved, is
transferred to a separate auxiliary electro de. Indeed, in the case of
an n-type semico nducto r co nsidered here, the catho dic reactio n,
in itself, is almo st no t accelerated due to illuminatio n (because
F
n
F), so that the who le "acting fo rce" of a pho to electro de is
co ncentrated on the ano dic partial reactio n taking place with mino r-
ity carriers (ho les) being invo lved. It is therefo re co nvenient to
carry o ut the catho dic partial reactio n (e.g., hydro gen evo lutio n)
on a metal electro de, which po ssesses go o d electro catalytic pro per-
ties for this reactio n.
Let us now turn to the case where an equilibrium is established
between the semico nducto r and so lutio n, even in darkness. This
usually takes place when the so lutio n co ntains a well-reversible
redo x co uple. Then, the semico nducto r attains the equilibrium
po tential of this co uple: <p = <p?
edO
x o r F = F
redo x
, which is the same.
Co nsideratio ns similar to tho se presented abo ve show that
illuminatio n of a semico nducto r leads to a shift of bo th the Fermi
level and the quasi-levels of ho les and electro ns, and bo th the
forward and reverse reactio ns, pro ceeding acco rding to Eq. (1), are
accelerated. In o ther wo rds, the result of illuminatio n is, abo ve all,
the efficient increase of the exchange current in the redo x co uple
57
;
but this is no t the only result. If a semico nducto r under illuminatio n
is an electro de in an electro chemical cell and is co nnected thro ugh
a lo ad resisto r with an auxiliary electro de, the catho dic and ano dic
reactio ns beco me spatially separated, as in the case of water pho to -
electro lysis (Fig. 11) co nsidered abo ve. The reactio n with the mino r-
ity carriers involved pro ceeds on the semico nducto r surface, and
that with the majority carriers invo lved, o n the auxiliary electro de.
Thus, the illuminatio n of a semico nducto r electro de gives rise to
an electric current in the external circuit, so that some po wer can
be drawn from the lo ad resisto r. In o ther wo rds, the energy of light
is co nverted into electricity. This is the way a pho to electro chemical
cell, called "the liquid junctio n so lar cell," o perates.
Co nsider in detail the perfo rmance of such a cell for a particular
case: n-type CdS/alkaline so lutio n of S
2
~+ S^/metal catho de
(Fig. 12). In darkness, the equilibrium
Sf-+ 2<T ;e 2S
2
~ (37)
is established in the cell.
Both electro des take the equilibrium po tential of this redo x
co uple, so that the Fermi levels of the metal and CdS, and the level
^Vedox
=
^V/s^"
m
the so lutio n, beco me equal. Go o d separatio n of
light-generated electro ns and ho les requires that a depletio n layer
- 0 --
225
'met
Metal Semiconductor (CdS)
Figure 12. Energy diagram of an illuminated "liquid junc-
tio n so lar cell" with a CdS pho to ano de and a S
2
~/Sl~
electro lyte. F (dark) is the Fermi level in no nilluminated
CdS.
sho uld be fo rmed in the semico nducto r and this, in turn, requires
that the equilibrium po tential o f the redo x co uple be mo re po sitive
than the flat-band po tential o f the semico nducto r, i. e. (p
Q
redox
> <Pn>.
When the electro de is illuminated, the bands unbend and the Fermi
level o f the semico nducto r F shifts (see Fig. 12), which is manifested
as a change in the electro de po tential. It can be seen fro m Fig. 12
that this change in the electro de po tential <p
ph
, i. e. , the pho to po ten-
tial, is equal to the shift o f the Fermi level o f the illuminated
electro de relative to the no nilluminated o ne divided by the electro n
charge e. In the simplest case (which, as experiment sho ws, is rather
frequent in practice), the po tential dro p acro ss the Helmho ltz layer
A
2
s
<f> under illuminatio n has the same value as in darkness;
mo reo ver, it do es no t depend o n (p
Tedox
. In o ther wo rds, the band
edges are pinned at the surface (see Sectio n III. 2). Under these
co nditio ns, the maximal value o f <p
ph
(which co rrespo nds to the
o pen-circuit pho to po tential) is equal to the initial (dark) po tential
dro p acro ss the space-charge layer, A$, i. e. , the difference |<p?
e
dox ~~
<Pfb|. In o rder to increase the co nversio n efficiency, the semico nduc-
to r and the redo x co uple in the so lutio n sho uld be cho sen such
that this difference be as large as po ssible.
Next, pho to generatio n of electro n-ho le pairs leads to the for-
matio n of quasi-levels of mino rity and majority carriers, F
p
and
F
m
as sho wn in Fig. 12. Since, at the surface, F
p
< F
S
2-
/S
2- and
F
n
> F
S
2-
/S
2-, illuminatio n results in the acceleratio n of bo th for-
ward and reverse reactio ns in a sulfide polysulfide co uple. If the
circuit is clo sed on an external lo ad R, the ano dic and catho dic
reactio ns beco me separated: the ho les are transferred from the
semico nducto r pho to ano de to the so lutio n, so that S
2
~ io ns are
o xidized to S2 , and the electro ns are transferred thro ugh the
external circuit to the metal co unterelectro de (catho de) where they
reduce S2 to S
2
~. The po tential difference acro ss a pho to cell is
i
ph
R, where i
ph
is the pho to current, and the po wer co nverted is
equal to il
h
R.
In certain cases, ho wever, the po tential dro p acro ss the Helm-
ho ltz layer do es no t remain co nstant under illuminatio n o r when
<P?edox changes. As a result, the po tential in the do uble layer is
redistributed and the pho to po tential beco mes lower than |<p?
e
dox ~
<Pfb|. This o ccurs, for example, on silico n, gallium arsenide, mo lyb-
denum diselenide, and certain o ther electro des in so lutio ns of
certain redo x co uples. In o ther wo rds, band-edge unpinning takes
place, which eventually goes over into Fermi-level pinning at the
semico nducto r surface. This is manifested in the fact that, as the
redo x co uple po tential <p gradually changes, the o pen-circuit
-1
OM 0.8 \y
ph
\V
Figure 13. Dependence of the abso lute value of
the o pen-circuit pho to po tential |^
ph
| on the redox
co uple equilibrium po tential:
58
WSe
2
pho to elec-
tro de (solid line, p-type; dashed line, n-type) in
aceto nitrile so lutio ns. Redox co uple (figures in
parentheses are charge numbers of the ox and
red co mpo nents): (1) anthracene (0/-1); (2)
phtalo nitrile (0/ - 1); (3) nitro benzene (0/ - 1);
(4) 2,2'-bipyridyl complex of ruthenium
(+2/+1); (5) azobenzene ( 0/ - 1) ; (6)
anthraquino ne (0/ - 1); (7) benzo quino ne (0/ -
1); (8) methyl viologen ( + 2/ + 1); (9)
tetracyano quino ne-dimethane ( + 1/0); (10)
tetramethyl-p-phenylenediamine ( + 1/0); (11)
tetraphenyl-/?-phenylenediamine ( + 1/0); (12)
I"/IJ; (13) Br7Br
3
'; (14) C1"/C1J; (15) thianthrene (+1/0); and (16) 2,2'-bipyridyl
complex of ruthenium (+3/+2). All the po tentials are given against the saturated
calomel electro de. (Reprinted by permission of the publisher, The Electrochemical
Society, Inc.)
pho to vo ltage of the cell <p
ph
first linearly increases with <p (band-
edge pinning) and eventually beco mes independent of <p (Fermi-
level pinning) (see Fig. 13).
The o rigins of this pheno meno n, which restricts significantly
the characteristics of pho to electro chemical cells for so lar energy
co nversio n into electricity, have no t so far been understo o d com-
pletely. Po ssible reaso ns might be the fo llo wing: (cf. Section III. 2):
stro ng charging of a semico nducto r electro de on appro aching the
Fermi level to the band-gap edges, for example, in the fo rmatio n
of an inversio n layer in a semico nducto r;
37
'
59
high density of surface
states;
35
'
36
and also the shift of the flat-band po tential in redo x
co uple so lutio ns because of partial o xidatio n (reductio n) of the
semico nducto r surface as a result of the chemical actio n of the
co mpo nents of these co uples, so that (p^ beco mes dependent on
<P?edox-
6
I
n
all these cases, the interphase po tential dro p is redis-
tributed between the space-charge layer and the Helmho ltz layer
in favor of the latter.
One may believe that for WSe
2
co nsidered here (see Fig. 13)
(and similar relatively wide-band-gap semico nducto rs), the seco nd
and third reaso ns seem to be the mo st pro bable (as far as the seco nd
reaso n is co ncerned, the assumptio n that the density of surface
states increases o n appro aching the band-gap edges is quite reaso n-
able). On the co ntrary, the fo rmatio n of a develo ped inversio n layer
in a sufficiently wide-band-gap semico nducto r (hence, the bulk
co ncentratio n of mino rity carriers is rather lo w), when the limiting
current of mino rity carriers flo ws in it, seems to be less pro bable.
In fact, mino rity carriers are efficiently extracted from a semi-
co nducto r so that their co ncentratio n appears to be negligibly
low even within the space-charge regio n and, under such co n-
ditio ns, this regio n represents an exhaustio n rather than an
inversio n layer.
1
The inversio n layer is, in fact, formed in a relatively narro w-gap
semico nducto r, germanium, in which the equilibrium bulk co n-
centratio n of mino rity carriers is sufficiently high. But the main
reaso n for band-edge unpinning in germanium, which is o bserved
practically over the who le po tential range accessible,
61
is either a
high density of energy-distributed surface states o r the change in
the dipo le po tential dro p caused by adso rptio n of water mo lecules
o n the electro de surface (for details, see Ref. 1).
3. P hotocorrosion and S tability
The quasi-thermo dynamic appro ach enables o ne to o btain a
criterio n fo r finding o ut whether a semico nducto r is liable to
(pho to )co rro sio n and suggest a way of preventing it.
15
Fo r example,
in the case of a binary semico nducto r MX (where M deno tes the
electro po sitive and X the electro negative co mpo nents) the equatio n
for a partial electro chemical reactio n of catho dic deco mpo sitio n
with co nductio n electro ns invo lved can be written in the form
MX + ne'^ M + X"~ (38a)
and the partial reactio n of ano dic deco mpo sitio n with ho les in-
vo lved as
MX+/ j
+
^ M
n +
+ X (38b)
If we cho o se for the example the hydro gen electro de as reference,
the o verall reactio n in a cell will pro ceed acco rding to o ne of the
fo llo wing equatio ns:
MX + ^H
2
M + n\\
+
+ X"- (F
dec
,J (39a)
MX + nW
+
* M"+ + X + ^H
2
(F
dec
,
p
) (39b)
(symbo ls in parentheses deno te the co rrespo nding electro chemical
po tential levels). Calculating the change in the free energy for these
reactio ns we can determine the standard equilibrium po tentials
<Pdec,n and <Pdec,
P
of the reactio ns of semico nducto r catho dic and
ano dic deco mpo sitio n, respectively (see Refs. 15-18).
The thermo dynamic co nditio n for an electro de reactio n to take
place (including the co rro sio n partial reactio n) can be written in
the form [cf. Eqs. (16a) and (16b))
 F
dec
,
n
(40a)
for a catho dic reactio n with co nductio n-band electro ns invo lved,
o r in the form
<P
O
dec,
P
o r F<F
dec
,
p
(40b)
for an ano dic reactio n with valence-band ho les invo lved.
r
dec,n
r
dec,p
r
dec,n
F
dec,p
''deep
E
c
F
dec,Ti
'
E
u
F
dec
y
p
(a) (b) (c) (d)
Figure 14. Diagram illustrating the thermo dynamic stability of a semico nducto r
electro de against deco mpo sitio n in the so lutio n: (a) semico nducto r is abso lutely
stable; (b) stable against catho dic deco mpo sitio n; (c) stable against ano dic
deco mpo sitio n; and (d) unstable.
In o rder to find o ut whether a semico nducto r is liable to
electro lytic o r co rro sio n deco mpo sitio n in any particular system,
let us co nsider the energy-band diagram which plo ts the
electro chemical po tential levels for the deco mpo sitio n reactio ns
(39a) and (39b).
Figure 14 schematically shows that vario us situatio ns are po ss-
ible here. The semico nducto r is stable against catho dic deco mpo si-
tio n if the electro chemical po tential level of the co rrespo nding
reactio n lies in the co nductio n band and against ano dic deco mpo si-
tio n if it lies in the valence band. In bo th cases, if the who le po tential
change o ccurs in the semico nducto r (band edge pinning at the
surface), this level is "inaccessible" to the Fermi level of the
semico nducto r. t Fo r example, in the case of Fig. 14a, the semico n-
ducto r is abso lutely stable because the levels of bo th deco mpo sitio n
reactio ns lie o utside the fo rbidden band. Ho wever, more frequent
are the cases where the semico nducto r is stable against only o ne
type of deco mpo sitio n: catho dic (Fig. 14b) o r ano dic (Fig. 14c).
Finally, if bo th levels F
dec n
and F
dec p
lie in the fo rbidden band
(Fig. 14d) the semico nducto r can, in principle, suffer deco mpo sitio n
bo th under ano dic and catho dic po larizatio n.
In the case of pho to co rro sio n, it is assumed within the
framework of the thermo dynamic appro ach that the shift of the
quasi-Fermi levels of electro ns F
n
and ho les F
p
is the cause of the
t The cases where Fermi-level pinning is observed are an exceptio n.
acceleratio n of a semico nducto r deco mpo sitio n reactio n under
illuminatio n. Co nditio ns (40a) and (40b) sho uld, therefo re, be
mo dified. The co nditio n for the reactio n of catho dic pho to -
deco mpo sitio n with co nductio n-band electro ns invo lved is no w of
the form [cf. Eqs. (36a) and (36b)]
F
n
> F
dec
,
n
(41a)
and fo r the reactio n of ano dic pho to deco mpo sitio n with ho les
invo lved
F
P
< F
deCtP
(41b)
If either (41a) o r (41b) is satisfied, the co rrespo nding reactio ns
beco me thermo dynamically favo rable.
It sho uld be no ted that kinetic restrictio ns may result in slo wing
do wn a reactio n. Indeed, in many cases it is the kinetic rather than
the thermo dynamic specific features of an electro de reactio n that
determine the co rro sio n (pho to co rro sio n) behavio r of semico nduc-
to r electro des.
While discussing the ways of preventing co rro sio n (pho to co r-
ro sio n), we have to take into acco unt that o ther reactio ns may take
place that co mpete with the pho to deco mpo sitio n pro cess. Fo r
example, as the illuminatio n intensity gro ws, amo ng all the po ssible
catho dic reactio ns the o ne that starts first is the reactio n who se
equilibrium po tential is mo st po sitive, while amo ng all the po ssible
ano dic reactio ns it is the reactio n with the mo st negative equilibrium
po tential that starts first. Thus, pho to co rro sio n of a semico nducto r
may, in principle, be suppressed if appro priate o xidizing o r reducing
agents are added to the so lutio n. Ano dic pho to co rro sio n can be
prevented by co uples who se redo x po tentials are mo re negative
than the deco mpo sitio n po tential: <p?
edox
< <Pdec,
P
(i-e., F
Tedox
>
Fdec,p) (see Fig. 15). As far as stabilizatio n against catho dic pho to -
deco mpo sitio n is co ncerned, the co rrespo nding co nditio n is
<Predox > <Pdec,n (OT F
r e d o x
< F
d e c n
) .
Such pro tecting systems are o xidized o r reduced, thereby
stabilizing semico nducto r pho to electro des, and this effect is used
in pho to electro chemical cells fo r so lar energy co nversio n.
62
"
65
The
so lvent (e. g. , water) can also act as a pro tecto r if it is o xidized
(reduced) easier than the semico nducto r electro de material. Situ-
atio ns like this arise with many o xide electro des (TiO
2
, SrTiO
3
,
E
231
Figure 15. Diagram illustrating pro tec-
tio n of an n-type semico nducto r against
ano dic pho to deco mpo sitio n with the aid
of a redox co uple intro duced into the sol-
utio n.
redox
r
dec,p
etc.) where o xidatio n of water to oxygen is the most pro bable ano dic
pho to reactio n.
Let us co nsider, as an example, the pho to co rro sio n behavio r
of GaAs and GaP in aqueo us so lutio ns. The levels of the
electro chemical po tential of deco mpo sitio n reactio ns for these
materials are shown in Fig. 16 to gether with the levels E
c
and E
v
.
-1.5
-1
'0.5
0.5
r
dec,n
r
dec,p
Electrolyte
dec,j\
F
de~
GaAs Electrolyte
&aP
Figure 16. Energy levels at the junctio n between GaAs, GaP, and an
aqueo us so lutio n (pH = 7).
66
All the po tentials are given against the
no rmal hydro gen electro de. (Reprinted by permission of the publisher,
The Electrochemical Society, Inc.)
Fo r GaAs, F
dec
co rrespo nds to the reactio n GaAs 4- 3H
+
4
3e ~ ^ Ga 4 As H
3
and F
de c p
to the reactio n GaAs + 5H
2
O 4
6h
+
zGa(OH)
3
4- HAsO
2
4- 6H
+
. In the case of GaP, F
decn
co rre-
spo nds to the reactio n GaP 4 3 H
+
4 3 e ~ ^ Ga 4 PH
3
and F
deCtP
to
the reactio n GaP + 6H
2
O + 6h
+
z Ga(OH)
3
4 H
3
PO
3
4 6H
+
.
Co mpariso n with Fig. 14 sho ws that the behavio r of GaAs co rre-
spo nds to the case of Fig. 14b, i.e., it is stable against catho dic
deco mpo sitio n, but po tentially unstable against ano dic deco mpo si-
tio n; o n the o ther hand, GaP is po tentially liable bo th to catho dic
and ano dic deco mpo sitio n, since the levels of the co rrespo nding
reactio ns lie in the fo rbidden band (the case of Fig. 14d).
4. The L imits of A pplicability of the Quasi-Fermi Level C oncept in
P hotoelectrochemical K inetics: A lternative A pproaches
It is clear from the abo ve co nsideratio ns that the quasithermo dy-
namic appro ach, based o n the co ncept of quasi-Fermi levels, is
sufficiently widespread and what is mo st impo rtant is that it is
efficient. Obvio usness and simplicityhere are its indisputable
advantages. At the same time, it sho uld be no ted that the use of
the quasi-Fermi-level co ncept canno t be justified in all cases. At
any rate, the applicability of this co ncept requires that the fo llo wing
inequalities,
r
c
, r
v
< r
cv
(42)
be satisfied. Here r
c
and r
v
are the times of the establishment of a
thermo dynamic equilibrium separately in an ensemble of electro ns
in the co nductio n band and ho les in the valence band, and r
CyV
is
the time needed fo r an equilibrium to be established between the
electro n and ho le ensembles. As was already mentio ned, the
o rdinary mechanism thro ugh which an equilibrium is attained in
the bands is the interactio n of excited electro ns and ho les with
pho no ns; in certain semico nducto rs this mechanism depends o n
the interactio n between pho to excited and thermalized carriers
o ccurring separately in each band. The values of r
c
and r
v
are of
the o rder of 10~
12
-10~
13
s. The time r
cv
is related to the interactio n
of electro ns and ho les with o ne ano ther and, in the simplest case,
it co incides with the reco mbinatio n time. Fo r mo st semico nducto r
materials this time is much larger than 10~
12
-10~
13
s so that co ndi-
tio n (42) is usually satisfied.
At the same time, these co nditio ns alo ne are insufficient to
describe electro n transfer pro cesses at the interface within the
framework of the appro ach discussed. Let us intro duce the times
r
ns
and r
ps
, which characterize the time interval between pho to exci-
tatio n of an electro n and a ho le, respectively, and co nsumptio n of
this particle at the surface thro ugh, for example, an electro de
reactio n. Apparently, the co ncept of the quasi-Fermi levels can be
used to describe such pro cesses if only these times are larger than
T
C
and T
V
. Otherwise, the quasiequilibrium do es no t have eno ugh
time to be established, and "ho t" particles will be directly involved
in the electro de pro cess. On the o ther hand, the times r
n s
and r
ps
must be less than r
cv
because, if this is no t the case, co mplete
equilibrium will be established in the electro n-ho le system, so that
the equality F
n
= F
p
= F will ho ld at the interface. Thus, the
following two systems of inequalitiest:
Tc < T
n
,
s
< T
cv
, T
v
< T
A S
< T
cv
(43)
must be satisfied in o rder that the co ncept of the quasi-Fermi levels
can be applied effectively to electro ns and ho les involved in a
hetero geneo us pro cess at the interface.
In the case of fast co nsumptio n of electro ns and ho les at the
surface, the times r
ns
and r
ps
co incide with tho se of the appro ach
of electro ns and ho les to the interface. Suppo se that the penetratio n
depth of light in a semico nducto r, a"
1
, exceeds the thickness L
sc
of the space-charge regio n. If L
sc
is much less than the mino rity-
carrier diffusion length (L
p
o r L
n
), then, by an o rder of magnitude,
T
p
,
s
a~
2
/2
p
and r
ns
a~
2
/Q)
n
. This implies, in particular, that
if a"
1
exceeds no t only L
sc
but also L
p
(o r L
n
) the co nditio n r
ps
< r
cv
do es no t ho ld for mino rity carriers. Fro m the physical po int of
view, this o bvio usly means that if a~
l
L
p
(o r a"
1
L
n
) an equili-
brium is established in a system during the time the carriers
appro ach the interface.
On the co ntrary, if the co nditio n a~
l
< L
sc
applies and when
a depletio n layer is fo rmed, the time for the carriers to appro ach
the interface is determined by migratio n in the space-charge field,
rather than by diffusion (as befo re). Under such co nditio ns, r
ps
(o r
r
ns
) is of the o rder of a"
1
/'v, where v is the migratio n velo city.
t If an electro de reactio n pro ceeds with only one type of carrier involved, it is
sufficient that only one system of inequalities be satisfied.
Estimates show that a~
x
/v is 10~
13
-10~
n
s, so that the inequalities
(43) may ho ld under such co nditio ns.
If the surface pro cess pro per canno t be co nsidered infinitely
fast, the times r
ns
and r
PtS
can be limited by the duratio n of this
pro cess; for example, by the duratio n of an elementary act of an
electro de reactio n.
Thus, since the time interval between r
c
and T
V
, on the o ne
hand, and r
CV9
on the o ther hand, is sufficiently large (from 10~
13
to 10~
8
s), the time characteristics of many electro de pro cesses
satisfy co nditio ns (43). Therefo re, the co ncept of quasi-Fermi levels
has a rather wide range of applicatio n. At the same time, quantitative
descriptio n (see, e.g., Ref. 67) requires that certain additio nal co ndi-
tio ns sho uld be satisfied. It is necessary, in particular, that the
quasi-level behavio r in the space-charge regio n be sufficiently
smo o th; the latter co nditio n ho lds true if a"
1
L
sc
and reco mbina-
tio n in the space-charge regio n is weak. It is o bvio us, on the o ther
hand, that if pho to generatio n of carriers o ccurs mainly near the
surface where a fast electro de reactio n takes place, a situatio n is
po ssible when pho to generated carriers will be extracted from the
semico nducto r more rapidly than they will come into equilibrium
with thermalized carriers in the co rrespo nding band. Under such
co nditio ns, they canno t be characterized by quasiequilibrium levels
F
n
and F
p
. Apparently, it wo uld be mo re co rrect to co nsider, in
this case, the transitio n of carriers from the electro de into the
so lutio n in a purely dynamical way, as individual independent
events, rather than thro ugh the quasiequilibrium stage.
49
'
68
"
70
As an illustratio n, let us co nsider an attempt
70
at a quantitative
descriptio n of this dynamical pro cess. Acco rding to the mo del used
in Reference 70, of major impo rtance are quantum levels which
arise near the interface in the case of stro ng band bending (see
Section II. 2). Only a fractio n of pho to generated electro ns (o r ho les)
is thermalized and then they beco me lo calized on these quantum
levels. Further thermalizatio n pro ceeds so slowly that an electro de
reactio n readily takes place befo re thermalizatio n. This reactio n
can be described as the tunneling of an electro n from a quantum
level in a triangular well near the interface thro ugh a o ne-
dimensio nal po tential barrier into a o ne-dimensio nal square well
which simulates the reactant in the so lutio n (Fig. 17). It is assumed
that after tunneling has o ccurred the so lvent rearranges aro und the
235
Fig. 17. Diagram elucidating the model for the
descriptio n of the tunneling of "ho t" electro ns from Electrolyte
the semico nducto r to the reactant in the so lutio n.
Semiconductor
reactant quite rapidly, so that the reverse electro n transitio n to the
electro de is impo ssible.
One may believe that in certain cases this mo del describes
adequately electro n (ho le) transitio ns in do ped wide-band-gap
semico nducto rs with a small effective mass for sufficiently stro ng
band bending. At the same time, the mo del emplo yed is to o ro ugh
for quantitative agreement with experiment to be expected
(especially if we take into acco unt that the descriptio n is o ne-
dimensio nal).
Using experimental data, we can, in principle, decide between
two appro achesquasithermo dynamic and dynamicto the
descriptio n of the kinetics of pho to electro chemical reactio ns. The
first appro ach (based o n the quasilevel co ncept) predicts the
existence of a certain thresho ld illuminatio n intensity for the case
where an equilibrium at the semico nducto r/so lutio n interface is
no t established in darkness. In fact, if an electro de reactio n is
slowed do wn in darkness, the levels F and F
redo x
take an arbitrary
po sitio n with respect to each o ther. Under illuminatio n, the level
F splits into F
n
and F
p
, so that F
p
moves farther away from F as
the illuminatio n intensity grows and may reach F
redo x
at a certain
thresho ld value of the intensity. Fo r lo wer illuminatio n intensities,
a pho to electro chemical reactio n canno t take place, acco rding to
the quasithermo dynamic appro ach. On the co ntrary, in the dynamic
appro ach a pho to reactio n do es pro ceed for any illuminatio n
intensity.
This thresho ld has no t so far beeen o bserved experimentally.
Fo r example, in the pho to evo lutio n of oxygen on TiO
2
the pho to cur-
rent grows mo no to no usly with illuminatio n intensity within a very
wide range of intensities (from 10~
6
to 4 x 10
2
Wcm"
2
).
69
On the
o ther hand, until quite recently, investigatio ns have been perfo rmed
on semico nducto rs with very wide band gaps and, hence, negligibly
low co ncentratio ns of mino rity carriers p
0
(o r n
0
). Fo r such
materials, the thresho ld illuminatio n intensity, determined by the
ratio Ap/po (
r
An/n
0
), can be to o low to be detected in an
experiment. Thus, no reliable data are available at present to decide
co nvincingly between the two appro aches discussed here. This
remains a pro blem for the future.
V. N E W A P P L I C A T I O N S
1. P hotoelectrochemical C onversion of S olar Energy
Since semico nducto r electro des are pho to sensitive, the semico nduc-
to r/electro lyte interface is po tentially applicable for interco nverting
the energy of light.
71
In Sectio n IV.2 we have co nsidered in brief
the mechanism of the o ccurrence of pho to currents on a semico nduc-
to r electro de for the two most impo rtant cases: namely, in the
presence of a highly reversible redo x co uple in the so lutio n and in
the absence of such a co uple (i.e., under co nditio ns when the
electro chemical reactio n is slowed down in darkness). In the first
case, the energy of the light is co nverted into electrical energy, and
in the seco nd case into chemical energy. Such pho to electro chemical
cells are called "liquid junctio n so lar cells" (o r pho to elec-
tro chemical cells of the regenerative type) and the pho to electro lysis
cell, respectively. Among vario us pho to electro lysis reactio ns of
most interest is pho to electro lysis of water as a po ssible so urce of
hydro gen fuel and raw material.
The mo st impo rtant advantage of pho to electro chemical cells
with semico nducto r electro des, as co mpared to , for example, so lid-
state semico nducto r so lar cells, is a relatively low sensitivity of their
characteristics to the crystalline perfectio n of the semico nducto r
and the degree of its purificatio n. Po lycrystalline semico nducto r
electro des in electro chemical "so lar cells" exhibit bo th high
abso lute and high relative (as co mpared to single-crystal electro des)
co nversio n efficiency. This o pens, at least in principle, the way of
pro ducing inexpensive and techno lo gically simple so lar energy
co nverters.
The mechanism of o peratio n of pho to electro chemical cells and
the characteristics of particular systems have been co nsidered in
detail in review articles
52
'
62
"
65
'
69
'
72
"
74
and in a mo no graphy
7
; there-
fo re, these to pics are beyo nd the sco pe of the present review. It
seems reaso nable, ho wever, to co ncentrate here on the most impo r-
tant pro blems, which are to be so lved befo re pho to electro chemical
cells find extensive practical applicatio n.
The main o bstacle to creating "liquid junctio n so lar cells" is
pho to co rro sio n of semico nducto r electro des, which reduces
co nsiderably their lifetime. In o rder to prevent, for example,
ano dic pho to co rro sio n, a well-reversible redo x co uple is intro duced
into an electro lyte so lutio n, so that the reactio n of o xidatio n of the
red co mpo nent co mpetes for pho to ho les with the reactio n of
pho to deco mpo sitio n of the electro de material (see Section IV.2).
With the aid of this metho d, pho to co rro sio n has been practically
prevented in certain types of pho to cells and the duratio n of their
co ntinuo us o peratio n has been increased up to abo ut o ne year. Yet,
there are o ther, mo re subtle mechanisms of electro de degra-
datio n,
65
'
75
which has hitherto prevented the lifetime of pho to -
electro chemical cells from beco ming co mparable with the 20-year
lifetime of so lid-state so lar cells.
The most essential pro blem in pho to electro lysis is the "match-
ing" of the energetics of an electro chemical reactio n with the
spectrum of so lar radiatio n. The energy distributio n of pho to ns in
the so lar spectrum is such that the o ptimal thresho ld energy for
the quantum co nversio n pro cess (and it is this type of co nversio n
that is o btained with semico nducto r electro des) lies in the range
1.1-1.4 eV. The change in the free energy of the reactio n of
electro chemical splitting of water into hydro gen and oxygen is
1.23 eV, i.e., it falls into this range but, in practice, this pro cess
pro ceeds with a co nsiderable o vervo ltage. If additio nal inevitable
energy lo sses are taken into acco unt, the energy of a quantum
needed for pho to electro chemical deco mpo sitio n of water increases
to abo ut 2 eV,
72
'
74
i.e., it exceeds significantly the abo ve value. In
o ther wo rds, only a relatively small fractio n of harder quanta in
the so lar spectrum can be used directly for pho to electro lysis of
water. We sho uld stress that this circumstance is in no way an
incidental o ne. On the co ntrary, the fact that precisely this situatio n
o ccurs in nature eventually ensures a relative stability of extremely
diverse animate and inanimate systems against so lar radiatio n.
Ho wever, this o bstacle can, in principle, be o verco me in several
ways.
1. Realization of the process in the photostimulated electrolysis
regime. In this case, the main fractio n of quanta of so lar radiatio n
is utilized to generate a pho to electro chemical reactio n, and the
deficient (for the necessary 2 eV) energy is supplied with the aid
of an external vo ltage so urce. The greatest pro gress in this directio n
has been reached in Reference 76.
2. Realization of a "two-quantum" type process. Co mbining
two semico nducto r pho to electro des (an n-type ano de and a p-type
catho de) in a single pho to electro chemical cell and cho o sing
appro priately the characteristics of bo th electro des, we can o btain
an effective summatio n of pho to po tentials develo ped acro ss each
of the electro des and pro duce the energy sufficient for pho to elec-
tro lysis of water.
77
'
78
An alternative way is to divide the o verall pro cess of water
splitting into two stages, each being co nducted in a separate pho to -
electro chemical cell. Both cells are co upled with the aid of a certain
intermediate substance, which acts as a charge transfer agent and
is no t co nsumed in the co urse of the o verall pro cess, but only
pro vides the co nnectio n in series of the chemical po tentials
develo ped in bo th cells.
7
'
79
Apparently, such a scheme imitates the
co mbinatio n of two pho to systems in pho to synthesis o ccurring in
green plants.
Each of the ways co nsidered abo ve utilizes two pho to elec-
tro des, so that the o verall pro cess is formally a two -quantum o ne,
which permits, in principle, the necessary gain in the energetics to
be o btained.
3. Division of the overall process into two stages:production
of electricity and water electrolysis proper*
0
*
2
Let us replace a single
pho to electro chemical cell by the co mbinatio n of a so lar cell (so lid
state o r "liquid junctio n") and an o rdinary electro lyzer. In this
case, pro ductio n of electricity and electro lytic deco mpo sitio n of
water, which are co mbined in a pho to electro lysis cell, appear to
be distributed between two specially designed devices. This enables
the necessary vo ltage to be attained by co nnecting in series several
so lar cells and also pro vides extensive po tentialities for cho o sing
the o ptimal pho to electric and electro catalytic pro perties of the
electro de materials emplo yed.
4. Dehydration of inexpensive and readily available organic
substances. Since hydro gen is, in fact, the only desirable final
pro duct, this appro ach is based o n giving up the idea that only
water sho uld necessarily be utilized in pho to electro lysis. Ano ther
electro chemical reactio n can be cho sen, which is characterized by
a lesser change in the free energy, for example, dehydratio n of
industrial waste pro ducts. Pho to electro chemical pro cesses of this
type have been studied intensively in recent years.
64
'
83
"
87
Of interest are also systems in which the thermal (IR) po rtio n
of the so lar spectrum is used besides visible light
88
and also systems
which emplo y no ntraditio nal pro cesses such as pho to intercalatio n
of ato ms into the crystal lattice of a semico nducto r.
89
One may believe that the current intensive efforts will event-
ually be cro wned with the develo pment of simple, eco no mically
reaso nable, pho to electro chemical pro cesses capable of co mpeting
with o ther, no nelectro chemical metho ds of utilizing so lar energy.
2. L aser E tching of S emiconductors
An intensive develo pment of quantum o ptics has led to the emer-
gence of a new field, laser electro chemistry of semico nducto rs (for
reviews see Refs. 90 and 91). It covers the range of pro blems related
to electro chemical pro cesses on semico nducto r electro des stimu-
lated by laser radiatio n. The greatest pro gress in this directio n has
been achieved in the light-sensitive etching of semico nducto rs by
co herent laser radiatio n, which can be used for reco rding o ptical
info rmatio n, for example, for pro ducing ho lo grams.
92
Light-sensitive etching with po larizatio n from an external
so urce is called pho to ano dic etching, and that in an o xidizing
so lutio n, pho to chemical etching.
Light-sensitive etching is based o n the change, due to illumina-
tio n, in the mino rity-carrier co ncentratio n, which determines the
rate of ano dic disso lutio n and co rro sio n of semico nducto rs. Fo r
example, under illuminatio n of an n-type semico nducto r in the
ano dic po larizatio n regime, the etching rate can be limited by the
rate of ho le supply to the electro de surface. In darkness, a certain,
usually lo w, disso lutio n rate is established o n such electro des.
Illuminatio n is an additio nal so urce of ho les (pho to generatio n), so
that illuminated areas are disso lved mo re rapidly than no nillumi-
nated o nes.
Illuminatio n of a semico nducto r under o pen-circuit co nditio ns
in an etching (o xidizing) so lutio n gives rise to co rro sio n even in
darkness. In the simplest case where the catho dic partial reactio n
of a co rro sio n pro cess pro ceeds exclusively thro ugh the co nductio n
band and the ano dic o ne thro ugh the valence band, the co rro sio n
rate for specimens of any co nductivity type is limited by the mino r-
ity-carrier supply to the surface and is therefo re low in darkness.
Illuminatio n accelerates co rro sio n pro cesses. Co mpariso n with the
case co nsidered abo ve shows that here the "chemical" po larizatio n
of the semico nducto r by an o xidizer intro duced into the so lutio n
acts as ano dic po larizatio n.
In laser etching, the initially flat surface of a semico nducto r
in an electro lyte so lutio n is illuminated (thro ugh the so lutio n) by
two co herent light beams of the same intensity and wavelength
incident at equal angles and lying in the same plane (Fig. 18).
Interference of these beams pro duces illuminated and dark regio ns
(fringes) at the interface and stimulates no nunifo rm etching of the
surface.
In simple cases but o nes that are impo rtant for practical appli-
catio ns, the theo ry of laser etching
90
'
93
yields an analytical
expressio n for the characteristics of the relief pro duced as a functio n
Beam 2
BeamU
Electrolyte
Figure 18. Schematic diagram of the
illuminatio n of a surface in laser light-
Semiconductor sensitive etching.
of radiatio n parameters, semico nducto r pro perties, and specific
features of the electro de reactio n. In brief, the results of the calcula-
tio ns are as fo llo ws. The profile of the relief pro duced (diffraction
grating) is rather close to a sinuso idal o ne. In the case of "surface-
abso rbed" light (large value of the abso rptio n coefficient) and fast
electro chemical reactio n (large value of the rate co nstant) the spatial
frequency of the relief d (its dimensio n is the inverse length) is
very high. Fro m the physical po int of view this means that if ho les
are generated in close pro ximity to the surface and are co nsumed
immediately, the diffusion of pho to generated ho les can be neglected
beyo nd the limits of illuminated areas of the surface.
Thus, the reso lutio n of light-sensitive etching, i.e., the maximal
value d~
x
attained, is no t determined, in acco rdance with the abo ve
co nsideratio n, by the diffusion length L
p
, as might be expected a
priori (a'
1
L
p
), but is much higher.
In practice, the laser beam of an appro priate wavelength is
first expanded to a diameter of 10-20 mm and then is split (with
the aid of two mirro rs) into two beams of equal intensity, which
intersect at the surface of an electro de immersed in an electro lyte
so lutio n (Fig. 18).
The quality of the relief o btained can be evaluated directly in
the co urse of etching because the light reflected from the grating
pro duces a diffraction pattern, which characterizes the depth and
shape of the grating profile at any mo ment. To this end, o ne simply
measures the reflected light intensity. The sensitivity of the metho d
is high: the o ccurrence of the relief can be o bserved when its depth
is only 0.01/u.
Light-sensitive laser etching has been emplo yed to pro duce
diffraction gratings on many single-crystal semico nducto rs (Ge, Si,
GaAs, GaP, CdS, CdSe) and also o n semico nducting films, includ-
ing po lycrystalline CdSe, CdTe, As
2
Te
3
, InSe, GaSe, Cu
2
O, and
GeO and glassy Ag
2
Se
3
.
The profile of the relief etched is usually rather close to a
sinuso idal o ne. The po tentialities of the metho ds can be seen from
Table 1, which presents for certain of the afo rementio ned materials
the following parameters: the maximal spatial frequency d^l*
attained for the gratings reco rded (the maximal number of
gro o ves/mm), the wavelength of the reco rding light A, and the
diffusion length L
p
of mino rity carriers in the specimens.
T able 1
C haracteristics of Diffraction Gratings P roduced by the
L ight-S ensitive E tching M ethod
Semico nducto r
CdSe
CdS
Si
As
2
Se
3
GaAs
GaAsP
As
2
Te
3
Ge
A (nm)
Pho to ano dic etching
2600
6150
2500
2600
632. 8
441. 6
514.5
632. 8
Pho to chemical etching
5000-6000
2700
2600
1000
441. 6
632. 8
632. 8
L
p
(cm)
10"
4
10~
4
10"
2
10"
4
10"
1
References
94
95
92
96
93
97
96
53
The table shows that the reso lutio n of the pho to electro chemical
metho d of info rmatio n reco rding is sufficiently highmore than
6000 mm"
1
. It sho uld be stressed that for materials with large
diffusion lengths, L
p
(germanium, silico n), the reso lutio n, as was
predicted by the theo ry, pro ves to be much higher than might be
expected from the values of L
p
.
Co mpariso n of light-sensitive laser etching with the most wide-
spread no nelectro chemical metho ds, such as ho lo gram reco rding
on plates and also pho to litho graphy (i.e., etching thro ugh a mask
pro duced with the aid of pho to resists), shows that reso lutio n of all
these metho ds is appro ximately the same. As the spatial frequency
of the reco rding light beam increases, the pho to etching metho ds
are expected to beco me mo re advantageo us o ver, in particular,
pho to litho graphy, since the relief is pro duced directly on the semi-
co nducto r surface, rather than in an auxiliary pho to resist layer.
The latter circumstance also makes it easier to o btain a regular
sinuso idal profile of the diffraction grating.
Let us no te in co nclusio n that light-sensitive etching is by no
means the o nly pro blem in the field of laser electro chemistry. It
includes, for example, thresho ld electro chemical reactio ns stimu-
lated by intensive laser radiatio n. Such reactio ns may pro ceed via
new schemes and, therefo re, yield new pro ducts because bo th highly
excited so lutio n co mpo nents and a no nequilibrium electro n-ho le
243
plasma of the semico nducto r are invo lved. This o pens an o ppo r-
tunity for develo ping unusual pro cesses in chemical techno lo gy.
3. T he I on-S elective Field-E ffect T ransistor
Jo ining of an io n-selective electro de and a field-effect transisto r
(FET) in a single device has made it po ssible to create a new type
of io n co ncentratio n detecto r called the io n-selective field-effect
transisto r (ISFET. ) High sensitivity and selectivity, as well as the
very small size of this device, have resulted in its co nstantly growing
applicatio ns in recent years in industry, medicine, bio lo gy, scientific
research, etc.
Since the ISFET is based o n the field-effect transisto r, let us
recall briefly how the latter o perates (see, e.g., Ref. 98). The field-
effect transisto r (Fig. 19a) represents the so -called MIS (metal-
insulato r-semico nducto r) structure (hence the abbreviatio n MIS-
FET), i.e., a semico nducto r base, o nto which an insulating layer
and a metal "electro de" (gate) are depo sited. The base usually is
a p-type silico n plate and the insulato r, a SiO
2
o r Si
3
N
4
layer. With
a thickness of 100-200 nm, the resistance of this layer is of the
o rder of 10
13
Cl. Two regio ns are pro duced in the base by lo cal
Figure 19. Schematic diagram of the (a) field-effect transisto r and
(b) ion-selective field-effect transisto r: (1) base, (2) source and drain,
(3) insulating layer, (4) gate, (5) low-ohmic electric circuit, (6)
high-ohmic electric circuit, (7) io n-selective membrane, (8) reference
electro de, and (9) electro lyte so lutio n under investigatio n.
do ping with an appro priate impurity, in which the type of silico n
co nductivity is made reverse. These regio ns (o f n-type) are called
so urce and drain. Co nnecting external vo ltage so urces to the gate
base and so urce-drain circuits, as sho wn in Fig. 19a, we can realize
a field effect in the transisto r. Namely, with no vo ltage o n the gate,
the current in the so urce-drain circuit is practically absent, since
o ne of the p-n junctio ns in this circuit is reverse biased. Let us
no w apply a vo ltage to the gate of such a po larity and magnitude
that an inversio n layer is fo rmed in the base near the silico n/insu-
lato r interface (in the case of Fig. 19a a po sitive vo ltage, with respect
to the base, must be applied to the gate). An n-type "channel,"
which arises in this case sho rt circuits the so urce and drain, thereby
enabling an electric current to flow in the so urce-drain circuit who se
o hmic resistance appears to be rather lo w, o nly several tens of
o hms. Thus, by varying the vo ltage in the high-o hmic gate-base
circuit we can efficiently co ntro l the current in the lo w-o hmic
so urce-drain circuit. In o ther wo rds, this device has a very large
current multiplicatio n facto r.
This feature of the FET is transfo rmed into high sensitivity in
the ISFET. That is, in o rder to go o ver from the FET to the ISFET
it is sufficient to replace the insulating layer by an io n-selective
membrane permeable o nly to o ne so rt of io nt and the metal gate
by an electro lyte so lutio n, which co ntains a reference electro de
needed to sho rt circuit the electric circuit (Fig. 19b). The po tential,
which develo ps acro ss the membrane in the presence in the so lutio n
of that so rt of io ns for which the membrane is selectively permeable,
acts here as an external vo ltage o n the gate. This po tential can be
determined from Nernst's equatio n [cf. Eq. (4)]
RT
<P=<Po + \na (44)
where a and z are the activity (co ncentratio n, in the simplest case)
and charge number of po tential-determining io ns, respectively, and
<Po is the standard po tential (i. e. , the value of <p fo r a = 1 mo l dm"
3
).
With this mechanism of the fo rmatio n of po tential acro ss the
membrane, the current in the measuring circuit depends o n the io n
activity a, which makes the ISFET a very sensitive io n detecto r.
t In certain types of ISFET, the membrane is depo sited directly o nto the insulating
layer, so that we deal with a "fo ur-layer" structure.
Particular types of the ISFET are very diverse, since there is
a po ssibility of widely varying the membrane co mpo sitio n, the type
of reference electro de, the mo de of o peratio n (e.g., an additio nal
po larizing vo ltage can be used), etc.
The survey of the most impo rtant systems of this type, their
characteristics, and po ssible applicatio ns can be fo und, for example,
in the reviews.
90
'
100
4. C haracterization of S emiconducting M aterials
A certain relatio nship, which exists between the bulk and surface
pro perties of semico nducting materials and their electro chemical
behavio r, enables, in principle, electro chemical measurements to
be used to characterize these materials. Since 1960, when Dewald
39
was the first to determine the do no r co ncentratio n in a zinc o xide
electro de using Mo tt-Scho ttky plo ts, differential capacity measure-
ments have frequently been used for this purpo se in several
materials. If po ssible so urces of erro rs that were discussed in Section
III. 3 are taken into acco unt co rrectly, the capacity metho d enables
o ne to determine the distributio n of the do ping impurity co ncentra-
tio n over the surface
40
and, in co mbinatio n with the layer-by-layer
etching metho d, also into the specimen depth.
101102
The impurity
co ncentratio n profile can be co nstructed by this metho d. It has
recently been develo ped in greatest detail as applied to gallium
arsenide crystals and multilayer structures.
103
Several metho ds of ano dic (pho to ano dic in particular) etching
have been suggested in the literature to reveal vario us
inho mo geneities in the structure and co mpo sitio n of semico nduct-
ing crystals (see, e.g., Refs. 104-106).
VI . C O N C L UDI N G R E M A R K S
It has no t been po ssible in the present review to cover all the
diversity of new ideas and appro aches that have been develo ped
in the electro chemistry of semico nducto rs. Therefo re, in co nclusio n
we wo uld like to no te tho se directio ns which seem to us the most
interesting and pro mising (tho ugh so me of them have no t so far
been develo ped extensively because of o ne reaso n or ano ther which
are frequently of mo mentary character); several such directio ns
have been discussed in o ur mo no graph.
7
1. New systems. Among new (for electro chemistry) semi-
co nducting materials, tho se with so -called layered crystal lattices
107
seem to be quite pro mising in view of their practical applicatio ns.
It is assumed that, being d-semico nducto rs, they may be mo re
stable against pho to co rro sio n than s/?-semiconductors that were
mainly co nsidered abo ve; mo reo ver, they allow photoelec-*
tro chemical reactio ns of no ntraditio nal types to be realized, for
example, (pho to )intercalatio n of ato ms from the so lutio n into the
semico nducto r electro de crystal lattice. As far as materials for
pho to electro des of pho to electro chemical cells are co ncerned, d-
band semico nducto rs are of great interest. Synthesis and investiga-
tio n of new materials with appro priate pho to electrical and
electro chemical pro perties are impo rtant directio ns in the
"electro chemical materials science" of semico nducto rs (see, e.g.,
Ref. 108).
Quite pro mising may be the study of pho to electro chemical
pro perties of micro hetero geneo us semico nducto r systems (po ro us
electro des, suspensio ns of different degrees of dispersio n up to
co llo idal so lutio ns), in which pho to sensitivity inherent in semico n-
ducto rs is co mbined with high electro catalytic activity typical of
systems with a develo ped surface.
Mo dificatio n of the surface of semico nducto r electro des by
catalysts (mediato rs) "attached" to it
109
also deserves intensive
investigatio n.
Finally, in recent years there has been a new surge of develo p-
ment in the field of thin-film electro chemistry, especially in view
of practical applicatio ns. The thickness of films in such systems
ranges from several angstro ms to hundreds of angstro ms; in the
latter case, the films often po sess semico nducting pro perties.
2. New methods of investigation. It may be expected that
fresh impo rtant info rmatio n will be gained with the aid of new
metho ds, bo th develo ped directly within the framework of the
electro chemistry of semico nducto rs and metals and bo rro wed from
o ther fields, foremost of which is the physics of surfaces; the latter
metho ds are usually called no ntraditio nal.
Among traditio nal electro chemical metho ds we may no te the
estance metho d based o n the elastic change in surface stress
110
(it
has recently been used
111
to study semico nducto r electro des), and
also the metho d of the ro tating ring-disc electro de
112
in its vario us
special mo dificatio ns.
113
In recent years, co mputer-based measuring
devices have been designed for determining vario us characteristics
of semico nducto r electro des.
114
"
116
The no ntraditio nal metho ds are mainly related to the effect of
illuminatio n on the interface. Here we sho uld mentio n foremost
pho to temperature spectro sco py, which permits o ne to determine,
by measuring the change in the pho to electro de temperature, what
fractio n of the energy of light abso rbed is co nsumed in a pho to elec-
tro chemical reactio n and what fractio n is co nverted into heat, and
thus permits o ne to find the "true" quantum yield
117118
; hightime-
reso lutio n measurement of pho to currents induced by nano seco nd
laser pulses
119120
; and electro generated luminescence allo wing re-
co mbinatio n pro cesses in electro des to be studied
121
as well as
pho to emissio n of electro ns from semico nducto rs into electro lyte
so lutio ns
25
and electro reflectio n of light at the semico nducto r/elec-
tro lyte interface.
122
To this gro up of metho ds we may also refer
pho to aco ustic spectro sco py, which reveals mo re subtle features of
light abso rptio n in semico nducto rs.
123
'
124
Thus, o n the o ne hand, it may be believed that a mo re o r less
adequate picture of the electro chemical behavio r of semico nducto rs
has already been established; but, o n the o ther hand, as far as the
number and impo rtance of new pro blems are co ncerned, the elec-
tro chemistry of semico nducto rs may be co nsidered still a rapidly
develo ping branch of mo dern science.
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S urface-E nhanced Raman S cattering (S E R S )
S. Efrimaf
Department of Chemistry, Ben-Gurwn University of The Negev, Beer-Sheva, Israel
84105
I . I N T R O DUC T I O N
Surface-enhanced Raman scattering is a pheno meno n where the
cro ss sectio n for Raman scattering for mo lecules adso rbed on some
surfaces is enhanced by many o rders of magnitude co mpared to
the scattering cro ss sectio n for the same mo lecule in the bulkin
so lutio n, for example.
This pheno meno n was stumbled upo n in the quest of elec-
tro chemists for techniques which will allow identificatio n of
mo lecular species in the interphase and which will yield structural
info rmatio n o n the mo lecular level.
1
"
4
The initial pio neering work
was quickly fo llo wed
57
by the realizatio n that some unexpected
behavio r was being o bserved. Imaginatio ns were immediately
kindled and much work has been do ne and repo rted, most of which
was directed to attempts to understand the mechanism (o r mechan-
isms) respo nsible for the "giant" enhancements of the scattering
seen.
In this review it is no t the intentio n to deal with the past per
se, so no attempt will be made to give an histo rical presentatio n of
SERS. Rather, a descriptio n of the present state of experimental
kno wledge and theo retical understanding will be given with
emphasis o n the electro chemical systems studied. The aim is to
t B at S heva fellow
253
254 S . E frima
present a summary of the experimental results and a simple expo si-
tio n of the theo retical mo dels, having in mind physical insight
rather than rigo r. A seco nd part of this review will be devo ted to
a discussio n of po ssible ways SERS has been used and can be used
for the investigatio n of interfaces and surface pro cesses. We will
see that tho ugh the main thrust of the field in the past was no t in
this directio n, many interesting results pertaining to structure and
chemistry at the interface have been o btained.
The gro wth of research in the area called to day "surface-
enhanced Raman scattering (o r spectro sco py)" (SERS) has no t
been a regular o ne. One may co mpare it mo re to an irregular, almo st
chao tic, depo sitio n from a supersaturated so lutio n rather than to
a smo o th, epitaxial well-co rrelated gro wth. Many gro ups, from a
variety of disciplines, have jo ined the SERS game in a very sho rt
time. This bro ught to the field the blessing of much interesting work
in many different directio ns. However, this very same "dendritic"
activity has led to much confusion and misunderstanding. An
epito me of this situatio n is the very frequent use of the sentence:
". . . it is a co mmo n co nsensus t hat . . . ( . . . electro chemical pretreat-
ment is an abso lute prerequisite . . . ; o r . . . the sho rt-range interac-
tio ns are by far; o r . . . the major pro po rtio n . . . o riginates from the
large electro magnetic fields . . . ) , " etc. Fro m a careful screening of
the literature, which will be presented here, it will beco me clear
that, as yet, there is no general co nsensus regarding either the
enhancement mechanism o r some of the major experimental facts.
The clo sest we are to some kind of co nsensus is in ackno wledging
the po ssibility that several mechanisms may be o perative, and that
the co ntributio n of the "o ther" mechanisms (each from his o r her
po int of view) is the mino r o ne.
This review is no t intended to put an end to the raging co n-
tro versy. It is felt that we are still a (lo ng?) way from fully under-
standing SERS. Ho wever, now that some of the dust has settled,
it is time to critically review the work do ne and the theo ries pro -
po sed, and perhaps attain a state of better understanding of what
has already been achieved. This article comes to co mplement and
update the reviews already published
8
"
19
and the co llectio ns of
papers dealing with SERS.
20
"
23
This review is updated to early 1984. At the time of pro o fread-
ing, several excellent papers have appeared in print, which are no t
S urface-E nhanced Raman S cattering (S E R S ) 255
reviewed here. Ho wever, by and large, they do not change the
general picture of SERS as drawn here.
No do ubt, the present autho r has his own private "co nsensus"
which, in spite of his efforts, may inject itself into the review. In
o rder to offset such an undesirable bias, as much as po ssible, and
perhaps putting the cart befo re the ho rse, the autho r will state here
his own co nclusio ns and beliefs: "I am co nvinced that electric field
amplificatio n and enhanced emissio n near SERS-active surfaces
due to reso nating metal excitatio ns (surface-plasmo n po larito ns,
plasmo nlike mo des, shape reso nances, o r electro n-ho le pairs) is an
active mechanism in mo st of the systems studied. Ho wever, in most
systems, this co ntributio n, tho ugh an impo rtant o ne, is mino r com-
pared to the to tal enhancement po ssible in SERS. The major
mechanism, in my o pinio n, must be a reso nance mechanism, in the
sense of a reso nance Raman pro cess, i.e., a mechanism by which a
part of the system (mo lecule, mo lecule-metal ato ms, metal surface)
beco mes a stro ng scatterer by virtue of its large reso nance po lariza-
bility and no t as a result of stro ng fields exerted by the o ther parts
of the system".
This review will emphasize SERS in the co ntext of
electrochemical systems. The liberty has been taken of including in
this catego ry work do ne o n co llo ids suspended in (mostly aqueo us)
so lutio ns. Co llo ids, anyway, have many co mmo n features with
systems in electro chemistry. Thus SERS at the so lid-electro lyte
interface is the main questio n of interest here. Of co urse, o ne canno t
igno re the work on o ther systems, no r do es o ne want to . Therefo re
we will also discuss the o ther systems, such as vario us films in
ultrahigh vacuum, in air o r in tunnel junctio ns, on specially pre-
pared litho graphic structures, o n metal clusters trapped in a no ble-
gas matrix, o r on an o xide in catalytic systems, tho ugh they will
no t be at the main focus of this review.
I I . S E R S E XP E R I M E N T A L S T UDI E S
In this sectio n we discuss in a critical manner the experimental
evidence accumulated. Discussio n of po ssible enhancement
mechanisms will be given o nly in a later sectio n, so that separatio n
of facts and interpretatio n, can, as much as po ssible, be made.
256 S . E frima
Silver, being the most widely studied metal in the co ntext of SERS,
will play the leading ro le also in this sectio n and in the entire
review. Nevertheless, o ther metals and substrates will also be dis-
cussed. The o ther leading part is played by pyridinethe telltale
mo lecule of SERS. Other mo lecules will also be discussed, a few
in some detail, to intro duce new o r impo rtant behavio r no t shown
by pyridine, o r to substantiate some evidence for mechanisms of
SERS.
1. E stimate of the E nhancement Factor
(i) General
There is no clear definitio n of what magnitude of enhancement
entitles a system to be classified as a SERS-active system. In this
review we will arbitrarily set the demarcatio n line for SERS at a
100-fold enhancement level. Any enhancement higher than that will
be co nsidered as SERS, while lower enhancements will be igno red.
The reaso n for this limit is that it is within simple surface co verage
effects (ro ughness facto r) and "trivial" enhancements resulting
from reflectivity of metal surfaces and po ssible o rientatio n
effects.
24
"
26
The estimate of the degree of enhancement in every o ne of
o ur experiments is of prime impo rtance for understanding SERS.
First, the enhancement facto rs vary from system to system and that
may reflect different co ntributio ns of the vario us po ssible mechan-
isms. Seco nd, the sensitivity of the Raman systems has impro ved;
thus, detectio n of a signal do es no t necessarily mean that an
enhancement of four to six o rders of magnitude o ccurs. No wadays
o ne can detect signals which are enhanced by a facto r of only 100
to 1000 o r less.
27
'
28
The Raman scattering of dyes adso rbed o n
surfaces can be detected even witho ut any enhancement at all.
There are four main pro blems which arise when enhancement
facto rs are evaluated. The first pro blem is that we generally do no t
know the amo unt of material on the surface, especially in
electro chemical, co llo id, and thin-film studies co nducted in the
ambient o r in so lutio n. There are only a few studies which have
used radio chemical techniques for electro des
29
"
32
o r co llo ids.
33
'
34
A few studies attempted to measure surface coverages from the
depletio n of the co ncentratio n in the bulk so lutio n in equilibrium
with the surface.
33
'
35
'
36
Such studies may give only a lo wer limit of
the amo unt adso rbed, especially when the so lid and liquid phases
are separated in the co urse of the experiment. Electro chemical
techniques are also used, such as reducing o r o xidizing the adso rbed
species,
37
'
38
o r also spectro sco pical measurements.
37
In ultrahigh-
vacuum (UHV) systems there are so me independent techniques
which may indicate the amo unt of material adso rbed by Auger,
39
XPS,
40
'
41
and wo rk-functio n techniques
41
o r by using the micro bal-
ance.
42
Such metho ds, at times, yield info rmatio n regarding the
number of layers but no t the amo unt in a layer.
43
"
45
The seco nd pro blem o ne faces when estimating the degree of
enhancement is that the geo metry of the SERS system is generally
different than that of o ur reference system. The pro blem is that we
usually canno t see a signal from the reference mo lecule adso rbed
at a SERS-inactive surface of similar geo metry, and we have to
reso rt to a measurement at high co ncentratio ns in the bulk. This
may intro duce a large uncertainty in the evaluated enhancements.
In UHV systems this is circumvented by co mpariso n with thick
layers of the same adso rbant, preserving the same geo metry.
44
Also ,
in co llo id systems, o ne can, in principle, measure the scattering of
the reference in the bulk in the same geo metry as that of the co llo id
measurement itself. Ho wever, in this case o ne generally needs very
high co ncentratio ns which are detrimental to the stability of the
co llo id. An alternative, in this case, is to precipitate the co llo id o r
measure a separate liquid sample. But then o ne needs to co rrect
for the difference in transmittance between the co llo id suspensio n
and the clear supernatant o r so lutio n. This is the third difficulty in
evaluating enhancement facto rs. It is also of impo rtance for clusters
trapped in matrices
46
and for arrays where the SERS-active metal
o verlays the adso rbed molecules.
47
*
48
Fo r weakly transmitting sys-
tems, the uncertainty in the enhancement facto r can easily be an
o rder of magnitude if special precautio ns are no t taken.
A fo urth, trivial, pro blem in the determinatio n of enhance-
ments, results from changes in relative band intensities of the
adso rbed mo lecules. Generally, o ne co mpares the stro ngest bands.
Ho wever, due to the (so metimes large) changes in relative
intensities, the real meaning of such an estimate is no t alto gether
clear. This co nsideratio n may add to the uncertainty ano ther facto r
258 S . E frima
of 2-5. Thus, at best, enhancement facto rs can be determined o nly
to an accuracy of o ne o rder of magnitude o r wo rse.
A po tential difficulty is how to distinguish the signals from the
surface and from the bulk in co ntact with it. It turns o ut that it is
no t a pro blem at all in most cases. The following criteria can be
used, in part, or so metimes in full, to distinguish a surface spectrum
from a bulk signal:
1. Band-frequency shifts o ccur;
49
'
50
2. The relative band intensities are different.
49
3. New bands appear in the surface spectrum.
49
'
51
'
52
These
may be vibratio nal bands of the adso rbed mo lecule which
were weak or fo rbidden in the bulk
51
'
53
"
55
o r may result
from chemical changes in the adso rbed mo lecule, such
as, e.g., disso ciatio n.
56
4. The excitatio n profiles are different.
49
5. The surface spectrum is generally depo larized while that
from the so lutio n often has a large po larized co mpo nent
(i. e. , the depo larizatio n ratio is small).
5
'
8
'
57
"
60
In fact,
using an analyzer which passes the depo larized com-
po nent only is a neat way to discriminate against the
scattering from the bulk in the experiment itself.
61
6. Often using /^-polarized incident light results in higher
scattering intensities from the surface species as co mpared
to s-po larizatio n.
58
'
62
This do es no t always wo rk.
8
7. A high co ntinuo us backgro und is asso ciated with the
surface scattering.
63
"
81
A lo ng list of references is given
here as the co ntinuum will no t be discussed in this review
due to space limitatio ns.
8. In the case of electro chemical systems, a dependence of
the signal on the electric po tential may indicate a scatter-
ing from an adso rbed mo lecule;
82
this may be a result of
electric-po tential-dependent adso rptio n and deso rptio n,
mo rpho lo gy changes of the electro de, an intrinsic depen-
dence of the scattering pro cess itself on the electric po ten-
tial, and an electro generatio n of new species. In the latter
case, o ne sho uld co nsider the po ssibility of the creatio n
of multilayers o r the presence of pro ducts in the diffusion
layer (which will give a detectable signal if they manifest
reso nance Raman behavio r).
9. Fo r cases of surfaces in co ntact with a so lutio n, for
instance, the co ncentratio n dependence of the surface
signal is generally different than that of the signal from
the bulk species.
10. The surface scattering from a mo lecule may be affected
by the presence of o ther chemical species in a much
different way from that of the same mo lecule in so lutio n
for instance, the o bservatio n of stro ng dependence of
the scattering of pyridine from a silver electro de o n the
presence and co ncentratio n of chlo ride io ns (see Sectio n
II. 3. (i) o r the interdependence of the pyridine signal o n
the presence of CO co adso rbed o n a silver film in UHV
co nditio ns
83
'
84
o r on the presence of cyanide anio n in an
electro chemical system;
85
to such a dependence o ne can
add also the dependence o n the pH.
52
11. Dye mo lecules adso rbed o n metal surfaces generally show
o nly a very weak fluo rescence backgro und.
86
An applicatio n of several of these criteria by Campio n and
Mullins
27
sho wed that the signal they saw was that of a no rmal
scatterer, no t the SERS effect. They o bserved unshifted frequencies,
unchanged intensity ratio s, linear dependence on co verage, and
low depo larizatio n ratio s.
A word of cautio n: in additio n to the uncertainties and pro b-
lems discussed abo ve, o ne sho uld take no te that all the enhancement
facto rs quo ted in the literature are merely average values. The
average is over the to tal amo unt of adso rbed material, be it at
submo no layer, mo no layer, o r multilayer co verages. If there are
special SERS-active sites which are a small fractio n of the surface,
then the "true" intrinsic enhancement facto r per mo lecule may be
much larger than the estimated o ne. We sho uld be aware of this
fact when interpretatio n of results are co nsidered in Section III.
( I I ) Electrochemical Systems
The o riginal o bservatio n and evaluatio n of the enhancement
by Jeanmaire and Van Duyne
5
inferred an enhancement facto r of
five to six o rders of magnitude. Van Duyne
8
has impro ved o n that
estimate by a careful study of the adso rptio n and scattering of
pyridine co mpared to an internal referencedeuterated pyridine.
260 S . E frima
The surface co verage was determined from chro no co ulo metric
measurements of 4-acetylpyridine, which gave 1.95 x 10
14
mo lecules cm"
2
on an eiectro chemically treated silver electro de. A
special electro de allo wed direct co mpariso n of surface Raman
scattering and that of the reference. The calculated enhancement
facto r was 1.3 x 10
6
. Schultz et a/.
87
estimated the enhancement of
pyridine scattering at an unano dized, mechanically po lished silver
electro de with 514.5-nm illuminatio n to be ~10
4
x. They based
their estimate o n the co unt rate of abo ut 100 cps co mpared to a
co unt rate of 10
4
cps they usually o btained from ano dized surfaces
for which they assume an enhancement facto r of 10
6
. In their
experimental results they show (Fig. 2 in their paper) spectra from
3 mm of a 0.5 M pyridine so lutio n which is shown to be superim-
po sed on the surface spectrum (Fig. 3 in their paper). Assuming a
surface co verage of 5 x 10
14
mo lecules cm"
2
o ne can directly derive
from these data an enhancement factor of ~2000. If o ne co rrects
for the so mewhat bro ader bands in the surface spectrum, a value
of 3000 is o btained. Taking a lower value for the surface co verage
brings this enhancement facto r even clo ser to their estimates.
87
After
ro ughening by electro chemical ano dizatio n the surface signal
increased by a facto r of 100 (no t shown in the paper), indicating
a to tal enhancement of 10
5
up to 10
6
. A similar wo rk,
88
for pyridine
on co pper, using 647.1 nm illuminatio n, gives a facto r of 1700 for
smo o th co pper and an additio nal facto r of abo ut 35 after eiectro -
chemically ro ughening the electro de, giving a to tal enhancement
of 6 x 10
4
.
Albrecht and Creighto n
6
estimated an enhancement facto r of
appro ximately 10
5
, based o n an adso rptio n iso therm and the scatter-
ing intensity from pyridine in the absence of the electro de. A
near-grazing incidence and no rmal detectio n co nfiguratio ns were
used, which are no t the o ptimal for SERS. Powers of 15 mW were
used! Hexter and Albrecht
89
have estimated the enhancement by
measuring the Raman signals in an electro chemical system where
the silver electro de was immersed in neat pyridine. Taking into
co nsideratio n the co llectio n geo metry, the focusing of the beam,
the surface co verage of pyridine (9 x 10
14
mo lecules cm"
2
), and a
ro ughness facto r of 3.5, they find an enhancement facto r of 2 x 10
4
for 488-nm light. In this case, incidence was at the o ptimal 70 but
the scattering angle was 90 which is no t o ptimal. It is also no t
clear whether chlo ride anio ns were present. They are kno wn to
increase the signals.
Busby and Creighto n
37
in their investigatio n of 2-amino -5-
nitro pyridine (ANP) o n silver fo und, using in situ electro chemical
metho ds, which were co rro bo rated by spectro sco pical measure-
ments, that an equivalent of many layers of ANP was adso rbed o n
the electro chemically treated surface. They find enhancement fac-
to rs of 1.5 x 10
4
at 647.1 nm. If o nly the first layer was SERS active
(which canno t be determined from this experiment), then the
enhancement facto r grows to >10
5
.
Laufer, et al
90
fo und for cyanide o n co pper no dependence
of the Raman signal on the number of layers of co pper cyanide,
at least beyo nd 10 layers. They estimate an enhancement facto r of
100-1000, o r 10
4
if o nly a mo no layer is assumed to give enhance-
ment. A disturbing result in their repo rt is an increase of the signal
for decreasing wavelengths. This may indicate a bulk and no t a
co pper surface species to be the main scatterer (see Sectio ns II. 4
and II.5 for SERS excitatio n profiles o n co pper). In this work a
relatively large amo unt of charge was passed in the preparatio n
stage, abo ut 1.2 C cm"
2
. This sho uld be co mpared to 10-25 mC cm"
2
which is co mmo nly used (see Sectio n II. 2(ii)). Finally, o ne sho uld
no te that the electro de preparatio n co nsisted of ano dizatio n o nly,
witho ut reductio n. This further indicates that o ne is no t seeing a
surface species but maybe a thick layer.
Bunding et al.
91
repo rt an enhancement of 10
4
-10
6
for methyl
pyridines o n a silver electro de at 514.5 nm. No detailed estimate is
given. Billman et al
92
repo rt enhancements for cyanide on silver
on the o rder of 10
6
-10
7
. They give no details except a surface
co verage of ~10
15
mo lecules cm"
2
, as repo rted by Bergman et al
29
This high value is especially large co nsidering the fact that bo th
the incidence and scattering geo metries are no rmal to the surface.
Naaman et al
93
studied enhancement of the scattering of pyridine,
benzene, and cylco hexane o n mercury (mainly a hanging dro p);
514.5-nm light was used, with no co ntro l over the electric po tential.
Fo r the electro de in co ntact with the saturated gas of each of
the mo lecules, a large Raman signal was seen, abo ut 10-20 times
mo re intense than that measured from the gas alo ne. Assuming
mo no layer co verage and typical surface co ncentratio ns of ~-10
14
mo lecules cm
2
, the enhancement is evaluated as 10
5
, taking into
262 S . E frima
co nsideratio n the vo lume of the gas co ntributing to the scattering.
There is a high pro bability for multilayer fo rmatio n at the pressures
used (100-200 To rr), as ackno wledged by the autho rs themselves.
A co ntro l experiment was co nducted with the electro de immersed
in neat pyridine. The Raman signal detected was twofold mo re
intense than that of the pyridine liquid alo ne. This was taken as
evidence for the co ntributio n of the adso rbed layer to the scattering.
Ho wever, it may also be due simply to the beam being reflected
from the metal and causing mo re bulk mo lecules to scatter.
Intro ducing the electro de into the neat liquid may also easily result
in slight geo metric and illuminatio n and light-co llectio n changes,
which co uld cause the facto r of 2 or so in the measured Raman
signal. No te also that there are no shifts in po sitio n o r changes in
intensity ratio s of the bands between the electro de and the mo lecule
in the bulk. Furthermo re, the bands attributed to the surface do
shift between the gas and the so lutio n experiments, fully mimicking
the spectra of the bulk. Similar remarks to these abo ve are relevant
to the experiments where the electro de was immersed in an aqueo us
so lutio n and facto rs of 2 in the scattered intensities, co mpared to
the so lutio ns in the absence of the electro de, were seen.
Blo ndeau et al
30
used radio chemical measurements in co njunc-
tio n with Raman scattering. They find that the amo unt of adso rbed
pyridine is the equivalent of several layers (based o n the assumptio n
of a co verage of 1.5 x 10~
9
mol cm"
2
, i.e., 9 x 10
14
mo lecules cm"
2
).
Even witho ut almo st any electro chemical treatment they see abo ut
two to three layers, while at typical co nditio ns for SERS
(25 mC cm"
2
) the equivalent of eight layers is seen. This, of co urse,
decreases the values calculated for the enhancement facto r based
o n mo no layer co verage. Fo r cyanide only a mo no layer of Ag(CN)
2
"
io n is seen, emphasizing the large enhancement facto rs evaluated
for this io n.
Tom et al
94
repo rted 10
4
enhancement facto rs for pyridine on
a 400-nm-thick film of silver, when the film was given a mild
electro chemical treatment and a facto r of 10
6
for the usual pretreat-
ment. Their evaluatio n is based on a co mpariso n with the scattering
from the so lutio n befo re the treatment, but they give no further
details. Chen et al
95
estimate the enhancement by co mparing the
scattering from neat pyridine at the same co nfiguratio n as in their
SERS studies. They assume mo no layer co verage of 4 x 10
14
mo lecules cm"
2
and state that they have acco unted for the co llectio n
vo lume. They find an enhancement facto r of 1.4 x 10
6
.
(iii) Colloidal Systems
Kerker et al
96
calculated the enhancement effect for citrate
adso rbed o n a silver co llo id, assuming a unifo rm size distributio n
of the co llo id and a full-mo no layer co verage of the citrate io ns.
They co mpared the signal to the intensity of the scattering from
the so lutio n in the absence of the co llo id. They find values of
<3 x 10
3
at 350.7-nm excitatio n, 3 x 10
4
at 406.7-nm excitatio n, and
(3-6) x 10
5
in the excitatio n range of 457.9-647.1 nm. It is no t clear
how they co rrected for the transmittance of the co llo id suspensio ns.
Also , taking a full mo no layer of the charged anio ns may be an
o verestimate, tho ugh this is co rro bo rated by a later study.
33
This
requires extremely high charges o n the 21 nm particles with no
electro lyte to reduce the energy of the system. Thus it is pro bable
that the enhancements are even larger than their estimate. A very
tho ro ugh study of citrate co llo ids was carried o ut by this same
gro up.
33
They have investigated several co llo ids prepared in vario us
manners and have directly determined the amo unt of adso rbed
citrate by radio chemical techniques. By co mpariso n with an external
standard and co rrecting for the abso rptio n of the suspensio n (details
no t given) they find essentially the same results as repo rted earlier,
96
except at the lo nger wavelengths. Fo r 647.1-nm excitatio n, they find
7 x 10
4
instead of 6 x 10
5
fo und befo re. Fo r several of the prepar-
atio ns the estimated enhancement at 647.1 nm was loweras low
as 2000.
Suh et al
91
investigated p-amino benzo ic acid (PABA) adso rbed
o n a silver co llo id. They assume a specific unifo rm shape and size
of the co llo idal particles, from which they calculate a surface area.
Then, assuming o ne-full-mo no layer adso rptio n and estimating the
focal vo lume from which the scattering arises, they deduce an
enhancement facto r o n the basis of co mpariso n with a so lutio n of
PABA. They find a value of 4 x 10
6
. They are well aware of the
appro ximatio ns and assumptio ns made and therefo re claim this
value is a lo wer limit to the enhancement facto r.
Creighto n et al
36
estimated the enhancement of the scattering
of pyridine from a co pper co llo id at 647.1 nm excitatio n to be
264 S . Efrima
1.5 x 10
5
. This estimate was based on the determinatio n of the
amo unt of pyridine adso rbed by ultracentrifugatio n of the sus-
pensio n and measurement of the amo unt of pyridine which
remained in the supernatant so lutio n. This, of co urse, assumes that
the precipitatio n of the so lid do es no t release any of the initially
adso rbed mo lecules. Co rrectio n for the laser light abso rptio n by
the co llo id was carried o ut, tho ugh no details are given. The com-
pariso n was pro bably made with respect to a so lutio n of pyridine
in a separate experiment.
Estimates of the degree of enhancement were carried o ut also
on metal clusters suppo rted on silica (and o ther) substrates. As an
example, co nsider the repo rts of Krasser et a/.
98
" who investigated
CO, hydro gen, and benzene adso rbed on nickel particles. Fo r CO
in a 1:1 CO-hydro gen mixture they repo rt an enhancement of
abo ut 10
4
as deduced from a co mpariso n of the intensities at an
exciting frequency which gave the maximum signal (457.9 nm) and
at a frequency which gave only a very weak signal. Fo r the 1:4
mixture that maximum was at 488 nm and indicated an enhance-
ment of only two o rders of magnitude. The precise meaning of
these estimated enhancement facto rs is unclear. Fo r benzene on
Ni " a mo re detailed estimate of the enhancement was do ne. The
surface intensities were co mpared to tho se from neat benzene
measured with the same o ptical arrangement (as far as this is
po ssible). A surface co verage was assumed (no details given) and,
from the co mpariso n of the Raman intensities, an enhancement
facto r of 500 can be o btained (the repo rted value of 2000 is pro bably
a typo graphical erro r). These enhancements, therefo re, are no t
classified as SERS in the present review.
(i) UHV Systems
UHV systems pro vided SERS studies with the full po wer of
mo dern surface techniques. These systems are in principle better
co ntro lled and characterized than electro chemical and co llo id sys-
tems. Thus o ne can perhaps o btain go o d evaluatio ns of the
coverages and therefo re mo re precise enhancement facto rs. Ano ther
impo rtant feature of UHV (and also of film) studies is the po ssibility
of perfo rming experiments where o ne goes in a co ntro lled manner
from submo no layer co verages to multilayers. This can give distance-
dependence info rmatio n. One can also relatively easily insert
spacers between the scattering mo lecule and the surface, again
extracting the distance dependence of the SER effect.
An early effort in that directio n was repo rted by Smardzewski
et al.
100
In this study the abso lute amo unt of the adso rbed mo lecules
was no t kno wn, but there was a go o d co ntro l over the relative
amo unts, quo ted in langmuirs (L). 20 L of perdeutero pyridine was
adso rbed o n a silver slug and its Raman scattering signal was
registered (at 488 and 514.5 nm and after bo mbarding the surface
with argo n io ns). Then, varying amo unts of pyridine were depo sited
o nto the substrate, and the jo int Raman signal was measured (the
spectra do no t o verlap and allo w a co nvenient determinatio n of
bo th species simultaneo usly). The pyridine and deutero pyridine
gave equal signals when the co verage of the pyridine was 5000 L,
indicating an enhancement of 250 of the mo lecules clo ser to the
metal over tho se which are further away. The autho rs also no ticed
that the scattering intensity of the perdeutero pyridine did no t
change between co verages of 5 and 20 L, which indicated an even
higher relative enhancement of 1000. This number must also be a
lower limit to the abso lute enhancement. Similar results are o btained
when mo nito ring the scattered intensity as a functio n of the amo unt
of pyridine depo sited directly on the silver surface. The intensity
changes by a facto r of 4 between 10 and 3000 L, giving a lo wer
limit of the enhancement of 75. In a later study
101
of pyridine o n
silver, co pper, and go ld films and single-crystal substrates, a
mo no layer co verage was assumed when the samples were heated
to 230 K, abo ve the sublimatio n temperature of pyridine (170 K).
In this case, an o verlayer of (estimated, no details) 10
4
layers of
pyridine gave a signal abo ve the detectio n limit, which was still
10-fold weaker than that of the first layer o n pretreated silver. Thus,
a relative enhancement facto r of 10
5
is indicated. Again this is a
lo wer limit of the enhancement, if the po ssibility of lo ng-range
enhancement is co nsidered. On a sputtered silver single crystal, a
5500 nm-thick layer of pyridine (measured by interfero metry) pro -
duced a signal two to three times as intense as the surface (frequency
shifted) species. Depending o n what o ne takes for the thickness of
a mo no layer, o ne can calculate enhancements of 10
4
to 2 x 10
4
.
Rigo ro usly, these are relative enhancements, relative to the thick
layer. Ho wever, as in a separate experiment no bulk Raman signal
266 S . E frima
was seen from ~ 40-nm thick layers; this is pro bably also the
abso lute enhancement.
Rowe et al.
101
studied pyridine o n silver ro ughened by a pho to -
chemical reactio n with io dine in UHV co nditio ns o r, alternatively,
electro chemically treated as usual for SERS and then sputtered.
They determined surface coverages by Auger spectro sco py (disre-
garding po ssible damage to the adso rbed layer; Ref. 43). They
fo und a mo no layer has abo ut 3 x 10
14
mo lecules cm"
2
and that
co rrespo nded to a break in the Auger signal vs. expo sure plo t at
the 7- to 8-L range. They seemed to use this mo no layer value for
all their surfaces, smo o th as well as ro ugh. Thus they interpret the
rise in the 991-cm"
1
band (bulklike band of pyridine) up to an
expo sure of 18 L as evidence for a lo ng-range enhancement effect.
Alternatively, o ne may argue that on the ro ugh surface with a
reaso nable ro ughness facto r of 3 o ne has no t yet co mpleted a
mo no layer at this expo sure. Furthermo re, this study pro ves very
nicely that extremely small coverages give exceptio nally large sig-
nalsthe 1006-cnrT
1
band is saturated already at an expo sure of
~1 L, which is much smaller than a mo no layer, even neglecting
the ro ughness facto r. This po int seems to have been o verlo o ked.
This shows co nclusively that only a small fractio n of the adso rbed
mo lecules can give most of the signal, at least for o ne of the adso rbed
forms of pyridine o n the surface in these systems. The form that
gives the 991-cm"
1
band shows a mo re gradual buildup of the
signal, tho ugh also for it no real evidence for lo ng-range enhance-
ment is seen.
A further co nfirmatio n of this analysis can be found in the
interesting study of pyridine and deutero pyridine o n silver carried
o ut by the same gro up.
102
First, they sho wed that deutero pyridine,
like pyridine itself, has two forms on the surface, with slightly
different frequencies, at 962 cm"
1
co rrespo nding to the 991-cm"
1
band of pyridine, and at 976 cm"
1
co rrespo nding to the 1003-cm"
1
band. Then they depo sited what they referred to as two mo no layers
of deutero pyridine on to p of a "mo no layer" of pyridine. The
976-cm"
1
band of deutero pyridine did no t appear, while its 962-
cm"
1
band was abo ut twice the intensity of the 991-cm"
1
band of
pyridine. They interpret this result as evidence for the
deutero pyridine being depo sited on a co mplete mo no layer of
pyridine, with the same stro ng enhancement for the seco nd and
third layers as for the first. Ho wever, clearly these results can be
explained by the deutero pyridine being depo sited on the bare metal
side by side with the pyridine. In this case the 976 cm"
1
wo uld no t
appear as it was shown to saturate at extremely low coverages of
either mo lecule. In additio n, o ne sho uld no te that in the results
repo rted
102
there is only a very small change in the signals upo n
additio n of deutero pyridine up to five "mo no layers. " This shows
that there is no co nsiderable lo ng-range effect, but merely enhance-
ment of the first mo no layer o r so .
Essentially similar experimental results were o btained by Pock-
rand and Otto
45
for pyridine o n silver films, co ld depo sited. They
find the 1006-cm"
1
mo de gro wing in at very small expo sures and
saturating at abo ut 2 L. The 994-cm"
1
band is intially much weaker
but grows linearly with expo sure (o n a silver slug) up to 10
5
L.
They interpret their results in terms of sho rt-range effects for the
enhancement, and special sites which pro duce the 1006-cm"
1
band,
which is also enhanced to a large degree. By co mparing the 996-cm"
1
band intensity at large expo sures to the 1006-cm"
1
intensity, an
enhancement facto r of > 10
4
is evaluated. Po ckrand
103
has co rro bo r-
ated these results, asso ciating a mo no layer in his system to 4.3 x 10
14
mo lecules cm"
2
o r abo ut 11 L. He, to o , finds saturatio n at several
langmuirs.
Sanda et al,
44
in a UHV system, determined the surface cover-
age by UPS and find a saturatio n of the signal by the seco nd layer,
with some enhancement (abo ut two o rders of magnitude less than
for the first layer) of the farther layers. One sho uld no te that the sur-
faces they used are smo o th single crystals, with only a lo ng-wave-
length mo dulatio n. Signals from a smo o th, unmo dulated surface
were undetectable, meaning in their system an enhancement of < 500.
Tsang et al.
54
used a similar surface with a grating pro file.
Using the estimates of Sanda et al. for the surface co verages,
44
they
find large enhancements even at six layers. No te that they co uple
to the surface at the plasmo n angle. Co mparing to the scattering
from a thick layer of benzene, they estimate an enhancement of
only ^500 and it is no t clear how well the coverages are really
kno wn. Fo r pyridine, a surface signal is no t seen for less than abo ut
a "mo no layer" unless some silver is co ld depo sited o nto the grating
surface. Then a frequency-shifted signal co mparable in intensity to
that of abo ut five layers of the bulklike band (the present autho r's
268 S . E frima
estimate from Fig. 5 in Ref. 54) is seen. This signal do es no t change
significantly in intensity between 0.5 "mo no layer" and seven layers.
There is no indicatio n what happens at lo wer expo sures; ho wever,
it is clear from the spectra given in the paper that this band saturates
at low co verages and is abo ut 40 times mo re intense than the bulklike
band. Thus its enhancement is at least 2 x 10
4
. This enhancement
is what is co nsidered SERS in this review.
Eesley
43
investigated pyridine on a silver foil treated by argo n
io n sputtering. He finds that using Auger spectro sco py with 2-3 keV
for mo nito ring coverages is damaging. Instead, he uses work-func-
tio n measurements and finds a mo no layer at abo ut 4 L. This was
confirmed by XPS studies.
40
'
41
A saturatio n of the Raman signal
for all the bands, 990, 1002, and 1032 cm"
1
, is seen at abo ut
0.5-mo no layer co verage. Measurements were carried o ut up to 21 L,
i.e., appro ximately five mo no layers.
Bobrov et al
104
find for ethylene on silver films in UHV that
an expo sure of 1 L leads to a mo no layer, based on a kinetic theo ry
estimate, assuming a sticking facto r of 1. They see Raman signals
already at expo sures of 0.03 L which saturate at 2 L. By co mpariso n
to the scattering from a crystal of naphthalene (!) they estimate the
enhancement as 10
4
-10
6
(no further details are given).
DiLella and Mo sko vits
105
find that several butenes on a co ld-
depo sited film of silver show a 2000-fold enhancement relative to
a thick (abo ut 200 layers) film of the butene o n the same silver
surface. This is judged on the basis of a co mpariso n between a
surface-frequency-shifted band and a bulklike band. DiLella et a/.
58
also investigated CO o n co ld-depo sited silver and found a 10
6
enhancement of the first (frequency shifted) layer co mpared to the
thick o verlayer with co rrectio n for geo metric facto rs. This gro up
summarizes their findings
106
where they discuss the unique behavio r,
in general, and enhancement, in particular, of the first adso rbed
layer. They emphasize, ho wever, that also mo re distant layers give
enhancement (10
2
fo ld?).
(v) Films in Air
In a series of very elegant studies, spacer techniques were used
by Murray et a/.
47
'
48107
to pro be the enhancement from vario us
mo lecules on silver films. They co nclude that large enhancements
are in effect even for mo lecules lo cated 8-10 nm away from the
silver surface and that there is a slow expo nential decay of the
enhancement upo n moving away from the surface. They have
essentially two types of experiments. One set uses a spacer, a weak
Raman scatterer, po ly(methylmethacrylate) (PMMA), to separate
p-nitro benzo ic acid (PNBA) from a ro ugh silver film. Tho ugh
studies of po ssible penetratio n of the PNBA thro ugh the spacer
were co nducted, the po ssibility of a small percentage of penetratio n
canno t be ruled o ut. It is even reaso nable to perceive that the degree
of penetratio n will depend (expo nentially?) o n the spacer thickness.
It was already discussed in this review that a small amo unt of
adso rbed mo lecules is eno ugh to give eno rmo us signals. Also ,
even tho ugh PMMA is a weak scatterer, it is no t clear why under
the lo ng-range enhancement assumed, and co nsidering the large
thickness, it will no t co ntribute to the Raman scattering (o r perhaps
it do es?).
The seco nd set of experiments studied the thickness depen-
dence of the Raman scattering of a layer of po ly(p-nitro styrene)
(PNNS) on to p of which a silver film was depo sited. No saturatio n
of the signal was seen to abo ut 40 nm. The autho rs o nce again infer
a lo ng-range enhancement. Ho wever, the po ssibility of changing
the surface area of the silver o verlayer due to the different texture
of vario us thicknesses of the PNNS, and as a result the scattering
itself, is no t co nsidered. Indeed, as the investigato rs state, the films
are of irregular structure and are no t easily co ntro lled o r well
characterized, in spite of the efforts in that directio n. These pro blems
are reflected also in the difficulties o ne has in trying to estimate the
abso lute enhancements in these systems. Using a stro ngly mo del-
dependent calculatio n and estimates of the extinctio n of the over-
layers and the geo metric parameters, values of 10
4
-10
7
are repo rted.
It is reaso nable to summarize these studies by saying that they have
indicated a po ssibility of large lo ng-range enhancements; ho wever,
they have no t excluded the po ssibility of a sho rt-range mechanism
being the main cause of the repo rted experimental results.
(vi) Smooth Surfaces
Ano ther set of studies o ne sho uld co nsider is tho se measuring
the enhancement on smo o th surfaces. The work of Schultz et al.*
7
270 S . E frima
which sho wed large enhancements for "smo o th" silver surfaces,
was already discussed here. Udagawa et a/.
108
studied the Raman
scattering of pyridine from a silver single crystal o riented in the
100 directio n. The substrate was mechanically po lished, then mildly
sputtered in UHV co nditio ns, followed by high-temperature anneal-
ing. The surface was clean under Auger spectro sco py (less than
0.5% impurities) and pro duced a clearly defined LEED (low-energy
electro n diffraction) pattern. Using Auger spectro sco py, a mo no layer
was asso ciated with an expo sure of abo ut 5 L. The measured inten-
sity from the 1004-cm"
1
band was co mpared to the scattering from
gas-phase pyridine at the same geometry setting. The size of the
scattering vo lume from the gas, the area illuminated o n the surface,
and the number of mo lecules in o ne full mo no layer (3 x 10
14
) were
estimated. Thus an enhancement facto r of 440 was calculated.
There are four main uncertainties in this evaluatio n:
1. A mo no layer co verage may be different than the assumed
3 x 10
14
.
2. The intensity o btained for the 10-L expo sure, from which
the evaluatio n of the enhancement was do ne, may have
been reached at lower expo sures. As we have previo usly
discussed, the signal often saturates at submo no layer
co verages.
3. The scattering vo lume and illuminated area are only esti-
mates.
4. s-po larizatio n was used with bo th incidence and detectio n
appro ximately no rmal to the surface. This highly disfavo rs
scattering from smo o th surfaces
109
(no t very much from
ro ugh o nes).
Co rrecting for the last po int alo ne co uld increase the estimated
enhancement by a facto r of abo ut 10-30, giving a to tal enhancement
of 4000-10
4
(see Ref. 26). Co rrecting for po int (2) wo uld give even
higher values. Po ints (1) and (3) may change the estimated value
bo th ways.
Tsang et al
110
have also measured the Raman scattering from
pyridine o n silver films using an o ptical multichannel analyzer
(OMA). They find an enhancement of abo ut 100 (no details are
given as to how this was calculated and what was the geo metry of
the system). They attribute this enhancement to a "residual"
ro ughness.
Campio n
109
also measured the Raman scattering of pyridine
from a smo o th silver (111) surface by using an OMA. He o ptimized
the geo metry, incidence angle, and detectio n directio n. No reference
was used. The co unt rate was directly used to calculate a cro ss
sectio n. Fo r that, assumptio ns were made regarding the co verage
and the efficiency of the detectio n system was taken from indepen-
dent experiments. The final sco re was virtually no enhancement. It
sho uld be no ted that the spectra Campio n reco rded was identical
to a bulk spectrum (no frequency shifts, no changes in intensity
ratio s, low depo larizatio n values, linearity with co verage). This is
no t usual for SERS.
(vii) Summary
There are many o ther impo rtant studies of the degree of the
enhancement and its distance dependence, some of which are
discussed in vario us reviews.
20
"
23
. We have reviewed here a rep-
resentative sample, which demo nstrates bo th the results and the
pro blematics related to their extractio n. The following po ints rep-
resent a summary of the main findings:
1. Large enhancements are measured for the Raman scatter-
ing of mo lecules adso rbed o n (silver) metal surfaces; com-
mo n enhancement facto rs are 10
4
-10
7
.
2. An extremely large enhancement is seen for the first
mo no layer o r fractio ns of it, of abo ut 10
4
-10
5
.
3. The scattering from the seco nd layer may be also enhanced,
by facto rs such as 100 o r so .
4. The enhancement on smo o th surfaces seems to be small,
tho ugh it can be as high as 10
3
o r mo re. Further work on
this po int is clearly needed.
2. S urface P reparation
(i) General
Fro m the very first studies of SERS,
5
it was clear that the
mo rpho lo gy of the metal substrate has a significant influence on
the SERS activity, much larger than o ne wo uld expect from the
changes in area available for adso rptio n. Vario us preparato ry
272 S . E frima
schemes were develo ped, some of which will be described belo w,
which lead to giant Raman signals.
In spite of the large amo unt of work directed to the develo p-
ment of SERS-efficient surface mo rpho lo gies and understanding
their ro le, there is as yet, no general agreement, especially regarding
the latter. Disregarding the present autho r's warning, o ne can safely
say that there is general co nsensus that ro ughening the surface
affects the SERS activity, generally favorably (if o ne do es no t o verdo
it). Ho wever, there is stro ng disagreement as to the nature of the
ro ughness required for large enhancements; directly related to the
co ntro versy over "the" SERS mechanism. We will refer to this
questio n as the "scale-o f-ro ughness" issue.
Let us, for co nvenience, distinguish between four types of
ro ughness: (1) the ato mic scale ro ughness (ad-ato ms and small
clusters); (2) the 0.5 to 10-nm range; (3) the 10- to 50-nm size
range; and (4) the big structures (micro sco pic dimensio ns). The
dimensio n given here is that of some typical dimensio n of the
ro ughness feature, such as its diameter o r height abo ve the smo o th
plane surface. One sho uld co nsider the limits given here only as a
guide which will pro vide a framework for tho ught and understand-
ing. The limit at 50 nm was cho sen because that is when retardatio n
effects start to be impo rtant, in the sense that fields emanating from
different parts of the ro ughness structure are significantly o ut of
phase with each o ther. At this size also the dipo le appro ximatio n
serio usly fails. The seco nd limit of 10 nm was cho sen as that is
ro ughly the mean free path of an electro n in silver and also co nven-
tio nal electro n micro sco py has a reso lutio n of that o rder of magni-
tude. Also , silver films at this average thickness begin to be co n-
tinuo us, instead of island films. Obvio usly, this limit is less sensible
for metals o ther than silver. The lower limit is that of a small cluster
o r single ato m.
Ano ther questio n o ne may ask in the present co ntext is whether
a ro ughening pretreatment is an abso lute requirement for SERS.
Alternatively, o ne may ask what is the magnitude of SERS from
smo o th surfaces (as far as these can be pro duced), and what is the
added enhancement upo n ro ughening? We have already discussed
this questio n and found that there is no unambiguo us answer to it.
The experimental evidence po ints to a small enhancement (belo w
100) on a smo o th surface, but mo re work in this directio n is required.
(ii) Surface Preparation in Electrochemical Systems
In o rder to o btain high-quality SERS on silver (as well as on
o ther metals exhibiting SERS) the electro des have to be electro -
chemically pretreated. As Schultz et a/.
87
and o thers
92111
have
sho wn, this is no t an abso lute requirement, but it certainly helps
in pro ducing extremely large signals.
The treatment generally begins with mechanical po lishing with
decreasing sizes of alumina (o r equivalent). Then an etch with a
mixture of ammo nia and hydro gen pero xide
111
o r with a so lutio n
of so dium cyanide and hydro gen pero xide
112
may be carried o ut.
After a further wash with water, the electro de is immersed in the
electro lyte so lutio n, so metimes under catho dic po tential co ntro l
(-0. 6 to -0. 2 SCE). All the electric po tentials in this review are
referenced with respect to the standard calo mel electro de (SCE),
unless stated o therwise.
In the next step, an electro chemical treatment is perfo rmed,
which is basically co mpo sed of two distinct stagesan o xidatio n
of the electro de and a reductio n. The treatment is therefo re often
referred to as the ORCo xidatio n-reductio n cycle. The name
remains even tho ugh the seco nd step is no t always perfo rmed, and
the treatment can also co nsist of vo ltage steps o r current pulses
instead of cycling the po tential.
The ORC calls for a cycle of the vo ltage between -0. 3 V or
so , to abo ut +0.2 V, where the silver is o xidized to silver io ns. In
the presence of chlo rides in the so lutio n, a layer of silver chlo ride
is fo rmed. On the return to catho dic po tentials the silver is reduced
back to the metal. In most cases, the charge is fully reco vered,
indicating a co mplete reductio n of the initially o xidized metal. This
ho lds true, of co urse, only within the accuracy of the measurement
which is o n the o rder of 0. 1%. The amo unt of charge passed in
this cycle is of major impo rtance in determining the degree of
enhancement of the Raman scattering. A charge of 20-50 mC cm"
2
is o ptimal. At lower and higher charges, the Raman signals are
generally smaller. This o ptimal charge co rrespo nds to 100-200
layers of silver o xidized and then reduced. Upo n reductio n, a
spo ngelike ultrapure silver surface is created, as determined from
SEM studies,
113
with submicro n structures appro ximately ellip-
so idal in shape. The true surface area increases by a facto r of
274 S . E frima
10-15; ho wever, it may be that a large fractio n of the adso rbed
mo lecules are no t expo sed to the light, being shado wed by the deep
crevices.
114
Blo ndeau et al.
31
have sho wn, using radio chemical tech-
niques, that there is an eight-layer equivalent of pyridine on silver
treated in the usual ORC. At very high charges, they find the
equivalent of 100 mo no layers, ho wever, that is at charges
>50mCcm~
2
. Hupp et al
115
found from lead underpo tential
depo sitio n (UPD) on silver that the surface ro ughness facto r is
only -1. 5-2 at 20 mC cm"
2
. However, it is no t clear that UPD will
o ccur ho mo geneo usly on the whole ro ugh electro de. A simple
calculatio n shows that for the co ncentratio n of lead io ns used and
the sweep rates and po tential scans emplo yed an amo unt of abo ut
40 nM lead, per 1 cm
2
apparent area, will reach the electro de by
diffusion. A surface facto r of 10 requires abo ut 15 nM lead for full
coverage of the surface. Thus, there is no large io n surplus in the
so lutio n to ensure full co verage, even neglecting lo cal differences
in io n co ncentratio n which can result in a further reductio n in the
amo unt of material avaiable to the UPD. Co nsequently, the estimate
for the ro ughness facto r repo rted by this metho d is pro bably a
lower limit. There is reaso n to believe, as will be shown belo w, that
also small clusters and ad-ato ms are prevalent on the surface
following the electro chemical surface preparatio n.
The SERS usually, but no t always, appears only after the
reductio n has begun and pro ceeded to some degree.
116
The ORC
can be carried o ut also by stepping the po tential to the ano dic
regio n and stepping back after the pro per amo unt of charge has
passed.
Two types of ORC can be applied.
117
The usual way is to carry
o ut the pretreatment in the same so lutio n where the SERS will be
measuredthe "internal ORC," Alternatively, o ne may employ the
"external ORC" where the ORC is perfo rmed in o ne so lutio n and
then the electro de is transferred to ano ther so lutio n with the
mo lecule studied, or the so lutio n is changed, o r an additio nal
mo lecular species is added. Do rnhaus et al
114
have sho wn, for
instance, that o ne co uld add pyridine after the ORC and still o btain
the same intensity as in the "internal" metho d. Actually, the seco nd
"so lutio n" may even be air.
118
Blatchford et al
119
(see Ref. 39 in
their paper) repo rted that washing off the chlo ride so lutio n after
the ORC still pro duced SERS from pyridine, following a gradual
buildup of the signal.
Kunz et al.
120
fo und for silver in an azide so lutio n that no ORC
was needed to see a Raman signal. The spectrum appeared on the
first po sitive scan as so o n as the disso lutio n of silver began. They
estimate that at the early stage of the disso lutio n, where the signal
is already very large, there was no t eno ugh disso lved silver to form
large structures. Therefo re they feel the enhancement, in that case,
was due to fo rmatio n of special (perhaps, ato mic size) sites.
Barz et al.
121
found that stepping the po tential to the regio n
of rapid hydro gen evo lutio n immediately prio r to an ORC can
result in a further enhancement of the SERS, by almo st an o rder
of magnitude as co mpared to an electro de subjected to ORC alo ne.
They attribute this to an effect the presence of hydro gen bubbles
on the electro de have on the surface mo rpho lo gies created by the
ORC. No identificatio n of the precise structures was repo rted.
ORC was also used for o ther metals, with the appro priate
changes due to the different chemical nature. Co pper allows a less
ano dic sweep, 0 V is quite eno ugh,
116
while for go ld o ne must go
as high as +1 V o r even higher.
116
Marinyuk and Lazo renko -Manevich
122
have shown that a full
ORC is no t really needed. They electro depo sited silver on a silver
electro de and measured stro ng Raman signals, 100-fold mo re
intense than from the "smo o th" surface. The intentio n was to
depo sit submo no layer quantities, ho pefully creating ad-ato ms o r
small clusters (the actual quantity depo sited is no t given). Similar
results were o btained by them for co pper and gold (at 632.8 nm).
They also fo und the spectrum to be stable, even after impo sing
negative po tentials (less than -1. 0 V) which are kno wn to irrevers-
ibly quench ORC-induced SERS (see belo w).
Furtak et a/.
111
went o ne step further and have shown that a
SERS-inactive gold electro de pro bed with 514.5-nm light reveals
an adso rbed pyridine signal (1008 cm"
1
) band after o ne depo sits
on it submo no layer quantities of silver. The signal disappears after
the electro so rptio n of the silver. They do no t give any estimate of
the enhancement, but o ne sho uld no te that the spectrum is no t
intense. Fro m their Figure 2, o ne can infer a depo sitio n of abo ut
5 x 10
14
silver ato ms. Fo r a 1-cm
2
electro de this means a mo no layer;
ho wever, their electro de area is no t given. In any case, mo no layer
o r submo no layer quantities canno t form large structures, o r even
fo rmatio ns on a scale larger than a fractio n of a mo no layer,
especially in this system.
123
276 S . E frima
A very interesting feature of the surface electro chemical prepar-
atio n is its dependence on illuminatio n. An early repo rt saw no
difference in the SERS whether the electro de was illuminated during
the ORC o r no t.
124
Wetzel et al
61
no ticed that illuminatio n was
needed during the ORC in o rder to o btain SERS from EDTA on
silver. Ho wever, in the absence of the EDTA ("external ORC")
illuminatio n did no t have any no ticeable effect. Co o ney et al
125
suggested that pho to graphitizatio n may play an impo rtant ro le in
SERS. Fleischmann and Hill
126
have pro po sed that pho to lysis of
silver chlo ride during the ORC is instrumental in creating SERS-
active sites. Maco mber et al
121
have shown that illuminatio n during
the ORC results in a 10-fold enhancement over the usual ORC
enhancement. The illuminatio n of the electro de during the ORC
was especially effective during the reductio n stage. They also
showed this additio nal enhancement was apparent even in the
absence of pyridine during the ORC. However, they found that the
presence of a halide is required to o btain any illuminatio n effect.
They felt this indicated pho to reductio n of the silver halide, perhaps
similar to pho to graphic pro cesses. Barz et a/.
128
find similar behavio r
and also sho wed that the effect is frequency dependent. Green light
seemed to be very effective while light of 647.1-nm wavelength was
hardly effective at all. Chen et al
129
again find the additio nal
enhancement due to illuminatio n. They also no ted that under illumi-
natio n, changes o ccur in the vo ltammo grams, namely, less charge
was passed in the reductio n stage, indicating, perhaps, pho to reduc-
tio n. Using SEM the illuminated surfaces showed much smo o ther
features than tho se seen on the areas no t illuminated, but which
went thro ugh the same ORC. Devine et al.
130
have also studied the
illuminated surfaces using SEM. They find 200- to 800-nm particles
on the irradiated surfaces. They repo rt no ticeable effects with a
He-He laser and even with regular room illuminatio n! Finally, we
no te that Fleischmann and Hill
131
have seen illuminatio n effects
on the appearance and destructio n of chemiso rbed pyridine (asso ci-
ated with the 1025-cm"
1
band); Maho ney and Co o ney
132
discuss
metal damage as a result of the illuminatio n; and Stacy and Van
Duyne
133
repo rt illuminatio n effects.
The sto ry of illuminatio n effects is only at its beginning. Except
for the close resemblance to pho to graphic pro cesses, we do no t
really know eno ugh abo ut the structural changes invo lved,
especially o n the ato mic and small cluster range. Further work will
certainly be of great impo rtance.
(I I I ) Electric Potential Dependence of SERS
After creating a surface which yields SERS signals, by the
pro per mechanical, chemical, and electro chemical treatment, o ne
still has the electric po tential of the electro de as an independent
parameter. This capability is a unique feature of electro chemical
systems (and less so of co llo ids). It gives ano ther very powerful
handle to affect and pro be the metal-electro lyte interface.
The SERS spectra are all dependent on the electric po tential,
and bo th intensity changes and vibratio nal frequency shifts are
seen. A special technique
8
'
62134
'
135
[po tential difference spectro s-
copy (PDS) o r po tential mo dulated spectro sco py (PMS)] takes
advantages of the po tential dependence to o btain a high surface
sensitivity. The electric po tential also has an interesting influence
on the excitatio n profiles (see Sectio n II. 5).
The electric po tential can affect SERS in vario us ways:
1. By changing the amo unt of adso rbed materials.
2. By directly affecting the SERS enhancement mechanism
itself, whatever that may be.
3. By influencing the structure of the adso rbed mo lecules.
4. By creating, thro ugh electro chemical reactio ns, new
mo lecular species, pro ducts of the mo lecules initially put
into the so lutio n.
5. By changing the surface mo rpho lo gy which then can
influence any o ne of the four facto rs enumerated abo ve.
This last po int is the reaso n why the electric po tential dependence
of SERS is included in this sectio n, and the focus of the discussio n
will be on it. No te that such mo rpho lo gical changes may be asso ci-
ated with irreversible behavio r as a functio n of po tential, while o ne
may expect a mo re reversible dependence for the first three effects.
One sho uld keep in mind that it is no t always po ssible to determine
which of these abo ve po ints is o perative in a given system.
Fleischmann et al.
1
'
3
already in their early papers, have no ticed
the dependence of the spectrum of pyridine on the electric po tential.
A shift of the band po sitio ns to lo wer values for the mo re catho dic
278 S . E frima
po tentials was explained in terms of the pyridine being displaced
from the electro de by o ne layer of water. This interpretatio n was
based o n the fact that of the two pro minent bands of the pyridine
(the breathing mo des), the lower o ne at abo ut 1008 cm"
1
was shifted
to 1005 cm"
1
at -1. 0 V, a value identical to the vibratio nal band
seen in an aqueo us so lutio n of pyridine. They, ho wever, mentio n
that the shift of the o ther stro ng band, from 1036 cm"
1
to 1033 cm"
1
,
away from the value in so lutio n, 1037 cm"
1
, do es no t suppo rt this
explanatio n. As we shall see, such interpretatio ns are no t straightfo r-
ward. Fleischmann et al. also no ted the appearance of a 1025-cm"
1
band in the SERS spectra and its eventual disappearance at -1. 0 V.
At this po tential all the SERS bands have decreased in intensity.
The maximum of intensity o ccurs at abo ut -0. 6 V, which is ano dic
to the po tential of zero changes (PZC) (at -0. 95 V). On palladium
hydride electro des a similar behavio r was fo und,
136
an increase of
the pyridine signal up to abo ut -0. 6 V, and then an irreversible
loss of the Raman signal negative to -0. 7 V.
The irreversible loss of signal was no ticed earlier by Jeanmaire
and Van Duyne,
5
'
8
who also repo rted that different mo des had a
different intensity dependence on the electric po tential. However,
all the mo des gave a maximum signal at -0. 55 to -0. 85 V. An
impo rtant experimental po int to no te is that such po tential-depen-
dent measurements sho uld be, and were, carried o ut with a wide
bandpass of the spectro meter, to allow for the shift of the band
po sitio ns with po tential.
Ho ward et al
137
no ted the reductio n of "graphitic" Raman
bands and a simultaneo us appearance of bands asso ciated with
C-H stretch. At po tentials negative to -1. 2 V, the C-H bands also
disappeared. This was explained in terms of the reductio n of surface
carbo n into hydro carbo ns and their subsequent deso rptio n.
Furtak
138
repo rted similar behavio r for cyanide as well. The
Raman intensity maximized at 0.9 V, reversibly decreasing at mo re
po sitive po tentials, and irreversibly slowly decreasing in time. This
was an impo rtant o bservatio n, because cyanide is mo re favo rably
adso rbed at the more ano dic po tentials. Thus, the SERS-intensity
dependence is determined by facto rs o ther than the surface co verage
alo ne. Furthermo re, Furtak et al.
ul
have also shown that the signal
intensity from cyanide on silver is stro ngly and irreversibly
quenched by po tentials negative of -1. 4 V. These results were fo und
also for thio urea.
57
In spite of its high dipo le mo ment which shifts
the PZC to po tentials some 400 mV negative of its "usual" po sitio n,
and its anio nic nature in adso rptio n,
139
the thio urea pro duced
maximum surface signals o n silver at abo ut -1. 1 V. There was an
irreversible lo ss of intensity for po tentials negative of -1. 4 V.
Benner et al.
140
followed the develo pment and changes in the
SERS of cyanide chemiso rbed o n a silver electro de as a functio n
of the electric po tential. They see a band at 2165 cm
1
appear at
abo ut -0. 1 V, which is replaced by a band at 2140 cm"
1
catho dically
to -0. 3 V. This band is eventually replaced by a band at 2110 cm"
1
.
These different bands are asso ciated with AgCN, Ag(CN)2, and
Ag(CN)3~ o r Ag(CN)4~, respectively, o n the basis of vo ltam-
mograms and the po sitio n of the bands (see also Plieth et al
141
).
At slow sweep rates the cyanide anio ns have time to diffuse away
from the electro de, so the higher co mplexes are no t fo rmed, as
indicated by the absence of the relevant bands from the SERS
spectrum. Do rnhaus et al
114
followed in a similar metho d the
develo pment of the signal for pyridine, pyrimidine, and pyrazine
o n silver. The first sho wed the usual reversible dependence up to
abo ut 1.0 V, catho dic to which an irreversible quench of the signal
to o k place. Pyrimidine was mo re sensitive to the electric po tential,
and exhibited the irreversible behavio r already at 0.8 V. Pyrazine
reaches its maximum of SERS intensity at -0. 4 V and was irrevers-
ibly quenched at -0. 7 V. Po tential-dependent frequency shifts of
the vibratio nal bands were also no ticed. Benner et al.
74
have fol-
lowed in a similar fashio n the develo pment of SERS bands on a
co pper electro de as the po tential was changed, and asso ciated the
vario us bands seen with po ssible co pper cyanide co mplexes and
co pper o xides.
Billmann and Otto
85
have sho wn that the po tential dependence
of SERS depends also on the presence of o ther co nstituents beside
the Raman scattering mo lecule. Thus, pyridine pro duced a lo wer
signal at -0. 8 V than at -1. 0 V in the presence of cyanide, while
in its absence the inverse was seen. Similarly, the cyanide signal
(at 2113 cm"
1
) was higher at -0. 8 V than at -1. 0 V in the presence
of pyridine, and vice versa in its absence. This behavio r can perhaps
be understo o d on the basis of co mpetitio n of the two species over
the available surface. The cyanide is mo re stro ngly adso rbed at the
less catho dic po tentials.
280 S . E frima
Wetzel et al.
142
fo und that SERS of cyanide bands from silver
shifted to lo wer frequencies when the po tential changed catho di-
cally to -0. 9 V. The shift was of abo ut 17 cm"
1
for the 2111-cm"
1
band and abo ut 8 cm"
1
for the 221-cm"
1
feature (asso ciated with
the metal-cyanide vibratio n). The spectrum was irreversibly
quenched for electric po tentials more catho dic to -1. 4 V, and
showed a reversible behavio r with po tential up to this limit. Similar
results were found for thio cyanate on silver, except that the po int
of irreversibility was at -0. 9 V. The quench at -1. 4 V for the cyanide
was achieved in less than a seco nd, indicating a fast pro cess.
Interestingly, after the quench, if silver cyanide was added to the
so lutio n at po tentials ano dic to -1. 2 V, most of the Raman signal
was reco vered.
Weaver et al
143
investigated thio cyanate on silver. They esti-
mate the surface co verage by capacitance measurements (which
sho uld be co nsidered only as an o rder-o f-magnitude evaluatio n
due to the inherent pro blems of measuring and interpreting do uble-
layer capacitance of so lid electro des). They find that the thio cyanate
saturated at the surface aro und -0. 7 V (vs. Ag/AgCl electro de). Its
surface Raman signal, tho ugh, increased from -0. 1 to -0. 5 V and
stro ngly decreased at -0. 7 V. Part of the decrease was reversible
but for times o n the o rder of hundreds of seco nds a clear irreversible
trend at -0. 7 V was apparent. These autho rs also repo rt frequency
shifts (20-30 cm"
1
) to ward lo wer frequencies as the po tential was
changed catho dically. One sho uld remark that no t all the mo des
seen exhibited frequency shifts with po tential: the CN and metal-
thio cyanate did, while the CS stretch and the NCS bend did no t.
Do es this indicate different adso rptio n sites with different adso rp-
tio n co nfiguratio ns? This may be suppo rted by the relatively large
width of the bands seen (abo ut 30 cm"
1
), which may indicate
inho mo geneo us bro adening.
Stacy and Van Duyne
133
repo rt time-reso lved investigatio n of
SERS of pyridine o n silver. They find that at -0. 7 V and catho dic
to it the signal decays in a biexpo nential manner, with characteristic
times of the o rder of 0.1 s and tens of seco nds. At -0. 6 V there is
a time-dependent increase of the signal which saturates with the
lo nger time co nstant.
Sanchez et al
144
studied piperidine adso rbed on silver. They
find that the frequencies of mo st of the bands are independent of
electric po tential; ho wever, there are large variatio ns in the
intensities. Two gro ups of bands are no ticedo ne asso ciated with
symmetric vibratio ns, the o ther asso ciated with antisymmetric
mo des. The SERS of the symmetric mo des is maximized at -0. 7 V,
while the antisymmetric mo des pro duced maximum signals at
0. 4 V. A ratio nalizatio n based o n the mixing between the mo des
of different symmetry under the influence of the electric field at the
interface was pro po sed. It is no t clear, tho ugh, why the different
symmetry mo des are gro uped as they are. This interesting o bserva-
tio n sho uld be investigated further.
Hagen et al.
145
have sho wn for /?-nitro so dimethylanaline (p-
NDMA) that its surface Raman signal is maximal at -0. 3 V and
dro ps stro ngly for mo re catho dic po tentials. However, it is no t
clear that this mo lecule, which is a reso nance Raman scatterer,
exhibits the usual SERS enhancement [see Section II. 3(iii)].
Kotz and Yeager
146
have also repo rted the dependence of the
frequencies of the vibratio nal mo des seen in SERS of pyridine,
pyrazine, cyanide, and p-NDMA to ward lower energies for in-
creasingly catho dic electric po tentials. They present a co mpre-
hensive discussio n of the vario us explanatio ns pro po sed for this
pheno meno n, which is co mmo n in SERS, and also add the po ssi-
bility of changes in the degree of back-bo nding.
147
No ne of the
interpretatio ns is fully satisfacto ry and this po int remains for
further study.
Hutchinso n et a/.
l4h
presented interesting results of SERS of
pyridine o n silver, in co ntact with a no naqueo us so lutio n of
iV,Ar'-dimethylformamide (DMF). They find stro ng signals at
catho dic po tentials as high as -1. 9 V, thus co rrelating the
irreversible quench seen in aqueo us so lutio ns with some pro perty
of water (perhaps its reductio n, o r specific interactio n with the
surface). In additio n, the vo ltage dependence of the intensity of
the three main bands (at 1007, 1024, and 1040 cm"
1
) is stro ngly
dependent o n the mo de. The 1024-cm"
1
mo de maximizes at -0. 2 V,
the 1007-cm"
1
mo de shows a minimum of intensity at -0. 4 V and
the 1040-cm"
1
mo de gives maximum scattering at -0. 8 V.
Furthermo re, o n additio n of 1% water, this behavio r changed
dramatically, with all bands giving maximum intensity in the range
-0. 6 to -0. 8 V. No changes in the frequencies themselves were
detected.
282 S . E frima
The electric po tential dependence of SERS of pyridine on a
co pper electro de was investigated by Temperini et al
149
They find
(with 647.1-nm excitatio n) that the bands seen exhibit qualitatively
similar dependence on the po tential. The behavio r depended on
the sweep rate. At low sweep rates (1 mV s"
1
) the signal was co nstant
in the range -1. 2 to -0. 9 V and decreased mo no to no usly as the
vo ltage was changed to -0. 3 V. At a 10-fold-higher scan rate the
SERS sho wed a maximum at abo ut -0. 7 V. The ratio between the
band intensities did no t remain co nstant, indicating a different
quantitative dependence on the po tential.
To summarize this sectio n it was fo und that:
1. SERS intensities depend on the electric po tential reversibly
and also in an irreversible manner.
2. The reversible dependence canno t be explained on the
basis of adso rptio n and deso rptio n o r chemical reactio ns
alo ne but must reflect also some intrinsic dependence of
the SERS mechanism on vo ltage.
3. The irreversible behavio r in the catho dic regio n is pro bably
a result of changes in the surface mo rpho lo gy. Ho wever,
there is no t eno ugh independent evidence to determine
the scale of the structure changes, for sizes smaller than
abo ut 10 nm.
4. Different mo des may show similar o r different behavio r as
a functio n of po tential. In the irreversible regio n most
behave in a similar fashio n.
5. The dependence on electric po tential is affected by the
presence of different co nstituents and the so lvent.
6. The Raman frequencies are o ften, but no t always, a func-
tio n of the electric po tential, changing to lower energies
when the po tential is changed catho dically.
(it?) Surface Preparation in Colloidal Systems
The questio n of "surface preparatio n" in co llo idal systems
takes the form of co llo id preparatio n and stability. Several questio ns
are of interest:
1. How to pro duce the specified co llo id with the specified
mo lecule adso rbed on it?
2. What is the size unifo rmity (o r distributio n) of the co llo id
preparatio n?
3. Is there any aggregatio n and what is its characteristics and
its effect on SERS?
4. How do es o ne stabilize the co llo id suspensio n and slow
do wn time-dependent changes in its state of dispersio n,
o r, alternatively, measure the SERS fast eno ugh?
Some of the questio ns raised are lo ngstanding o nes in the field
of co llo id science, and they will no t be addressed in any detail in
this review. Synthesis of the co llo ids is generally perfo rmed (in the
co ntext of SERS) by reductio n of the metal salt. Specific pro cedures
are to be fo und in each of the repo rts which pertain to SERS o n
co llo ids. The adso rbed mo lecule for the SERS study can be present
during the reductio n stage and even participate in it (citrate o n
silver,
33
'
96
for instance). Alternatively, the adso rptio n may be carried
o ut after the reductio n (pyridine on silver and go ld,
60
for example).
The later pro cedure often causes no ticeable changes in the co llo id,
such as aggregatio n and precipitatio n.
There is some experience in preparing mo no disperse co llo id
suspensio ns,
150
'
151
ho wever, mo st preparatio ns repo rted in the SERS
literature are po lydisperse. Siiman et al.
33
have used separatio n
metho ds to o btain suspensio ns of mo re well-defined particle-size
distributio ns. The size ranges o ne often enco unters are from a few
nm up to several hundreds of nm.
The characterizatio n of the co llo ids is carried o ut by several
metho ds:
1. By UV-visible transmissio n and elastic scattering spectro s-
co py which can yield info rmatio n abo ut sizes
152
and
changes in it. This is a co nvenient in situ metho d, which,
ho wever, needs elabo rate numerical handling to extract
quantitative info rmatio n.
2. By electro n micro sco py, usually TEM, which yields precise
info rmatio n regarding the distributio n of sizes. The pro b-
lem is that in preparing the sample for micro sco py drastic
changes may o ccur in it.
3. Chemical analysis is used to find the co mpo sitio n and
quantity of the metal co llo id.
Aggregatio n is a very co mmo n o ccurrence in co llo id systems.
Any slight change in the co mpo sitio n of the suspensio n can readily
284 S . E frima
cause aggregatio n and precipitatio n. Thus the co llo ids studied in
SERS are often unstable and time-dependent effects are superim-
po sed o n the Raman results. One has to take special care to
overcome this pro blem. One metho d is to work fast eno ugh on the
time scale of the changes in the co llo id. An OMA is most beneficial
in this respect. One may add stabilizers such as gelatin or agar-agar.
Ano ther metho d is to take advantage of the structural changes and
mo nito r the SERS as a functio n of time, thus, hopefully extracting
the dependence of SERS on the structure in o ne experiment. Blatch-
ford et al.
35
studied such time changes upo n additio n of pyridine
to a gold sol pro duced by the reductio n of a go ld salt by citrate.
They no ted a gradual change in the extinctio n of the suspensio n
the o riginal band centred at abo ut 520 nm slowly declined while a
new band centered at ~670 nm grew in. In parallel, the elastic
scattering at wavelengths larger than 700 nm grew and pro duced a
band. TEM has shown that chainlike structures were appearing
with larger and larger lengths and at the expense of the well-defined
12 to 18-nm spherical particles. Simultaneo usly, the Raman scatter-
ing from the adso rbed pyridine was mo nito red and showed a
gradual increase in intensity, especially for excitatio ns in the neigh-
bo rho o d of the lo ng-wavelength extinctio n features. This demo n-
strates the dependence of SERS on the same parameters which
determine the extinctio n of the lo ng chains, i.e., plasmo n excitatio n.
No te, ho wever, that the to tal additio nal enhancement at 700-nm
excitatio n due to the aggregatio n is a facto r of abo ut 7, even tho ugh
the number of chains has increased by o rders of magnitude. (The
present autho r is tempted to add that this indicates that the enhance-
ment related to plasmo n excitatio n adds, in a multiplicative manner,
to a very large enhancement which is due to ano ther, as yet
unspecified here, mechanism. However, this is still the purely
experimental sectio n, so this remark sho uld be cro ssed off the
pro to co l!).
Creighto n et al.
36
have measured SERS on co pper hydro so ls
which underwent a slow aggregatio n affected by the additio n of
pyridine. Dynamic light scattering revealed a gradual growth in the
particles in parallel to the buildup of an extinctio n band at abo ut
570 nm. Again the SERS signal (evaluated to be enhanced 1.5 x
10
5
-fold) grew with time, using a 647.1-nm excitatio n. The to tal
increase in the intensity between 5 and 25 min is large, a facto r of
abo ut 50, which may be co nnected to particle gro wth, or to the
adso rptio n kinetics of the pyridine, or to bo th pro cesses. It wo uld
be extremely interesting to try and separate these two pro cesses,
so that the co nnectio n to the co llo id mo rpho lo gy and extinctio n
can be carried o ut on a mo re rigo ro us basis.
In a unique experiment Wetzel et al.
153
determined the depen-
dence of SERS of pyridine o n a silver sol on the electric po tential,
which was maintained by a reversible redo x system (euro pium
+3, +2) added to the suspensio n. The relative co ncentratio n of the
euro pium io ns was maintained by means of an electro de who se
po tential was co ntro lled with standard electro chemical equipment.
They fo und that the ratio between the two main bands behaved
similarly o n an electro de and o n a so l. Also frequency shifts were
seen. They interpreted these results as indicating that the same
SERS mechanisms are o perative on the sol and in electro chemical
systems.
Blatchfo rd et al.,
154
in a similar experiment, co ntro lled the
po tential of a silver sol with so dium bo ro hydride. The effects they
saw were co rrelated with UV-visible extinctio n measurements. They
found that aggregatio n and disaggregatio n are impo rtant in the
changes detected bo th in SERS and UV-visible spectrum. This
wo uld mean that the close resemblance to the electro de behavio r
seen by Wetzel et al.
153
may be fo rtuito us. Evidently, mo re work
in this directio n is warranted.
In principle, using co llo ids for SERS studies offers a unique
o ppo rtunity to study size effects. Ideally, o ne may co nsider the
co llo id as a co ntro lled and characterized "ro ughness feature witho ut
the surface," while in the usual electro chemical and film work o ne
has a surface with a ro ughness which is generally no t well defined.
In practice, ho wever, this go al has no t been achieved yet.
(t;) Surface Preparation of Substrates in UHV SERS Studies
In UHV co nditio ns two main different substrates are used:
vacuum-evapo rated films and single-crystal or po lycrystal bulk
samples.
One can distinguish between several types of films which
exhibit SERS:
286 S. Efrima
1. Island films
63155
"
159
fo rmed when a small amo unt of sil-
ver is depo sited on a substrate. Depo sitio n of up to 8- to
10-nm average width of silver pro duces this system.
2. Co ld-depo sited co ntinuo us films
72
'
75
'
77
'
160
, pro duced when
mo re than abo ut 10-nm-average-width silver is depo sited
o n a substrate co o led to below -190C.
3. Co ntinuo us films depo sited on micro sco pically ro ugh sur-
faces
161
(generally at room temperature).
Smardzewski et al
100
repo rted SERS studies of pyridine adso r-
bed on a po lycrystalline silver sample treated by argo n io n sputter-
ing at 77 K. Prio r to intro ductio n to the UHV system, the silver
substrate was po lished using the mechanical treatment described
abo ve. Zwemer et a/.
39
-
101102
have used io dine vapo r illuminated
by 488-nm laser light to ro ughen single-crystal substrates. Using
Rutherfo rd backscattering revealed ~50-nm silver particles on the
treated surface. Fo r surfaces with larger particles (200 nm), the
SERS was weaker by a facto r of 10 as co mpared to the smaller size
case. These autho rs also mentio n that electro chemical ro ughening
(no details were given) was used to o btain SERS-active surfaces in
UHV. In this case argo n io n sputtering was used to clean the surface
after intro ductio n into the UHV system. A similar electro chemical
treatment was used also by Eesley.
162
Po ckrand and Otto
69
mechani-
cally po lished their po lycrystalline and single-crystal silver sub-
strates and then ion sputtered them. The samples were co o led to
150 K. The po lycrystalline sample showed stro ng signals of "car-
bo nate" structures which reduced in intensity after annealing at
800 K. A single-crystal (110) face was initially annealed at 550 K
and did no t show any evidence for SERS. The inelastic scattering
seen was attributed to thick layers of pyridine. Sanda et al.
44
pre-
pared their single-crystal [(111) face] by mechanical po lishing,
followed by chemical etching in chro mic acid and HC1 which was
then followed by several UHV sputter/anneal cycles. Finally, a
1000-nm perio dic mo dulatio n was fabricated using litho graphic
metho ds. The co mpleted system was again sputtered and annealed
at abo ut 500 K. Eesley
43
has used a silver foil, mechanically po lished
and then sputtered in UHV. He fo und (using SEM) 100- to 300-nm
silver plateaus, between which there were smo o th areas covered by
silver balls of abo ut 20-nm diameter and fewer balls of 40-nm
diameter.
Silver island films are prepared by evapo ratio n of an average
thickness of abo ut 10-nm silver on a substrate (quartz, for instance)
and was described in detail elsewhere.
157
"
159
The films are often
characterized by their reflection o r abso rptio n spectra. Similar to
the co llo id case o ne can use Mie theo ry to understand the o ptical
behavio r of the films and its relatio n to their structure.
155
One can
also use electro n micro sco py.
155
Bergman et al
155
follow the
develo pment of a silver film as a functio n of the average thickness,
and mo nito r, in parallel, also the abso rptio n, the structure (using
SEM), and SERS of adso rbed cyanide. They find that the film is
co mpo sed of hemiellipso idal islands which grow gradually with
the average thickness depo sited. The maximum of SERS (for 514.5-
nm light) was seen for an average thickness of 6 nm, which gives
silver islands of appro ximately 30 nm diameter. Fo r o ther film
thicknesses, the Raman signal co uld be as low as three o rders of
magnitude less than for the maximum. No co rrectio ns for difference
in co verage of the vario us film thicknesses were repo rted. One
wo uld expect it to maximize at some intermediate thickness, as a
co mpro mise between the amo unt of silver depo sited and its ro ugh-
ness facto r. That, of co urse, wo uld have to be taken into co nsider-
atio n when analyzing the dependence of the Raman signal on film
thickness, and pro bably wo uld result in a less steep dependence of
the SERS o n the film parameters than that given in the paper.
Ho wever, witho ut detailed kno wledge of the cyanide co verage (o r
equivalently, the ro ughness facto r) o ne canno t attempt any further
analysis.
Seki
42
investigated silver island films with pyridine, and fo und
that at 10 K no Raman signal is seen, while warming up to 100 K
and co o ling back to 10 K, causes intense bands to appear. This
indicates that close pro ximity to the metal surface is no t eno ugh
for pro ducing SERS. It seems that migratio n and attachment of the
scattering mo lecules to specific sites is of prime impo rtance for
stro ng SERS in these systems.
The seco nd type of films used in UHV studies of SERS are
the films depo sited o nto co ld substrates. Wood and Klein
163
evapo r-
ated silver (unkno wn thickness) on a co pper substrate co o led to
78 K and detected a surface Raman signal at 2134 cm"
1
(presum-
ably, asso ciated with adso rbed CO o r carbo nate) which was
independent of CO pressure. That band was seen to gether with
288 S . E frima
Raman bands from bulk CO. A fter warming to ro o m temperature
this band disappeared.
Wo o d
164
focused on this pheno meno n, by mo nito ring the film
thickness, using a micro balance, and maintaining strict UHV co ndi-
tio ns. The co ld-depo sited silver was depo sited on a thick silver film
previo usly annealed at ro o m temperature, which showed no SERS
(under the detectio n sensitivity, of co urse). Raman signals from
adso rbed pyridine were detectable (at 180 K) only after abo ut 15 nm
of silver was depo sited. This was interpreted as meaning that ato mic
sizes and small clusters are of limited impo rtance in SERS, and
that large structures [size scale (2) and (3) in Section II. 2(i)] are
do minant in SERS. No te, that no mo nito ring of the number of
adso rbed pyridine mo lecules was carried o ut, and thus no co rrec-
tio ns for increasing surface ro ughness were perfo rmed. Also , the
Raman signal which is measured is relatively po o r as co mpared to
the no ise. This may mean that the to tal enhancement is pro bably
small and that small changes near the detectio n limit beco me
magnified. Wood and Zwemer
165
have shown the utility of these
films for detectio n of ethylene adso rbed on silver.
Wood et al?
9
co mpared co ld-depo sited films of silver (o n
co pper at 100 K) to bulk-ro ughened surfaces (by a pho to chemical
reactio n with io dine). They found that the enhancement on the
former was abo ut 5 times larger than on the latter. They also found
that with equal expo sures to pyridine the evapo rated films exhibited
predo minantly a first-layer enhancement, while the ro ughened sur-
face sho wed co mparable signals from the first and subsequent
layers. These co nclusio ns stro ngly depend on the abso lute coverages
on the surfaces and the relative coverages of the two systems studied,
bo th of which are no t kno wn precisely.
Po ckrand and Otto
72
'
77
no ted that pyridine on a silver film
depo sited on co pper at 120 K, pro duced a very large SERS signal
which was irreversibly quenched after annealing at 270 K, even
tho ugh mo re pyridine was added to co mpensate for any deso rptio n
at the higher temperatures. This behavio r was explained as an
annealing of ato mic-size ro ughness (ad-ato ms and small clusters)
at the high temperatures. They further no ted that, as a function of
temperature, SERS has increased up to abo ut 210 K, while the
elastic scattering co ntinued to increase up to abo ut 270 K. The high
backgro und seen in the spectrum also had a different temperature
dependence from that of the SERS. The initial increase of the SERS
signal is explained as ato m migratio n to steps to create SERS-active
sites, to gether with a gro wth of the larger surface features, which
co ntributes to the elastic scattering.
This annealing behavio r is very similar in nature to the
electro chemical "annealing" which pro duced an irreversible
quench of the SERS when catho dic po tentials were reached [see
Section II. 2(ii)].
DelPrio re et al.
166
have sho wn that in film depo sitio n, carbo n
and oxygen impurities may po se a pro blem, in fact, may cover most
o r all of the surface (ho wever, Po ckrand and Otto ,
72
for instance,
have relatively small "cathedral" peaks indicating only slight sur-
face co ntaminatio n). Mo nito ring the Raman signal from the
impurity bands, co mbined with SEM, DelPrio re et al co nclude
that stro ng SERS is seen with a surface ro ughness scale smaller
than 10 nm (their reso lutio n limit).
Results similar to tho se of Po ckrand and Otto were repo rted
for silver by Lado uceur et al,
160
including the irreversible annealing
of the silver. Fo r gold and co pper the Raman signal remained stro ng
all the way to ro o m temperature. Do es this indicate an especially
stro ngly bo und pyridine to these metals?
Seki
75
has carried o ut a co mparative study of silver where he
had in the same UHV system an island film (7.5-nm average thick-
ness) depo sited at 300 K, a co ntinuo us film (30-nm average thick-
ness) depo sited at 150 K, and that same co ntinuo us film depo sited
on the island film. At 77 K the first substrate exhibits Raman
scattering from pyridine abo ut 10 times stro nger than for the co n-
tinuo us film, while the film depo sited o n the island film showed a
co mparable intensity to the island films themselves (tho ugh no t all
the bands were seen). Annealing at 200 K and measuring the Raman
scattering at 150 K pro duced an additio nal enhancement of 20 in
the cold films, while the signal from the island films decreased
co nsiderably. This is in agreement with the annealing behavio r
fo und by Po ckrand and Otto . Furthermo re, temperature deso rptio n
studies (TDS) sho wed
167
that o n the co ld films a stro ngly bo und
species exists, which is absent o n the island films and on a single
crystal. Seki attributes this to the presence of cavities, with which
he asso ciates especially high enhancements. Albano et al.
495
also
discussed the ro le of po res in co ld-depo sited films. Mo et a/.
168
290 S . E frima
investigated several silver films and found optimal enhancements
fo r silver particles o f abo ut 100 nm.
(vi) Preparation of Miscellaneous Surfaces
Fo r the sake o f co mpleteness, a few o ther systems which were
studied fo r their SERS activity will be briefly mentio ned. So me o f
these systems were discussed in o ther sectio ns o f this review.
Murray et a/.
47
'
48
'
107
'
169
have devised ingenio us systems where
they used CaF
2
to enfo rce the ro ughness. These systems were
discussed in the co ntext o f range effects and estimates o f the
enhancement. Tsang et al.,
110
in an early paper, have also used the
calcium fluo ride base fo r a ro ughness pro mo ter.
Krasser and Reno uprez
171
use catalytic systems where the metal
clusters are depo sited o n silica o r alumina o xides.
Hart et al
172
pro duce extremely interesting systems o f silver
evapo rated o n po lymer micro structures fo rmed by replicatio n o f
litho graphically fo rmed silica surfaces co nsisting o f a well-defined
array o f ho les in a square lattice. Two o ther unique litho graphically
pro duced systems were investigated by Liao et al
173
'
174
These sys-
tems have the po tential o f co ntro lling the lo cal micro sco pic struc-
ture, which is very impo rtant fo r the elucidatio n o f the enhancement
mechanism.
Evapo rated silver films o n gratings at ro o m temperature is
ano ther interesting layo ut. It was applied mo stly by Tsang et
a/
54,no,i75,i76
A s i n a n A T R
(attenuated to tal reflectio n) co nfigur-
atio n,
177
the gratings pro vide ano ther co ntro llable parameter o f
impo rtancethe incidence angle.
Lyo n and Wo rlo ck
178
pro duced a system where the behavio r
o f silver islands co uld be gradually mo dified. They used a wedge
silica spacer to separate silver islands fro m a graphite substrate.
They fo und that the SERS enhancement decreased stro ngly as
the silver was clo ser to the carbo n. The to tal effect was o f a fac-
to r o f 300. The ro le o f the graphite is believed to be to quench
the silver (plasmo nlike) excitatio ns; thus an upper limit o f 300
was believed to be fo und here fo r the ro le o f these excitatio ns
in SERS.
Finally, the mo dified co llo idal system o f Go udo nnet et al.
179
sho uld be mentio ned. They fo rmed a system o f ro ughly spherical
co ated Teflon particles co vered by silver. This offers the o ppo rtunity
to study SERS in well-defined co llo idal systems.
(vii) Summary
In Sectio n II.2 it has been shown that SERS-active systems
require a special surface preparatio n in o rder to exhibit large
enhancements. The preparatio n co nsists of ro ughening the surface
in some manner, o r creating it already in a ro ugh form. It is no t
entirely clear what so rt of ro ughness is needed, and what is its
scale. The experiments have no t been sufficiently co nclusive to
satisfy everyo ne's taste. Ho wever, it seems clear that large-scale
features (tens of nm) induce enhancements, tho ugh there are indica-
tio ns that they are limited to a maximum enhancement of two o rders
of magnitude, in most systems. Small-scale (ato mic, small cluster)
ro ughness was shown in many experiments to be of major impo r-
tance for the extremely large SERS enhancements. The pro blem is
that such small-scale features canno t be seen directly by present
techniques, but their existence must be inferred from the tem-
perature dependence, electric po tential dependence, etc., of the
SERS effect.
3. S ome M olecules and S E R S B ehavior
A large number and variety of mo lecules have been studied in
SERS and a go o d co mpilatio n was given by Seki.
180
As seen there,
a large variety of mo lecules exhibit SERS: nitro gen co ntaining,
sulfur co ntaining, aro matic, aliphatic, diato mic, po lymers, io nic,
neutral, large, small, chemiso rbed, physiso rbed, o rganic, ino rganic,
bio lo gical, symmetric, and no nsymmetric. Thus, SERS seems to be
rather mo lecule general. Mo lecular species which have no t shown
SERS activity yet, may, under the pro per co nditio ns, scatter in an
enhanced manner. A classical example for this is the water mo lecule
(see belo w). This do es no t mean, of co urse, that all mo lecules are
SERS active, no r that all the mo lecules already repo rted to exhibit
SERS have indeed do ne so . It is clear that the nature of the mo lecule
has an influence on the degree of SERS activity, pro bably an
impo rtant o ne (see, e.g., Ref. 17). Ho wever, in this sectio n we shall
co ncentrate only on several selected aspects. Some of the o ther
292 S . E frima
aspects are discussed at different places thro ugho ut this review and
some are to be found in the o ther excellent reviews published in
the past.
Two gro ups of "mo lecules" will be discussed in some detail:
(1) SERS of halides and their influence on SERS of o ther mo lecules;
and (2) SERS of mo lecules which are in reso nance with the exciting
light, dyes. The former will be discussed primarily because of the
central ro le of halides in SERS and also from the po int of view of
the utilizatio n of SERS. Dyes will be discussed because they show
some special features which stro ngly bear on the SERS enhance-
ment mechanism. They also have no t been reviewed in the past. In
additio n to these two gro ups, a specific single mo lecule will be
discussedthe water mo lecule. It is presumed that no explanatio n
for that cho ice is needed.
(i) Halides and SERS
The impo rtance of chlo ride io ns for SERS was realized in the
very first studies.
5
'
8
In fact, Jeanmaire and Van Duyne
5
have studied
the dependence o n chlo ride co ncentratio n and fo und that o ptimal
signals were o btained for a halide/pyridine co ncentratio n ratio of
abo ut 2. This is dependent on the metho d of surface preparatio n.
181
The ro le of chlo ride io ns in the ORC, essentially in facilitating the
fo rmatio n of inso luble silver chlo ride in the o xidatio n stage, was
already discussed in Section II. 2(ii).
Ho wever, there is the questio n of whether the chlo ride has any
SERS activity of its o wn? The o nly po ssibility is, of co urse, that a
metal-chlo ride vibratio n can be detected. This is of some interest,
because, if seen, it wo uld mean that SERS can be extremely useful
for surface studies where mo lecule-metal bo nds are created. Van
Duyne
8
has no ted a Raman signal at 239 cm"
1
at po tentials po sitive
of -0. 4 V, which was "replaced" by a band at 216 cm"
1
at mo re
catho dic po tentials. He asso ciated the first with an AgCl vibratio n
and the last o ne to an Ag-N stretch vibratio n. Creighto n et a/.
182
have made similar o bservatio ns. Bunding et a/.
183
asso ciated a
similar band to a silver-lutidine vibratio n, and Venkatesan et a/.
184
made similar assignments for a series of nitro gen-co ntaining com-
po unds. Venkatesan et al. have also tried to ratio nalize the stro ng
dependence of the band frequency on the electric po tential on the
gro unds that the changing static electric field interacts to varying
degrees with the dipo le of the adso rbed mo lecule.
Pettinger et a/.
185
have no ted that the 240-cm"
1
band appears
in SERS even in the absence of pyridine. Hexter et a/.
113186
have
identified the low-frequency band as that of silver chlo ride and
substantiated their assignment by a theo retical evaluatio n of the
expected frequency.
187
Do rnhaus and Chang
124
further showed that
the 240-cm"
1
band gradually evolves into the 216-cm
1
band as the
electric po tential is moved catho dically, thus establishing their
asso ciatio n to the same vibratio nal mo de. Marinyuk et al.
76
make
a similar asso ciatio n, and remark that it must be a surface AgCl
species. Wetzel et a/.
188
substantiate this co nclusio n by replacing
chlo ride by o ther halides. The vibratio nal band frequency dro pped
from 246 to 166 cm"
1
for bro mide and to 117 cm"
1
for io dide, in
ro ugh co rrespo ndence to the square ro o t of the ato mic masses. This
result was repro duced by Sanchez et al.
144
Do es this indicate that
the halide is attached to an ato m which is an integral part of the
surface, rather to an ad-ato m?
Regis et a/.
118
see a shift of the band frequency from 233 to
180 cm"
1
when changing from chlo ride to bro mide. This is a rela-
tively small change. Do es it mean that their surface preparatio n
and surface species are different (the spectra are reco rded in co ntact
with gas)? In fact, Regis and Co rset
189
asso ciate the 227-cm"
1
feature to a vibratio nal mo de of an anio nic chlo rine mo lecule
radical. Vario us gold chlo ride co mplexes on a gold electro de, as
seen by their Raman scattering, were repo rted by Lo o ,
190
but it is
no t clear whether it is a SERS o r simply multilayer scattering arising
in the ano dic scan emplo yed.
The low-frequency mo des asso ciated with the halides were
seen also in co llo idal systems. Wetzel and Gerischer
191
found on a
silver sol Raman features at 235, 163, and 112 cm"
1
for chlo ride,
bro mide, and io dide. Garrel et al
192
mo nito red the replacement of
chlo ride by bro mide on a silver co llo id.
The po ssibility of detecting metal-mo lecule vibratio ns in SERS
has induced several studies in the absence of halides. Lo mbardi et
al.
193
have investigated a silver sol and fo und for adso rbed pyridine
a wide band at abo ut 230 cm"
1
. This band was no t seen when acetate
or fo rmate io ns replaced the pyridine, but, instead, an unreso lved
feature at slightly higher frequencies (260 cm"
1
) appeared. They
294 S . E frima
infer that perhaps also in electro chemical systems there is a co ntri-
butio n from a metal-mo lecule mo de beside the metal-halide. They
also tabulate the frequencies seen in the presence of vario us
nitro gen- and o xygen-co ntaining mo lecules and co nclude, o n the
basis of reduced mass co nsideratio ns, that indeed a Ag-N o r Ag-O
mo de is seen. They further suggest that o ne can differentiate between
"direct" bo nding to the surface as o ppo sed to bo nding to an
ad-ato m, o n the basis of this analysis. Recently, Mo sko vits
194
has
po inted o ut the limitatio ns of this appro ach.
Lo o ,
195
basing his co nclusio n on a co mparative study of the
low-frequency mo de on Cu, Ag, and Au, revived the assignment
of this band to a metal-pyridine vibratio n. The arguments are:
1. A low-frequency mo de appears for Cu, Ag, and Au at 241,
237, and 232 cm"
1
, respectively, i.e., hardly metal
dependent.
2. In the absence of pyridine, Cu, for instance, exhibits two
bands at 273 and 203 cm"
1
, which are "to o " far from the
241-cm"
1
band to be co nsidered as having a common o rigin
(similarly for go ld).
3. The low-frequency mo des in the absence of pyridine disap-
pear at -0. 8 V, while in the presence of pyridine the
241-cm"
1
mo de is stro ng.
These co nsideratio ns, ho wever, canno t exclude the po ssibility that
a vibratio n of a pyridine-halide-metal (ato m o r surface) co mplex
is respo nsible for the debated Raman feature. This wo uld explain
the shift of the frequency from that of a metal-halide frequency,
the stability to catho dic po tentials
117
(and, perhaps, the relative
insensitivity to the metal itself). One sho uld mentio n in this co ntext
that Krasser et al.
196
repo rted a band at 240 cm"
1
in the Raman
spectrum of pyridine-silver cluster co mplexes, which they asso ciate
with a pyridine-Ag mo de.
This is an appro priate place to mentio n that besides the low-
frequency bands asso ciated with some adso rbed species, there are
several o ther Raman features which are related to the (ro ugh) metal
itself. Maco mber and Furtak
197
have repo rted weak and bro ad
features at 160 and 110 cm"
1
, which they asso ciated with silver bulk
pho no n scattering. These bands, and, in additio n, o ne at 73 cm"
1
,
have been seen earlier by Po ckrand and Otto ,
72
'
77
in an UHV
system.
Ano ther very interesting inelastic scattering was fo und at the
ultralo w frequencies of several cm"
1
. Weitz et a/.
68198199
no ticed
the Sto kes and anti-Sto kes wings of an extremely lo w-frequency
mo de. Its frequency depended o n the excitatio n wavelength, and
shifted from 4 to 12 cm"
1
as the light was tuned acro ss the visible
range, from the red to the blue. The intensity also depended o n the
pyridine co ncentratio n, gro wing with it. It was seen o n co pper and
silver and in an electro chemical system and at a so l. They attribute
that feature to the inelastic scattering of particles (several tens of
nm in size) off their aco ustic mo des. Fleischmann et al.
200
also see
ultralo w-frequency mo des at abo ut 8 cm"
1
, and repo rt their depen-
dence o n electric po tential and o n the catio n in the so lutio n.
Returning to halides and their effect o n SERS, Birke et al
201
have investigated that influence fo r several mo lecules. They repo rt
that chlo ride affects the intensity of different vibratio nal mo des
differently, indicating pro ximity of the scattering mo lecule and the
chlo ride. Further evidence fo r co adso rptio n of pyridine and
chlo ride was o btained from capacitance and SERS measure-
ments.
115
'
202
-
204
Halides are no t the o nly chemical species which can influence
the SERS of o ther mo lecules. Two o ther examples are CO co ad-
so rbed with pyridine in a UHV system, as repo rted by Seki,
83
and
the quenching effect of a small amo unt of TI depo sited o n the
surface.
117
There are many o ther examples.
(I I ) Summary of Effects
In this sectio n it was sho wn that: (1) SERS is dependent o n
the chemical co mpo sitio n of the system, in additio n to the depen-
dence o n the scattering mo lecule itself; (2) halides and pyridine
seem to have a co stabilizing effect and a co enhancing influence;
and (3) o ne can utilize SERS to investigate the bo nd fo rmed by
the adso rbates with the surface.
(iii) SERS of Water
One of the mo st interesting mo lecules from the po int of view
of an electro chemist is the water mo lecule, which generally co n-
stitutes the majo r co mpo nent of the so lid-electro lyte interphase.
Furthermo re, it was a great puzzle why SERS from water was no t
296 S . E frima
seen initially. When it finally was seen, the questio n still remains:
Why are very special co nditio ns needed? This, of co urse, has direct
bearing o n the SERS mechanism.
Billmann and Otto
85
have raised the questio n of the absence
of the water signal from SERS. Soon after, several gro ups managed
to see and repo rt the SERS of water. Pettinger et al
135
have used
high salt co ncentratio ns (saturated NaCl o r 10 M NaBr) in co njunc-
tio n with po tential difference spectro sco py, o n a co pper electro de.
Alternatively, they used an emersio n metho d. They have seen the
OH stretch at abo ut 3500 cm"
1
. Fleischmann et al
204
using 1 M salt
so lutio ns fo und the OH stretch at 3498 cm"
1
, with a no ticeably
smaller width than that of the analo go us bulk water band. Also the
water bend at 1610 cm"
1
was seen. This is a clear indicatio n that a
water mo lecule is invo lved rather than a hydro xyl species. Pettinger
and Wetzel
205
found similar results. A further enhancement for
water, as well as for pyridine and thio urea, by illuminating the
surface during the preparatio n, was repo rted by Maco mber et al
127
and by Chen et al
129
Po ckrand,
206
in a UHV system, detected Raman
signals of water o n co ld-evapo rated silver films. The stretch appears
at 3127 cm"
1
with a sho ulder at 3355 cm"
1
(a similar sho ulder was
repo rted also by the earlier wo rkers). The bend was seen at
1611 cm"
1
. As was no ted by o ther wo rkers the bend is much weaker
than the stretch. Fleischmann et al
201
detected water SER signals
also from 0.5 M cyanide so lutio ns. They discuss a mo del of electro -
static attachment of water to cyanide in o rder to explain the shifted
and narro w Raman features. At this po int, it is no t clear how
appro priate such a mo del can be. Chen et a/.
208
have used an OMA
to follow the develo pment of the water signal during the ORC in
1 M salt so lutio ns. Essentially, the SERS of water parallels the
adso rptio n and deso rptio n of the anio ns. Stro nger signals were
o btained when the anio n was known to be specifically adso rbed
(such anio ns also form inso luble salts with silver). Maco mber et
al
121
show that the SERS of water is a stro ng functio n of the electric
po tential, the pH, and the co ncentratio n of the catio ns (no ticed
also by Fleischmann and Hill
209
). These two gro ups try to infer the
interface structure, from the characteristics of the Raman spectrum.
The reader is referred to the o riginal papers for further details.
In general, the SERS of water is analyzed in terms of the
structure-breaking nature of the vario us io ns, so lvatio n, and degree
of hydro gen-bo nd fo rmatio n. Clearly, this is an impo rtant questio n
which warrants further investigatio n. Blatchfo rd et al
119
nicely
summarize the reaso ns for no t o bserving SERS of water under usual
SERS co nditio ns. Finally, let us no te that acco rding to Seki and
Chuang,
167
po res may be of predo minant impo rtance in SERS.
That, co mbined with the hydro pho bic nature of silver and go ld
surfaces,
210
suggests ano ther reaso n why water do es no t generally
show the SERS effect and why high salt co ncentratio ns are needed.
(it?) Surface Raman Scattering of Dyes
As is well kno wn,
211
there is a qualitative and quantitative
difference between no rmal Raman scattering (NRS) and reso nance
Raman scattering (RRS) for mo lecules in the bulk. The most pro mi-
nent feature is the intense scattering in the reso nance case, as
co mpared to the scattering of a mo lecule no t in reso nance. In fact,
the signals are so stro ng that extremely small quantities can be
detected in the RRS case, even witho ut the "help" of SERS (e.g.,
see Ref. 212).
In the early days of SERS, the studies were naturally directed
to ward mo lecules which were no t in reso nance with the incident
light. Ho wever, a few spo radic investigatio ns of the Raman scatter-
ing of dyes adso rbed in SERS-active systems were carried o ut.
These were, generally, aimed at the study of some reactio n of
interest, o r the study of some interesting mo lecular structure. Only
in few cases was the experiment with the dye viewed in the co ntext
of SERS and SERS mechanisms. In all these cases it was eno ugh
to see that the signal was of "better quality" than for the bulk
(better Raman/fluo rescence ratio s, lower laser po wers needed, etc.)
in o rder to pro claim it to be surface enhanced, witho ut any further
investigatio n. Only recently, since 1982, has it beco me apparent
that dye mo lecules do behave differently than no rmal Raman scat-
terers with regard to SERS. Furthermo re, this difference in behavio r
is directly related to the general type of enhancement mechanism
active in SERS, and can, perhaps, be emplo yed to elucidate it. At
the time of this writing, there is still a heated co ntro versy and a
large degree of disagreement over the experimental results (as
described belo w), and their theo retical interpretatio n in the co ntext
of SERS (to be described in Sectio n III).
298 S . E frima
The aim in the following presentatio n is to discuss the pub-
lished results on Raman scattering of adso rbed dyes, from to day's
perspective, and see whether a clear and unambiguo us picture can
be reached.
At the risk of triviality, the reader's attentio n is drawn to the
fact that being classified as a dye do es no t necessarily mean that
the mo lecule will exhibit reso nance Raman scattering. A dye is a
"ho mo centric" term used to describe a mo lecule which abso rbs
light in some part of the visible spectrum. A mo lecule may scatter
light in a reso nance Raman pro cess pro vided the incident light is
in the frequency range of its abso rptio n band. Outside that band
only prereso nance or no rmal scattering o ccurs. This simple o bserva-
tio n has been so metimes o verlo o ked in the past, which warrants
the remark here.
Jeanmaire and Van Duyne
5
and Van Duyne,
8
in their pio neer-
ing wo rk, have repo rted SERS from two dyes, crystal vio let and
methyl o range, adso rbed on silver. They do no t give an estimate
for the enhancement, but remark that the surface signal was seen
with 5-mW laser po wer! Co mpared to the signal intensities they
o bserved for pyridine at 80-mW po wer, we may estimate the
enhancement factor <10. Co rrecting for the extinctio n in the
so lutio n may give a so mewhat higher value.
Hagen et a/.
145
studied p-nitro so -dimethylaniline (p-NDMA)
on a silver electro de. p-NDMA exhibits a maximum abso rbance at
435 nm. In so lutio n it scatters reso nantly at 488 nm, but the scatter-
ing is 10-fold weaker at 514.5 nm. This indicates that the excitatio n
is very close to the abso rptio n edge. On silver, at +10 mV (electro de
pretreatment no t specified) a surface signal is seen, which resembles,
but is no t identical to , the so lutio n spectrum. It is difficult to evaluate
the surface enhancement, as only scarce details are given. Ho wever,
assuming the cro ss sectio n area of the incident beam is given by
A, the length from which the Raman signal in the bulk experiment
is co llected is given by L (appro ximately 1 cm), the co ncentratio n
in so lutio n is C, and the surface co ncentratio n at saturatio n is abo ut
4 x 10
14
mo lecules cm"
2
, then the ratio between the number of
mo lecules pro bed in the so lutio n and o n the surface turns o ut to
be abo ut 10
6
x C Co mparing Figure la and Figure 2c of Reference
145 gives an enhancement facto r of 100. At 514.5 nm it is 1000.
This is substantiated by the results on Pt, where appro ximately
10-fold-weaker signals were seen at 488 nm and hardly any at
514.5 nm. This enhancement is o rders of magnitude smaller than
the usual SERS enhancements. No te, ho wever, that the usual SERS
surface preparatio n has no t been carried o ut (o r at least repo rted).
Also , such an analysis is very appro ximate.
37
Thus, o ur qualitative
co nclusio ns are:
1. A dye, which in this case is nearly o ut of reso nance, can
show surface enhancements.
2. The enhancements are smaller than the usual SERS
enhancements on similar systems.
3. The enhancements, in this case, are larger the mo re the
light is o ut of reso nance with the dye.
4. The excitatio n frequency dependence of the scattering
intensity for the adso rbed mo lecule is radically different
than that of the mo lecule in bulk.
Kotz and Yeager
213
investigated co balt phthalo cyanine on a
SERS-prepared silver electro de. Stro ng surface signals were seen,
but no estimate of the enhancement was given. Reluctantly, we
reso rt to the appro ximate analysis used abo ve. Taking C = 0.01 M,
o ne finds from the spectra given in this paper a 10
4
enhancement.
Ho wever, the so lutio n at 0.01 M is abso rbing while in the
electro chemical case C = 10~
5
M. Thus this estimate is pro bably
an upper limit. No te, the excitatio n wavelengths used are within
the transmissio n windo w; thus o nce again the mo lecule is no t fully
in reso nance.
Pemberto n and Buck
214
studied the adso rptio n on a silver
electro de of diphenylthio carbazo ne anio n (HDz), a dye with its
abso rptio n maximum at ~470nm. An ORC was no t carried o ut.
Again, the enhancement was no t evaluated. Ho wever, if o ne com-
pares the surface spectra o btained, to tho se repo rted for a gold
electro de
215
using 488-nm light, it is immediately clear that the
Raman scattering is hardly surface enhanced at all on silver, as it
is no t, at least at this excitatio n, at go ld.
Busby and Creighto n
37
sho wed that 2-amino -5-nitro pyridine
anio n (ANP~) shows enhancement on a pro perly prepared silver
electro de of a facto r of 1.5 x 10
4
. This dye abso rbs at 450 nm, but
the excitatio n was at 647.1 nm, very much off reso nance. Blatchfo rd
et al.
216
no ted that the excitatio n spectrum of "ruthenium red" on
the surface of a silver electro de (after ORC) was shifted to 600 nm,
300 S . Efrima
while in so lutio n it peaks at abo ut 530 nm. This was co mpared to
the maximum seen in the excitatio n spectra of adso rbed pyridine
or that of chemiso rbed cyanide at 600 nm. They do no t give an
estimate of the enhancement facto r. Furthermo re, the electric po ten-
tial in this measurement was ~0V, while for the pyridine and
cyanide it was -0. 95 V. As will be shown later, the SERS excitatio n
spectra stro ngly depend o n the po tential, a fact that has to be
acco unted for in any co mpariso n such as abo ve.
Campbell and Creighto n
217
discussed the excitatio n profile for
several dyes adso rbed o n a silver electro de. They analyze the data
in terms of a product of two Lo rentzians: o ne for the reso nance
enhancement (RR) and the o ther for the SERS. The assumption is
that o ne can have bo th RR and SERS effects simultaneo usly. Their
co nclusio n is that the excitatio n band of the dye on the surface is
shifted co mpared to so lutio n. The effect of the surface is indeed
clearly seen. Ho wever, the same experimental spectra can be
analyzed equally well also in terms of a sum of two Lo rentzians,
meaning that o ne has either RR or SERS effects. Only a careful
estimate can distinguish between these two interpretatio ns of the
experimental results.
Co tto n et a/.
218
repo rt a 10
5
enhancement facto r for Cyto chro me
C adso rbed o n a silver electro de, treated by the usual ORC. They
do no t give details of the estimate. One canno t use the simple
scheme we used abo ve in this case, as here are large pro tein
mo lecules, with a much different surface coverage than that of small
mo lecules. The Raman scattering of myo glo bin was also measured,
tho ugh no estimates of its enhancement were given. Co tto n et al
219
measured the surface Raman spectrum of an even larger pro tein,
Cyto chro me C
dl
. They co nclude that its scattering is enhanced
similarly to that of the first two mo lecules. In all the cases, they
no te the dependence of the intensity on electric po tential and the
high depo larizatio n ratio s, indicating a surface species. However,
unless lo ng-range effects are co nsidered, o ne wo uld require the
po rphyrin mo iety, which is the center of the reso nant behavio r, to
be expo sed to the surface, at very close pro ximity. This may be
difficult to realize witho ut denaturatio n of the pro teins. The heme
gro up in Cyto chro me C is buried in the center of a nearly spherical
pro tein, 3.4 nm in diameter, and in myo glo bin it is in a crevice with
a pro pio nate side chain between it and the surface of the pro tein.
220
Ohsawa et al
62
investigated the n-heptyl vio lo gen mo no radical
catio n adso rbed on a silver (no t treated by ORC) and a platinum
electro de. They find stro ng surface Raman signals on bo th elec-
tro des, and can detect scattering for films as thin as 0.5 nm (judged
by the charge passed to reduce the dicatio n parent mo lecule). The
excitatio n spectrum co mpletely o verlaps the abso rptio n band. This
is a go o d example of a reso nance scattering seen on silver, witho ut
the SERS effect.
Co tto n et al,
221
studied meso -tetrakis (4-sulfo nato phenyl)po r-
phine, TSPP, and the 4-carbo xy derivative, TCPP, adso rbed on
silver. These mo lecules have a stro ng abso rptio n at 420 nm and a
weaker o ne at 514.5 nm. An intense surface spectrum was o btained
for bo th mo lecules. Co mpared to the scattering intensity from the
so lid, the enhancement was estimated to be appro ximately 10
5
. The
way that the abso rbance of the so lid was co rrected for was no t
specified. No te also that at 457.9 nm the mo lecules are no t entirely
in reso nance. The metalated form (suggested to be o ne of the surface
co mpo nents) is also no t really o n reso nance at 514.5 nm. The
lo ng-wavelength abso rptio n is a weak o ne. Furthermo re, silver is
no t no ted for pro ducing large enhancements at 457.9 nm! This, of
co urse, bears immediately o n the spectra o bserved at 514.5 nm.
Obvio usly, this po int needs further clarificatio n.
Itabashi et al
222
also studied TSPP adso rbed on silver, from
an acid so lutio n where it is fo und as a dimer. While the details,
dependence on electric po tential, for instance, are different, they
to o co nclude that the scattering of the dye is further enhanced by
the surface. No details of the estimate are given. This mo lecule, in
its aggregated form, abso rbs light at 490 nm and the mo no mer at
434 nm. Using 488-nm excitatio n, they see no scattering at 0 V (vs.
Ag/AgCl), while at catho dic po tentials (starting from -0. 1 V) stro ng
signals are seen. They co nclude that the scattering is enhanced, but
do no t give any estimate of the degree of enhancement.
Watanabe and Pettinger
86
estimated the enhancement of the
Raman scattering of crystal vio let (CV) adso rbed on a silver
electro de. They repo rt an enhancement of abo ut a 1000, but give
no details of their estimate, tho ugh they admit it is a ro ugh o ne.
They felt it co uld be even larger, in better agreement with the large
enhancements repo rted previo usly,
5
which only now we know are
no t "very large. " Furthermo re, they have no ted that relatively
302 S . E frima
intense Raman signals from CV adso rbed on smo o th silver elec-
tro des are seen. This may indicate an upper bo und to the enhance-
ment facto r o n the ro ugh surface, which is lo wer than their estimate.
One sho uld no te that s-po larizatio n was used, which is even mo re
detrimental for the scattering from smo o th surfaces than it is for
ro ughened o nes. The excitatio n spectrum fo und for the CV was
very similar to that in so lutio n.
McMaho n
223
sho wed that f-l,2-bis-(4-pyridyl)ethylene, (t-
BPE), adso rbed on a silver electro de exhibits an excitatio n profile
with a definite maximum at abo ut 600 nm, and then increases again
to ward the red. The intensities were no rmalized to perchlo rate io n
scattering. These maxima have no co unterpart in the so lutio n
abso rptio n spectrum. This is a case of an off-resonance SERS effect.
Stacy and Van Duyne
38
studied the Raman scattering of
tris(2,2'-bipyridine) ruthenium, TBPR, adso rbed on a silver elec-
tro de from an aceto nitrile so lutio n (ano ther electro chemical SERS
study repo rted recently is that in Ref. 224). They find that the
surface spectra at 457.9 nm (when the mo lecule is in reso nance)
and at 647.1 nm (when it is to tally o ut of reso nance) are co mparable
in intensity. As an internal reference o ne may use the aceto nitrile
band seen in bo th of the spectra, assuming it is from the no nad-
so rbed so lvent. At 647.1 nm, an enhancement > 10
6
is estimated. The
co nclusio n must be that the enhancement at reso nance is o rders of
magnitude smaller than at the off-resonance situatio n. An estimate
of the difference is no t given. An interesting po int is that at 457.9 nm
the Raman spectrum was identical in band po sitio ns and relative
intensities to that seen in so lutio n. At 647.1 nm there were large
changes in the relative intensities of the bands and several new
bands appeared. Ano ther po int of interest is that, as repo rted in
the paper, no signal was seen before the ORC (with a so lutio n
co ncentratio n of 5 x 10~
5
M). This indicates that: (1) this mo lecule
is no t a very stro ng reso nance Raman scatterer, and (2) even at
457.9 nm there is some surface enhancement (if o ne co nsiders 10 cps
to be the detectio n limit, then an enhancement facto r of abo ut 250
can be estimated from the figures given in the paper). Further
suppo rt to these co nclusio ns is supplied by a study of the Raman
scattering of TBPR adso rbed on a H-GaAs electro de with a silver
island o verlayer.
225
No Raman signal at 457.9 nm is detected in the
absence of the silver; thus po int (1) above is substantiated (ho wever,
it also may be that the dye is "baked" by the 100-mW po wer used,
or pho to reacted with the pho to active semico nducto r). A clear signal
is o bserved in the presence of silver (appro ximately two o rders of
magnitude abo ve the detectio n limit, as judged from the spectra
given in the paper). The silver can also pro tect the dye from a
pho to reactio n.
226
Now we turn to studies of dyes adso rbed on co llo ids. Lip-
pitsch
59
'
227
'
228
repo rted surface Raman spectra of several dyes ad-
so rbed on a silver sol (methyl vio let, biliverdine, pyrro methano ne,
and pyrro methane), and claimed they were enhanced, implying the
usual large surface enhancement. It is difficult to carry o ut an
estimate of the enhancement as the spectra in so lutio n are do mi-
nated by the stro ng fluo rescence.
Bachackashvilli et al
49
'
229
'
230
have sho wn for a series of azo
dyes adso rbed on a silver hydro so l that the enhancements were
significantly different, smaller, than tho se exhibited by no rmal
Raman scatterers. They circumvented the difficult pro blem of the
evaluatio n of the abso lute enhancement by coadsorbing a dye
mo lecule and a reference mo lecule which is no t in reso nance,
pyridine for instance. Thus o nly relative enhancements were deter-
mined, the dye co mpared to the reference mo lecule. Using co mpeti-
tio n of the two mo lecules over the surface they also co uld extract
relative surface co ncentratio ns, which are required for the calcula-
tio n of relative surface enhancements. This substitutio n experiment
also sho wed that bo th mo lecules adso rbed to similar sites on the
surface. They find that the reference mo lecule, pyridine, exhibits
enhancements larger than 5 x 10
5
. Azo benzene, which is almo st
co mpletely off reso nance (maximum of abso rptio n at 422 nm),
shows a similar enhancement, perhaps up to a facto r of a 100 less.
Methyl yellow (abso rptio n maximum at 447.1 nm) gives an
enhanced spectrum by a facto r of 300 less than co adso rbed pyridine.
4-dimethylamino -2-methylazo benzene (maximum at 453.5 nm)
gives enhancement 1000-fold less than pyridine. Methyl o range
exhibits an enhancement smaller by 3 x 10
4
. The scattering of
methyl red (maximum of abso rptio n at 515 nm) is enhanced 10
5
less than pyridine. Thus a clear trend evo lves: gradually smaller
enhancements the mo re the mo lecule's reso nance. All this is in the
presence of ano ther mo lecule which exhibits the usual large surface
enhancement. The excitatio n profiles of the dyes and the co adso rbed
304 S . Efrima
pyridine are also fundamentally different. While the pyridine signal
gains intensity to ward excitatio n in the red, that of methyl red has
a maximum aro und 550 nm. As the excitatio n profiles are measured
simultaneo usly for bo th co adso rbed mo lecules, o ne can rule o ut
mo rpho lo gical changes (aggregatio n) as a cause for the difference.
Lee and Meisel
231
investigated 4,5-benzo indo tricarbo cyanine,
BICC, which abso rbs in the red (o ne abso rptio n maximum at
700 nm and the o ther at 800 nm). On a silver co llo id they o btained
an intense spectrum at 514.5 nm, at which wavelength the dye is a
no rmal scatterer in so lutio n. They also o bserve intense Raman
signals at 647.1 nm when the dye is adso rbed on a gold so l. They
do no t estimate whether there is any further enhancement in addi-
tio n to that due to reso nance. Significantly, a co pper phthalo cyanine
dye, with abso rptio n maximum at ~670nm, exhibited a weak
Raman signal from a go ld sol with 647.1-nm excitatio n, while in
so lutio n it pro duces intense spectra.
Siiman et
a
i
34
>
232
>
233
studied dabsyl aspartate. On a silver co llo id
in ethano l and in water they repo rt enhancement facto rs ranging
from 20 to 2000, at vario us wavelengths. This is based on experi-
mental attempts to estimate the surface co verages.
Akins
234
repo rted an enhancement of abo ut 2000 for cyanine
chlo ride when adso rbed o n a silver so l. Ho wever, the dye abso rptio n
is centered aro und 530 nm, while for the Raman studies a 564-nm
excitatio n was used, i.e., a slightly off-resonance situatio n. An
abso rptio n feature, no t present for the dye by itself o r the sol alo ne,
was seen at abo ut 575 nm. Akins interprets it as due to a dye
aggregate. Ho wever, as will be seen in Sectio n II. 5, similar bands
are co mmo nplace in SERS systems. In a separate study, Li et al
235
tried to evaluate the enhancement factor for cyanine chlo ride at
488 nm (in the abso rptio n band) on a silver electro de and on a so l.
Their estimate is a facto r of abo ut 50 for the co llo id and 10
4
o n
the electro de. One sho uld recall the difficulties inherent in such
determinatio ns (see Section II. 1).
Kneipp et al
494
investigated several cyanine and mero cyanine
dyes adso rbed on a silver so l. The abso rptio n maxima of these dyes
were 422, 557, 655, and 468 nm, and they used the 514.5-nm line
of an argo n io n laser. They found that all these dyes gave intense
Raman surface spectra of co mparable intensity. It is especially
wo rthwhile to emphasize that the same intensity was registered for
the dye which was, mo re o r less, in reso nance and the dyes which
were far off reso nance. They also repo rt that the dyes, also the dye
which was on reso nance, exhibited surface enhancements larger
than unity. Ho wever, they do no t repo rt how large o r give any
details. Surface co ncentratio ns are also no t repo rted.
Aro ca and Loutfy
236
repo rt surface enhancement from
phthalo cyanine films with 15-nm silver o verlayers. They estimate
the enhancement at 1000, but give no details of their metho d of
deriving it. No te, further, that the dye was investigated at a "win-
do w"
237
of its abso rptio n spectrum. The dye in a film abso rbs at
~600nm, while the surface studies repo rted were at 488 and
514.5 nm.
Several studies of Raman scattering of dyes from island films
have been carried o ut. Chen et al.
23S
claim enhancement of
fluo rescein iso thio cyanate scattering, at vario us wavelengths (at
least over the fluo rescent backgro und). Full details are no t given.
Weitz et al.
239
'
240
have carried o ut a systematic study of the
behavio r of no rmal Raman scatterers and reso nance scatterers on
silver islands (incidentally, they also investigated fluo rescence as
well). They find an enhancement facto r of abo ut 1000, for
rho damine 6G and basic fuschin, co nsiderably smaller than that
fo und for p-nitro benzo ate in a similar but no t identical experiment.
Their estimate of enhancement is based o n a co mpariso n with the
Raman intensity of the same dye adso rbed o n a silica slide, assuming
the to tal co verages are equal. This last po int is investigated by
co mparing the fluo rescence from the silver-dye and silica-dye
systems. They exhibit the same peak po sitio ns for the same prepar-
atio n pro cedure. This was taken as evidence that, under similar
co nditio ns, bo th substrates have the same co verage, as fluo rescence
peaks shift with aggregatio n. Ho wever, this may only pro ve that
coverages per real surface area are equal; the to tal amo unt of the
adso rbed mo lecules may still be different. Actually, o ne expects
the silver island system to have mo re adso rbed mo lecules due to
its ro ughness. Co nsequently, the enhancement of 1000 is only an
upper limit, and a facto r of merely 300-500 wo uld no t be surprising.
Anyway, this is in agreement with the results fo und with co llo ids.
The excitatio n spectrum measured for R6G and for p-nitro benzo ate
peaked at the same frequency, but the former was much narro wer.
Both profiles were on the lo ng-wavelength sho ulder of the
306 S . E frima
abso rptio n band of the silver islands. Fo r high dye co verages
157
the
abso rptio n band of the system was found to split, exhibiting maxima
at abo ut 440 and 590 nm. The Raman excitatio n profile also sho wed
two peaks, this time very near the abso rptio n peaks.
Nimmo et al
241
measured the Raman scattering of co pper
phthalo cyanine in pressed silver, KBr, Cu, and Al disks. This is a
dye pro ducing intense signals at co ncentratio ns as low as 10~
6
M
The ratio of intensities measured for the four substrates was
abo ut 10: <1:1:2, respectively, which indicates (very) small
enhancements for silver. No te, ho wever, that the autho rs did
no t show that such silver disks exhibit SERS for no rmal Raman
scatterers.
Shoji et al.
242
investigated a po rphyrin and its co mplexes with
silver. The dye is adso rbed to a calcium fluo ride substrate and
o verco vered by silver. In the absence of silver no signal was detec-
ted, while in its presence a stro ng Raman spectrum was seen. This
may be due to a surface enhancement, o r to a degrading pho to -
chemical reactio n in the absence of the silver. The degree of
enhancement is no t given, but judging from the so lutio n and sur-
face spectra, and co nsidering the abso rptio n in the so lutio n, an
enhancement facto r of less than 1000, pro bably much less, can be
evaluated.
To summarize, it was shown that:
1. Mo lecules at reso nance show a significantly different SERS
behavio r than "no rmal" scatterers, especially as regards
the surface enhancement.
2. The enhancement of the surface Raman scattering of dyes
at their reso nance (which may be shifted on the surface
as co mpared to so lutio n) is that of "no rmal" Raman scat-
terers.
3. The additio nal surface enhancement is greater the mo re
the dye is o ut of reso nance.
4. A dye "fully" in reso nance exhibits a surface enhancement
of up to abo ut two o rders of magnitude.
5. The excitatio n Raman profiles for adso rbed dyes are gen-
erally different from tho se for the dyes in so lutio n, and
from that of "no rmal" scatterers exhibiting the SERS
effect.
4. M etals (or S olids) which E xhibit S E R S
(i) General
It is often wo ndered whether SERS is a useful to o l in the study
of so lid surfaces in general o r, perhaps, it is o nly a unique pro perty
of silver and its family. In the latter case the utility of SERS wo uld
be greatly diminished. Fro m the theo retical po int of view it is also
extremely interesting to kno w which so lid substrates suppo rt SERS.
This may be an impo rtant clue in elucidating the enhancement
mechanism itself.
One sho uld keep in mind several po ints when co nsidering the
experimental evidence for SERS activity o n vario us so lid substrates,
in additio n to the co nsideratio ns mentio ned in Section II. 1:
1. SERS is stro ngly dependent on the excitatio n frequency,
a dependence which varies from so lid to so lid (see Section
II. 5), and, in additio n, for the same substrate, it depends
o n the surface preparatio n pro cedure ado pted. Therefo re,
the practice is to scan for SERS activity thro ugho ut the
visible range and the near UV, the classical do main of
Raman spectral effects.
2. Merely detecting a Raman signal from a so lid substrate
surface do es no t necessarily mean that SERS is in effect.
Weak signals can be detected due to the impro ved Raman
systems, the larger surface areas o n ro ugh surfaces, multi-
layer fo rmatio ns, and simple reflectivity co nsideratio ns.
3. One is bo und to find from time to time unique, specific
systems where a special mechanism causes an enhancement
of Raman scattering. Such a case, for instance, is pro bably
the enhancement of the Raman scattering of oxygen on
po lydiacetylene.
243
It is tho ught to o riginate from a charge
transfer mechanism. In this review such systems will be
co nsidered SERS active only if several mo lecules (of differ-
ent types) show an enhancement.
4. Negative results are generally no t repo rted in the literature
and when they are, no details are given. There is always
the po ssibility that the pro per experimental co nditio ns were
no t achieved. As an example, detecting the Raman signal
in a no rmal directio n to the surface and using s-po larized
308 S . E frima
incident light discriminates against S E R S , especially fo r a
relatively smo o th surface.
() Coinage Metals
It is senseless to specifically list here the studies do ne with
silver; they are referenced thro ugho ut this review. Wo rk o n go ld
and co pper is also relatively abundant and full co verage o f all
pertinent references is no t attempted here. To detect SERS fro m
these metals, excitatio n in the red is required. A surface preparatio n,
ORC fo r instance, is o ften needed, as described in Sectio n II. 2.
Go ld and co pper have generally sho wn weaker maximum
intensities than silver. Several examples o f studies o n go ld in
electro chemical systems are to be fo und in References 116, 190,
195, 205, 244, and 245, and fo r co llo idal suspensio ns see References
35, 60, 78, 191, 246, and 247. Wo rk has also been do ne o n go ld
films.
73
'
79160
'
238
'
248
Several studies o n co pper as a substrate were
carried o ut in electro chemical systems (see Refs. 53, 88, 90, 116,
135, 149, 195, 205, 244, 245, 249, and 250), o n a co llo id,
36
and o n
films
79
'
160
'
248
and clusters.
251
'
252
Furtak et a/.
111
'
253
have sho wn that a go ld electro de which
sho ws no SERS activity with 514. 5-nm excitatio n (at least no t within
the detectio n limit), exhibits Raman signals fro m adso rbed pyridine
when submo no layer quantities o f silver are depo sited o n it. They
no te that under tho se co nditio ns no changes in the o ptical pro perties
o f the substrate are detected. Plieth et al.,
254
in a similar experiment,
repo rted SERS fo r cyanide, but o nly after an ORC was carried o ut
o n the depo sited silver. It seems that their depo sited films were
thick, co ntrary to the co nditio ns o f the previo us experiment. A
series o f silver-go ld allo ys was investigated by Kester and Furtak.
255
At 488- o r 514. 5-nm excitatio n, adding go ld, stro ngly quenched the
SERS signal o f pyridine. Starting fro m go ld and measuring at
647. 1 nm, increasing the silver co ntent slightly lo wered the signal,
which increased again as the limit o f fo rmatio n o f pure silver was
appro ached. No te that in this case po tential difference spectra were
repo rted, which may co mplicate the interpretatio n o f these results.
Murray
256
investigated the effect o f go ld layers depo sited o n
silver island films o n the SERS o f cyanide. Go ld island films did
no t suppo rt SERS o f cyanide (within the detectio n limit o f abo ut
a 1000 enhancement facto r) when 488-nm excitatio n was used.
However, the go ld-co vered silver islands did exhibit SERS of a
gold cyanide species. The signal decreased with gold thickness,
between 0.05 and 1 nm. If o ne assumes a smo o th coverage of the
gold over the silver, this can mean only that the silver exerts a
Raman enhancement effect at a distance (the thickness of the gold
layer), and that this effect decreases with distance and perhaps with
the change of the o ptical pro perties from tho se of silver to tho se
of go ld. Such a layer-by-layer depo sitio n was indeed seen for gold
on smo o th silver single crystals o r o riented films. However, the
details of the depo sitio n on the island films is no t really kno wn,
and there is a po ssibility that go ld starts pro ducing structures of
several layers in thickness befo re co mpletely filling in the first layer.
In that case, the Raman results can be explained on the basis of a
sho rt-range enhancement mechanism which enhances the scattering
of a go ld cyanide "mo lecule" o n the silver, just as with pyridine.
Thus, a co mplete layer of go ld cyanide will quench the silver cyanide
signal, as seen in the experiment at abo ut 0.5-nm thickness, simply
because there will be no silver cyanide. As the go ld layer grows to
1 nm, cyanide will be to o far from the silver to give an enhancement
effect. There sho uld be a smo o th transitio n, as is seen in the gradual
disappearance of the silver cyanide signal.
(iii) Other Substrates
Other metals have also been investigated as pro bable SERS-
active systems. Platinum, the co nventio nal electro de in many
electro chemical studies, was studied by Co o ney et al.,
257
'
258
with
electro generated io dine as the scattering mo lecule. Io dine is a
reso nance scatterer at 514.5 nm and, in additio n, the surface was
a ro ugh o ne. Thus, it seems that this result do es no t indicate a
SERS effect. (Is there a po ssibility that the 174-cnT
1
band seen in
this experiment belo ngs to a platinum-io dide surface "co mplex"?
Some platinum io dides are inso luble. ) As sho wn by Co o ney et al
259
the large surface area of platinized platinum is in itself eno ugh to
pro duce (weak but detectable) signals. The autho rs also no te that
the intensity of the "io dine" scattering was no t sensitive to a
frequency change from 514.5 to 488 nm. Heitbaum
260
measured the
310 S . Efrima
Raman scattering from the pro duct of the o xidatio n of phenyl-
hyrazine adso rbed on a slightly platinized platinum electro de. The
intensity is large; ho wever, how much of it is the co ntributio n from
the so lutio n species is hard to tell. Benner et a/.
81140
saw SERS of
silver cyanide from Pt electro des only after several layers of silver
were depo sited on them. Lo o
82
'
261
repo rted io dine and chlo rine
SERS from a platinum electro de, even in excitatio n frequencies
removed from the abso rptio n band. He further no tes that the
excitatio n profile for co adso rbed io dine and triio dide io n are sig-
nificantly different, suggesting that SERS is chemistry specific.
Benner et al
262
fo und a small (less than 20) enhancement effect
for platinum cyanide on a platinum co llo id.
Krasser and Reno uprez
171
have repo rted SERS for benzene
adso rbed o n a dispersed platinum catalyst. They estimate the
enhancement to be as high as 2000. This is based on the assumptio n
that 1 cps co rrespo nds to an enhancement facto r of unity. They
find that the enhancement increases to ward sho rter wavelengths,
up to 400 nm.
Lo o
263
has measured Raman scattering from pyridine adso rbed
on a cadmium electro de. Pettinger and Mo erl
264
co uld no t repro duce
these results. Lo o
82
has also measured the Raman scattering of
io dine and triio dide on palladium. He fo und a very bro ad excitatio n
pro file, similar to the o ne he repo rted for Pt. Fleischmann et al
136
repo rted SERS (abo ut 10
4
) from pyridine adso rbed on ro ughened
palladium hydride, under very special preparatio n co nditio ns,
including the presence of CO. The intensity at 514.5 nm was higher
than at 488 nm. Furtak and Kester
265
showed that allo ying silver
with Pd quenches the Raman signal of adso rbed pyridine already
at 5% palladium co ntent.
Two studies
93
'
266
repo rt SERS for mercury; ho wever, these
experiments have no t been repeated. It wo uld be very desirable to
have mo re data for this metal.
So dium,
267
lithium,
106
'
268
and indium
268
have been repo rted to
be SERS active. In a series of papers, Krasser et a/.
98
'
99
'
269
-
271
have
repo rted Raman scattering from CO and benzene adso rbed o n
high-surface-area Ni catalysts. Stencel and Bradley
272
o btained,
under relatively high pressures of CO, Raman spectra from nickel
single crystals. The spectra were very po o r, of abo ut 10 cps. The
apparent enhancement facto r is unrepo rted. Borov et al
273
also see
acetylene o n Ni films, but details of the intensities and co verages
are no t given.
Yamada and Yamamo to
274
repo rted surface Raman scattering
from pyridine adso rbed o n sputtered films of Ag, Au, Ni, and Pt.
The enhancements are no t estimated. There is a stro ng backgro und
which is very steep at abo ut 1000 cm"
1
. The signal/backgro und
ratio in this regio n is small. Nickel exhibits the stro ngest spectrum
of all! (at 514.5 nm; no signal at 600-nm excitatio n). In subsequent
wo rk,
275
"
277
Raman scattering of pyridine adso rbed o n evapo rated
films of Ni, Pd, and Pt was studied. Under SEM no ro ughness
larger than 20 nm was detected. Surface pyridine signals are repo r-
ted to be seen on all these metals, and judging from the excitatio n
pro file, their intensity is co mparable to that measured from silver.
Pt, Ni, and Pd had maximum scattering in the regio n 500-550 nm,
while on Ag and Au the intensity increased with exciting
wavelength. Signals of co mparable intensity to that measured on
the metals were repo rted also from single crystals of NiO and TiO
2
!
A weak scattering from pyridine adso rbed o n carbo n was also
repo rted. In all these studies the signals were co nsidered to be
surface signals due to the measured frequency of 1004-1014 cm"
1
which is shifted from the neat pyridine vibratio nal band at 993 cm"
1
,
and to the fact that the system was evacuated at ro o m temperature
to 10"
5
To rr. Ho wever, no te, for instance in Reference 275, that
befo re evacuatio n a signal is seen at 1009 cm"
1
.
Lo o
278
investigated Raman scattering of electro generated
io dine o n a titanium o xide electro de. He repo rts signals at 181,
190, and 360 (weak o verto ne) cm"
1
. Also the anti-Sto kes transitio n
is seen. The signals were no t seen at 488- o r 514.5-nm excitatio n,
but only for excitatio ns between 530.9 and 647.1 nm. This stro ngly
indicates reso nance scattering. Ho wever, that of "free" io dine is at
515 nm, and the band gap of the o xide is 3 eV (415 nm). Thus o ne
must co nclude that the interactio n of the io dine with the so lid shifts
the reso nance to lower frequencies.
Ano ther semico nducto r, n-GaAs, was studied by Van Duyne
and Haushalter
225
; ho wever, it was fo und to be SERS active only
after a depo sitio n of a silver island o verlayer. Furthermo re, the
mo lecule that was investigated was a dye at its abso rbance
wavelength. The silver can have a do uble ro le: (1) to enhance the
scattering, just as it is do ne on a silver electro de; and (2) to pro tect
312 S . E frima
the dye from a destructive pho to chemical reactio n with the incident
laser light.
There are claims that also aluminum pro duces enhancements.
Liao and Stern
174
saw Raman scattering of /?-nitro benzo ic acid
adso rbed o n o xide-co vered (~3-nm thickness) aluminum ellip-
so ids, which was 500-fold weaker than exhibited on silver. The
intensities o n aluminum increased by a facto r of 3 changing the
exciting energy from 2.2 to 2.7 eV, tho ugh the o ptical parameters
of aluminum are rather co nstant in this regio n. Lo pez-Rio s et al
279
also repo rted surface Raman spectra from (perhaps) mo lecular
oxygen and carbo n o xides adso rbed on aluminum in UHV co ndi-
tio ns. No SERS of pyridine was seen.
(iv) Summary of SERS-Active Substrates
To summarize this sectio n, the following po ints are pertinent:
1. The co inage metals are SERS active in all the systems
investigated, pro vided a pro per wavelength is used (for
go ld and co pper, in the red).
2. Other metals have been studied far less extensively, and
tho ugh there are indicatio ns that enhancements are po s-
sible, their general applicability has no t yet been demo n-
strated.
One wo uld like to see whether a given metal exhibits large
enhancements in vario us systems (electro chemical, co llo id, films,
etc.) and for several different mo lecules.
5. E xcitation P rofiles
(i) General
Raman scattering, in general, and SERS, in particular, depend
o n the frequency of the incident light. No rmal Raman scattering
is characterized by a fo urth-po wer dependence on the frequency.
This intro duces a facto r of appro ximately 6 between 700 and
450 nm. Reso nance Raman scattering in so lutio n has an additio nal
stro ng frequency dependence stemming from the frequency-depen-
dent mo lecular po larizability. This generally leads to an excitatio n
profile peaked at the neighbo rho o d of the abso rptio n band and
stro ngly falling off for lo wer and higher frequencies. Changing the
frequency in a range of 100 nm may result in o rders-o f-magnitude
changes in the Raman scattering intensities.
It was tho ught that measuring the excitatio n frequency depen-
dence of SERS may supply unambiguo us info rmatio n which may
then be interpreted in terms of a unique enhancement mechanism.
In additio n, such excitatio n profile studies co uld help in finding
the best co nditio ns for giant SERS effects, thus facilitating their
utilizatio n.
Several specific questio ns were of interest in such studies:
1. Is there any difference in the SERS excitatio n profile and
that of the same mo lecule in so lutio n?
2. How do es the excitatio n profile relate to the excitatio ns of
the so lid as seen in transmissio n o r reflection abso rptio n
spectro sco pies?
3. Are the SERS excitatio n profiles of vario us mo des in the
same adso rbed mo lecule different o r similar?
4. How do the SERS excitatio n profiles of different mo lecules
co mpare, especially for no rmal scatterers (in so lutio n) in
relatio n to reso nance scatterers, e.g., dyes?
Po ints (1) and (2) abo ve require determinatio n of abso lute
behavio r, in general, in two different enviro nments. Po ints (3) and
(4) call for relative behavio r, which is easier to study.
In general, abso lute intensity excitatio n profiles are no t
measured directly. One needs to co rrect for the accumulatio n,
dispersio n, and detectio n systems respo nse at the vario us frequen-
cies. These respo nse functio ns can be measured and tabulated for
future use. Ho wever, it is mo re co nvenient to use a reference signal
to co rrect for that as well as for laser intensity variatio ns and
changes in the system co nfiguratio n. In an electro chemical system
o ne may measure simultaneo usly with SERS a Raman signal from
a mo lecule in the so lutio n which is present in a high eno ugh
co ncentratio n (such as perchlo rate io n from the suppo rting elec-
tro lyte
185
'
223
o r perdeutero pyridine
88
). In film studies an oxygen
o verlayer was used,
267
for example, and in co llo ids the water signal
was emplo yed.
262
One can so metimes use the signal from thick
layers of the mo lecule as a reference.
58
'
106
In this case o ne generally
assumes that the enhancement is sho rt range.
Ano ther po ssibility is to have the reference mo lecule in a
separate cell, o r an entirely separate experiment co nducted just
314 S . E frima
prio r to o r after the SERS measurement.
35
'
36
'
60
'
97
'
216
This is o bvio usly
less desirable. In the case of so lutio ns o r suspensio ns (as with
co llo ids) a spinning technique may be used
246
with the reference
mo lecule in o ne-half of the cell in the absence of the co llo id,
separated from the co llo id suspensio n lo cated in the o ther half of
the cell. This has the disadvantage of having to co rrect for the
frequency-dependent transmissio n. Ideally, o ne wo uld want the
reference mo lecule to have a stro ng Raman band in the vicinity of
tho se of the SERS-active mo lecule, but no t o verlapping, of co urse.
In some cases, such as for films evapo rated on a base which
is no t SERS active, o ne may have a free base surface with the
adso rbed mo lecules as a reference for the adjacent metal-co vered
surface.
50
'
106
Tho ugh the real surface coverages may differ between
the bare base and the metal-co vered o ne, this po ses no pro blem
for the excitatio n spectra (except in extreme cases of highly adso rb-
ing mo lecules). Of co urse, for the determinatio n of abso lute
enhancement facto rs, this metho d sho uld be used with cautio n.
A unique reference signal used so metimes in SERS, is the
Rayleigh signal
254
or the backgro und co ntinuum.
86
No rmalizing the
detected Raman intensity with respect to either of these reference
signals co rrects for detectio n respo nse, geo metry changes in the
system, laser intensity, and even for surface ro ughness and trans-
mission of the system. Co rrecting with respect to the Rayleigh
scattering has the disadvantage of a very high signal which may
call for inserting an attenuating filter between the sample and the
entrance to the mo no chro mato r, o r partially clo sing the slits. It also
has the disadvantage that the no rmalizatio n is carried o ut with
respect to a frequency some 25-75 nm away from the Raman-shifted
frequencies. Referencing to the backgro und o r to the Rayleigh
scattering may no rmalize o ut many effects of the surface which are
common to these surface o ptical pro cesses. This may be a serio us
fault, especially if abso lute behavio r is of interest. Otherwise, it is
a very co nvenient metho d.
(ii) Excitation Profiles in Electrochemical Systems
In an early paper, Pettinger et a/.
185
measured the excitatio n
profile of SERS to gether with the reflectivity for pyridine on silver
single-crystal electro des. The Raman profile showed gradual
increase of the signal as the excitatio n frequency was changed from
457.9 to 647.1 nm, by a facto r of abo ut 20 for the 1008-cm"
1
mo de
and a facto r of abo ut 10 for the 1037-cm"
1
mo de. These profiles
were no rmalized to a perchlo rate internal standard. Thus, it is
apparent that the SERS profile is different from the excitatio n
behavio r in so lutio n, and that each mo de has its own dependence.
This is especially significant here as the two mo des are very close
in frequency and bo th are ring-breathing mo des. The reflectance
reveals a bro ad structure, peaking at 750 nm, with a sho ulder at
650 nm. Both were absent in the absence of pyridine o r befo re an
ORC was perfo rmed.
280
Thus, at least a circumstantial co rrespo n-
dence between the SERS excitatio n profile and the dielectric pro per-
ties of the metal-mo lecule system was established. The results for
the Raman excitatio n spectrum were measured also by Creighto n
et a/.
182
and co rro bo rated by o ther gro ups.
205
'
281
Tadjeddine and
Ko lb,
282
using surface-plasmo n excitatio n dispersio n metho ds, co n-
firmed the reflectance measurements. Marinyuk et al
244
attempted
to lo cate a po ssible abso rptio n, by analyzing the ratio of Stokes
and anti-Sto kes scattering. They repo rt a transitio n at abo ut 650 nm.
Ho wever, o ne sho uld no te that their analysis co nsiders the
frequency dependence to result only from the po larizability, and
assumes that the dependence of o ther system parameters, such as
metal reflectivity, is relatively weak.
Blatchfo rd et al.
216
extended the frequency range to abo ut
800 nm and fo und a maximum of the excitatio n spectra for adso rbed
pyridine, cyanide, and triphenylpho sphine. The maximum was at
600 to 750 nm and was so mewhat mo lecule dependent. Replacing
the so lutio n by nitro gen gas, made apparent changes in the excita-
tio n profile for triphenylpho sphine. The peak at 710-740 nm was
bro adened and in o ne experiment (o ut of the two repo rted) a shift
to sho rter wavelengths was no ted (to abo ut 630 nm).
A very interesting dependence of the excitatio n spectrum on
the electric po tential was repo rted by several gro ups.
117
'
283
"
286
Otto
et a/.
283285
sho wed for pyridine on silver a gradual shift of the
maximum of the excitatio n profile to higher energies as the electric
po tential was changed in the ano dic directio n. The shift was
appro ximately the same for all the bands (1006, 1215, and
1594 cm"
1
), except for the 623-cirT
1
band which was mo re weakly
affected. The shift is rather large, abo ut 2-3 eV V"
1
. As shown by
316 S . E frima
Furtak and Maco mber,
286
the co mpo sitio n of the so lutio n affected
the slo pe of the maximum frequency/electric po tential curves.
Higher chlo ride co ncentratio ns resulted in higher slo pes (tho ugh,
perhaps still within the experimental repro ducibility) and fluo ride
exhibited smaller slo pes (1.46 eVV"
1
). Furtak and Roy
117
have
shown that for co adso rbed chlo ride and pyridine, o r chlo ride and
thio cyanate, each mo lecule shows its own excitatio n po tential
dependence. Ano ther interesting po int was that the excitatio n
maximum of o ne of the mo lecules was "reflected" in the excitatio n
profile of the o ther co adso rbed mo lecule.
It is impo rtant to no te in this co ntext that electro reflectance
measurements on silver electro des (in the absence of pyridine) have
fo und structures attributed to surface states, which were unusually
and stro ngly dependent on the electric po tential.
287
'
288
No rmally,
we wo uld expect the energies of species in the interface to
change no t mo re than the change in the electric po tential. When
these findings are further verified, they may turn o ut to be very
impo rtant for understanding SERS and interface pro blems in
general.
The excitatio n spectrum for SERS from go ld and co pper elec-
tro des is characterized by a thresho ld behavio r. Wenning et al
245
detected SERS of pyridine on gold and co pper only at 647.1 nm,
while at 568 nm no signal was seen (o r a 200-fo ld-less-intense
scattering was measured
116
). Chang et al
si
measured a stro ng co p-
per cyanide scattering using 600-nm excitatio n, which was co mpar-
able in intensity to a signal from silver. Ho wever, below 575 nm
the Raman intensity dro pped belo w the backgro und. Allen et a/.
88
repo rt a thresho ld for SERS detectio n of pyridine from co pper at
abo ut 600 nm. Marinyuk et al,
244
using the measurements of the
anti-Sto kes transit as described abo ve, estimated the existence of
a transitio n at 1.77 eV for co pper and 1.55 eV for go ld, with adso rbed
pyridine. Laufer et al.
90
fo und for co pper cyanide a co ntinuo us
increase of the intensity with decreasing wavelength, between 514.5
and 457.9 nm. As discussed in Section II. 1, this result may be due
to multilayer scattering. The frequency dependence of SERS on a
silver gold allo y
255
was described in Section II. 4.
A unique frequency dependence was exhibited by the ultralo w-
frequency feature discussed in Section II. 3(i) (see also Ref. 199).
In this case the Raman shift itself depends on the excitatio n
frequency. The higher the excitatio n energy, the larger is the "vibra-
tio nal" frequency. This means that changing the excitatio n causes
a co upling to a different entity in the system with a different
characteristic vibratio nal frequency.
(I I I ) Excitation Spectra in Colloidal Systems
Creighto n et a/.
60
'
289
measured the excitatio n spectrum for
SERS of pyridine adso rbed o n a silver so l. It showed a clearly
parallel behavio r to that of the extinctio n of the so l. Fo llo wing the
additio n of the pyridine, the co llo id with an initial extinctio n
maximum at 400 nm gradually develo ped a feature at lo nger
wavelengths. This bro ad extinctio n peak shifted in time to lower
and lower energies. The Raman excitatio n maximum o verlapped
with this "red" feature. One sho uld no te, ho wever, that thro ugho ut
these changes the peak at 400 nm remained, by and large. Wetzel
and Gerischer
191
stabilized their silver co llo ids, and fo und the
400-nm peak in the extinctio n. The excitatio n profile showed an
increase to ward the blue, in parallel to the extinctio n, but in o ppo si-
tio n to the previo us results discussed abo ve. The reference was
internal, pyridine in the suspensio n, which is "filtered" o ut by using
pro per po larizatio ns at incidence and detectio n. This is a very
efficient metho d to co rrect for abso rptio n in the sample, besides
the detectio n-system respo nse. Kerker et al
96
'
290
fo und for citrate
adso rbed o n stable silver increasing SERS intensities to ward the
red, but an extinctio n band lo calized aro und 400 nm. In later wo rk,
33
different fractio ns of a citrate silver co llo id were investigated. All
exhibited Raman excitatio n maxima at abo ut 500 nm. Some prepa-
ratio ns had low sho ulders at 500 nm in the extinctio n spectra, o thers
had only the main peak at 400 nm.
The go ld sol of Creighto n et al
60
had a flat extinctio n respo nse,
but the SERS excitatio n spectrum was characterized by a thresho ld
at abo ut 570 nm, as seen for the electro des. In a mo re co mprehensive
study
35
go ld co llo ids exhibited a maximum of abso rptio n at 520 nm,
and when pyridine was added a band at lo nger wavelengths
increased gradually and shifted to abo ut 700 nm. TEM studies,
co nducted in parallel, indicated aggregatio n of some of the initially
spherical single gold particles into chains. The Raman signal of
318 S . E frima
pyridine appeared with an excitatio n spectrum closely following
the extinctio n. The abso rptio n of the co llo id was explained by
dipo lar co upling between adjacent gold particles, to pro duce a
lo ngitudinal plasmo n excitatio n in the gold chains. In the stabilized
gold sol of Wetzel and Gerischer
191
the extinctio n spectrum retains
the band at 520 nm, witho ut any feature at lo nger wavelengths. The
Raman signal of pyridine was higher at abo ut 650 nm than at
675 nm. The citrate go ld co llo id of Mabuchi et al
246
had the usual
stro ng extinctio n at 520 nm and a barely no ticeable sho ulder at
abo ut 700 nm. The Raman intensity increased from 500 to 670 nm.
An external reference was used. Extinctio n lo sses were reduced by
passing the incident beam close to the flank of the cell; ho wever,
this do es no t to tally co rrect for the lo sses.
Von Raben et a/.
78
investigated several gold co llo ids, o ne of
which was especially stable and co nsisted of single spherical par-
ticles. The extinctio n spectrum for this co llo id revealed only the
520-nm band; the o ther two co llo ids had a sho ulder at abo ut 700 nm.
The Raman excitatio n in all the co llo ids was characterized by an
o nset at abo ut 530 nm and large intensities at 700 nm. The intensities
of the mo re aggregated samples were up to two o rders of magnitude
larger than that of the no naggregated sample. In all cases, an
external reference was used. It is no t clear how co rrectio ns for
extinctio n lo sses were intro duced.
Recently, Creighto n et al.
36
studied a co pper co llo id, using
dynamic light scattering to characterize the size and size distribu-
tio n. When pyridine is added, the co llo id starts to change co lo r
and the light scattering shows aggregatio n pro cesses. However, for
up to abo ut 6 min, the average particle radius is no t significantly
different from that of the co llo id in the absence of pyridine (30
and 5 nmthe two dimensio ns inferred from the light scattering).
In that time the Raman signal of pyridine grows from a very low
value to a value which is only five times smaller than the intensity
after a lo ng time. This inductio n time seems to be needed for
pyridine adso rptio n, after which the co llo id starts to aggregate, the
main gro wth o ccurring in the next 6 min o r so . The mo rpho lo gical
changes bring abo ut only a facto r of 5 in the intensity change. Thus,
the co rrelatio n of the Raman excitatio n spectrum to the extinctio n
(which is asso ciated with the mo rpho lo gical changes) is relatively
weak.
(it?) SERS Excitation Profiles on Films
In this sectio n, a few examples of excitatio n spectra of SERS
on films are discussed.
Mo sko vits and DiLella
50106
measured the excitatio n spectrum
of ethylene adso rbed o n a co ld-depo sited silver film in UHV co ndi-
tio ns. Using the Raman signal from a thick layer of ethylene as a
reference, they find a mo no to no us increase of the SERS as o ne
changes the excitatio n wavelength from 457.9 to 620 nm. In that
regio n the signal changed by a facto r of 11. The same behavio r was
seen also for CO adso rbed o n a similarly prepared film. In a different
experiment by the same gro up,
58
ho wever, CO exhibited a sharp
maximum of SERS at abo ut 520 nm. The different behavio r can,
perhaps, be attributed to minute differences in the silver film. Yet
ano ther behavio r was o bserved for CO on a silver film depo sited
at 120 K o n a co pper substrate.
73
A mo no to no us increase of the
SERS by a facto r of abo ut 20 was seen when the excitatio n changed
from 1.9 to 2.6 eV. Incidentally, for CO o n go ld an o ppo site behavio r
was o bserved. The measurements were co rrected for the respo nse
of the detectio n system and the fo urth po wer of the frequency.
McBreen and Mo sko vits
291
fo und a bro ad feature in the reflection
spectrum of silver films evapo rated on co ld substrates with a
maximum at ~ 480 nm, which decreased and moved to higher
energies with annealing. Thus, it appears there is hardly any co rre-
spo ndence between the o ptical pro perties of the film and the
o bserved Raman excitatio n dependence in these experiments.
Bergman et al.
155
reach a different co nclusio n. They measured
the abso rbance, Rayleigh scattering, and Raman scattering from
adso rbed cyanide on a silver film as a functio n of the average
thickness of the film. A fixed wavelength of 514.5 nm was used.
They find a bro ad abso rptio n centered aro und 6.7-nm thickness, a
peaked Rayleigh band with a maximum at ~ 8 nm, and a Raman
band peaking at abo ut 6 nm. The Raman intensity changed by a
facto r of 5 between 2-nm thickness and the thickness of maximum
respo nse. It is no t clear whether a co rrectio n for the changes in the
adso rbed amo unt of cyanide was made or whether the backgro und
was subtracted. Anyway, the autho rs show a dependence on thick-
ness of their Raman signal and the imaginary part of the effective
dielectric co nstant, calculated from the abso rbance, using an
320 S . E frima
appro ximate appro ach. The co rrelatio n ho lds up to a thickness of
5.5 nm. This indicates some relatio nship between the dielectric
pro perties of the film and SERS; ho wever, due to the po ints men-
tio ned abo ve, it is no t clear how rigo ro us this co rrelatio n is. Cer-
tainly, it do es no t pro ve any cause-and-effect relatio nship.
Seki
75
'
292
'
293
found that the excitatio n profiles for SERS of
pyridine o n a silver island film and on a co ld-depo sited film are
different and unco rrelated to the abso rbance, which is also
measured. Fo r instance, CO on ro ugh co ld silver exhibits maxi-
mum scattering aro und 500 nm, while pyridine on a similar film
(but no t co adso rbed) scatters with maximum intensity at abo ut
600 nm.
Po ckrand et
a
l*>
l03
>
24
*>
294
measured SERS excitatio n profiles
for pyridine, o xygen, and ethylene adso rbed on "co ldly" evapo rated
silver films. The reference was a thick film of pyridine adso rbed on
a silver surface which was no t SERS active. All the spectra maxi-
mized aro und 550 nm. Ho wever, it is no ted that higher-frequency
mo des are characterized by maximum scattering at higher excitatio n
frequencies. Fo r instance, the difference between the excitatio n
maximum of the 808- and 3000-cm"
1
bands was ~ 0.35 eV, i.e.,
2800 cm"
1
. These shifts are to o large to be explained on the basis
of o ptical respo nse alo ne (see Ref. 294), co nsidering the large
widths of the excitatio n measured. The excitatio n maxima seem to
shift to sho rter wavelengths upo n annealing. A co rrelatio n with
measured reflectivity is carried o ut, and it is fo und that the Raman
maximizes at wavelengths red to the abso rptio n band.
Lado uceur et al
160
find for "co ldly" depo sited silver, go ld,
and co pper films an o verall increase in SERS of pyridine at lo nger
wavelengths, with gold and co pper exhibiting a mo re pro no unced
behavio r. Their reference is a thick layer of pyridine.
Tsang et al.
170
find for 4-pyridine-carbo xaldehyde adso rbed on
a ro ugh silver surface in a tunnel junctio n layo ut, that the intensity
is co nstant in the red to green regio n and stro ngly decreases in the
blue. They use a Raman line of quartz as a reference, but that do es
no t co rrect for the abso rbance in the silver o verlayer in this system.
Liao and Stern
174
show a relatio n of the Raman excitatio n
spectra from silver and gold particle arrays to the same value (see
Section III) calculated from experimentally determined abso rptio n
spectra.
In this co ntext of excitatio n behavio r and the relatio nship to
the o ptical pro perties, it is impo rtant to mentio n the work of Demuth
et al.,
295
'
297
who fo und new transitio ns which did no t belo ng to the
mo lecules o r the silver substrate alo ne, but to the mo lecule-silver
surface system. Such transitio ns were fo und for pyridine, CO,
o xygen, and ethylene. They were seen beside the (slightly perturbed)
kno wn transitio ns of the iso lated mo lecules and the bare surface.
These transitio ns were o bserved only when the surface was ro ugh-
ened. They were asso ciated with charge transfer transitio ns. The
justificatio n for this assignment was the appearance of a transitio n
for a CO-silver (cluster o r ato m) system at 3.1 eV co mpared to 3 eV
on the silver surface. Also , for ethylene on a small cluster, a 2.25-eV
transitio n was seen co mpared to the 2.8-eV transitio n on the surface.
It is extremely difficult in these systems to pro vide mo re direct
pro o f for the assignment to a charge transfer transitio n. An impo r-
tant po int is that the experimental data are entirely co nsistent with
the po ssibility that these new transitio ns are asso ciated with only
a small fractio n of the adso rbed mo lecules.
Finally, o ne sho uld no te that there are many published papers
that repo rt the o ptical behavio r of silver films
298
"
307
; these co ntribu-
tio ns will no t be discussed in detail here, but the reader may find
them helpful on the SERS jo urney.
(v) Summary of SERS Excitation Profiles
In spite of the so metimes conflicting experimental results, the
four questio ns which were po sed at the beginning of Section II.5
have been answered in full. It was unanimo usly fo und that the
excitatio n spectra in SERS are significantly different than tho se of
the mo lecules in so lutio n. Even for the case of dyes it was fo und
that the surface affects the pro file. There is evidence that in many
systems the SERS excitatio n profile do es no t follow the o ptical
behavio r of the system (as o bserved in abso rptio n o r reflectio n),
let alo ne that of the bare metal. On the o ther hand, there are systems
where such a co rrelatio n is apparent. At times the vario us mo des
of the same adso rbed mo lecule exhibit the same dependence on
the exciting frequency, while in many o ther cases, different mo des
behave differently. The mo des may be distinguished on the basis
of the vibratio nal frequency (large, small) o r their symmetry.
322 S . E frima
Vario us mo lecules exhibit in some cases similar dependence of
their spectra o n frequency, but mo re often than no t they appear to
have different behavio r. This is especially true for reso nance scat-
terers and no rmal Raman scatterers.
III. THEORETICAL MODELS OF SERS
1. General
In Sectio n II it was sho wn that there is a large number of experi-
mental studies of SERS pheno mena. It is no t surprising that there
is also an abundance of theo retical mo dels pro po sed to explain
these results. Several excellent reviews
10
'
12
'
1619
'
20
'
308
and, in addi-
tio n, some mo re specific papers (see, e.g., Refs. 21-23) have been
published. The reader is referred to them for a mo re co mplete and
rigo ro us presentatio n, o r for a different po int of view. The aim here
is to present the theo ries in as simple terms as po ssible in o rder to
facilitate co mpariso n of their predictio ns with the experimental
evidence. Also , an attempt is made to po int o ut the strengths of
each mo del and its limitatio ns.
Just as the previo us sectio n dealt with experiment alo ne, trying
to exclude theo retical interpretatio n, thus, in the present sectio n,
we try to discuss theo ry devo id of the experimental results.
Our theo retical so jo urn begins with the following expressio n,
which describes the intensity r
D
((*>
s
, l
s
) of the Raman-shifted light
with frequency w
s
scattered in directio n ft
5
:
r
D
(<
s
, ft,) = K Av{n
s
\G
s
(co
s
, fl
5
) a
s
(o>
s
, a>
n
ft
s
, ft,) E
p
(a>
n
ft,)|
2
}
(1)
It is given in terms of the lo cal field acting o n the scattering center,
E
p
(ft>
w
ft,), which depends on the frequency of the incident light,
a>,, its directio n ft,, and, of co urse, the characteristics of the system.
The scattering intensity also depends on the (Raman) po larizability
of the system, a
s
((o
s
, o>,, ft
5
, ft,), and on the pro pagato r G
s
(co
s
, ft
s
),
which pro pagates the scattered light from the scattering zo ne to the
detecto r. Finally, the measured Raman intensity also depends on
the number of scattering centers, n
s
. K is a co nstant, which depends
on the frequency, essentially to the fo urth po wer. The Av{- } in
Eq. (1) deno tes an average o ver all po ssible o rientatio ns and po si-
tio ns of the species which scatter the light. Fo r instance, we may
envisage mo lecules adso rbed o n a hetero geneo us surface, each
sensing a lo cal field, characterized by a po larizability and asso ciated
with a pro pagato r, all of which may be po sitio n dependent.
The enhancement of the Raman scattering, R, is given in these
terms by the ratio
R = (I
S
D
/N
S
)/(I
D
/N
Q
) (2)
where N is the to tal number of mo lecules and the index 0 deno tes
a measurement in the bulk, characterized by a
0
, G
o
, n
0
, N
o
, and
E
p
= when E
t
is the laser electric field. Fo r a ho mo geneo us field
bulk system, to which we generally make reference, o ne remains
only with the average over the o rientatio ns of a single mo lecule:
I
D
= Av{|G
0
K, ft
s
) a
o
(eu
s
, a>
n
H
5
, fl. ) E
t
(a>
n
n,)|
2
} (3)
In many cases in the SERS studies o ne do es no t have precise
kno wledge of the number of adso rbed mo lecules but only an esti-
mate, N
s
. Co nsequently, an apparent enhancement facto r will be
calculated which is different from the actual enhancement by a
facto r N
R
= NJ N
s
. Obvio usly, if N
R
1, then it will seem that
there are surface enhancements. In the inverse case (special active
sites) the real enhancements are higher than the apparent o nes. In
the following we assume that the surface co verage is kno wn exactly.
Any o ne of the terms in Eqs. (1) and (2) can be different o n
the surface than it is in the bulk, and thus result in R ^ 1. Fo r
SERS, as co nsidered here, R > 100 and, generally, R > 10
4
.
The difference between the o rientatio nal averages in so lutio n
and on the surface can be the reaso n (o r o ne of them) for the
specific angular and po larizatio n pro perties of SERS.
24
"
26
'
309
Ho wever, it can affect the intensity only to an insignificant degree
on the scale of the to tal enhancement. At the most it can cause an
enhancement of 3 x for a mo lecule with only o ne large Raman
po larizability principal axis which is o riented perpendicular to the
surface of a planar reflecting metal. Thus, for the sake of simplicity,
we disregard the angular average and the vecto rial pro perties of
all the quantities invo lved.
Thus, o ne must search the three quantities G
s
, a
5
, and E
p
, for
the so urce of SERS. E
p
and G
s
are essentially electro magnetic in
nature and can be o btained by so lving the Maxwell equatio ns with
324 S . E frima
the pro per input of the dielectric pro perties of the vario us com-
po nents of the system. Rigo ro us so lutio ns can be o btained in many
mo del cases. Ho wever, these so lutio ns use (sharp) bo undary co ndi-
tio ns at the face of the so lid, which may limit their validity very
close to the surface, where a gradual transitio n from phase to phase
is apparent.
The surface changes in the po larizability, a, can be due to
electro magnetic interactio ns, o r to "chemical" effects. By elec-
tro magnetic interactio ns is meant interactio ns given by macro sco pic
Maxwell equatio ns, o r their micro sco pic mo dificatio n, when the
adso rbed mo lecules and the substrate retain their own chemical
identity and integrity. Chemical interactio ns involve some o verlap
of the mo lecular o rbitals and tho se of the substrate.
One may classify the vario us pro po sed mo dels in several ways.
One way is to differentiate between mo dels that focus on the ro le
of the electric field E and the emissio n G terms (these two are
related), o n the o ne hand, and tho se that emphasize the ro le of
changes in the Raman po larizability tenso r, on the o ther. The former
discuss the enhancement in terms of amplified fields, due to the
presence of the surface, which act on the scattering mo lecule and
its emissio n being further amplified by the surface. These are the
lo cal field and emissio n enhancement mo dels (LFE). The difference
between the vario us mo dels which belo ng to this gro up is in the
identificatio n of the specific excitatio n in the so lid which is respo n-
sible for the amplificatio n: plasmo n po larito ns, shape reso nances,
electro n ho les, etc.
The seco nd main gro up of theo retical mo dels asso ciates the
SERS effect with a large intrinsic po larizability thro ugh a reso nance
mechanism (RE). The reso nating species depend on the specific
model and can be the mo lecule modified by the presence of the
metal, the metal itself affected by the mo lecular vibratio ns, o r some
mixed mo lecule-metal states.
Ano ther classification of the theo retical mo dels can be based
on the nature of the interactio n: "electro magnetic" vs. "chemical"
(for which we will be satisfied with the simplistic intuitive definition
given abo ve). Of co urse, o ne do es no t always have a clear
delineatio n between these two types of interactio ns.
One sho uld no te that most of the theo retical mo dels suggested
are no t mutually exclusive, at least no t in principle. Thus, it is
po ssible that the real situatio n is a co mpo site of several mechanisms.
The exact blend is, at present, a matter of dispute. There is also
the po ssibility that this blend changes from system to system.
2. R esonance M odels (R E )
To this gro up belo ng several mo dels of very different kinds such
as the "image" mo del (RE-IE), the charge transfer (RE-CT) mo del,
the electro n-ho le excitatio n mo del (RE-EH), and the Raman reflec-
tivity mo del (RE-RF). These mo dels have very little in common
except that they all lead to enhancements by virtue of a reso nance
scattering mechanism. The validity of the last statement is no t
always realized by peo ple, but it will be sho wn below to ho ld true.
An example of the mo dels in this catego ry is that pro po sed by
Mo sko vits.
310
'
311
He pro po sed that the SERS was a result of a
reso nance o r prereso nance Raman scattering, where the reso nating
mo ieties are the metal ro ughness featuresthe "bumps. " The lo cal-
ized, plasmo nlike states in these bumps are excited by the incident
field, and the vibratio ns of the mo lecules which are adso rbed on
their surface scatter as if they are in a reso nating mo lecule. Mos-
kovits sho wed that the characteristic frequencies of the excitatio ns
in small co inage metal particles sho uld be in the visible, especially
if interactio ns among them are co nsidered. Thus the special ro le
of silver, go ld, and co pper was stressed. Mo sko vits did no t specify
the mechanism that co uples the mo lecular vibratio ns to the metallic
bump. This mechanism can be any of tho se described belo w as
reso nance mechanisms. Ho wever, this same general o utline can
lead to SERS thro ugh enhancements of the lo cal fields, which we
classified as a LFE mechanism. This comes to emphasize the po int
that all the enhancement mechanisms suggested involve some type
of reso native pro cess. The difference between them is based on
their major effect: large fields (and amplified emissio n) vs. reso -
nance of the scattering center itself.
(i) Renormalization ("Image'") Model (RE-IE)
One of the earliest mo dels pro po sed to explain SERS was
suggested and develo ped by Efrima and Metiu
24
'
26
'
312
"
315
and also
by King et al.
316
It is based o n the classical theo ry of Raman
326 S . E frima
scattering and on classical electro dynamics. The main idea is that
an excited (o r virtually excited) mo lecule can be described by a
classical o scillating electric dipo le. It is induced by the inco ming
laser field. This dipo le exerts fields on the surro undings. One com-
po nent decreases as the first po wer of the distance and is the
radiative, scattered field. The o ther co mpo nents, the so -called near
field,
317
decrease as the square and the cube of the recipro cal
distance. They are extremely small far from the mo lecule, but can
beco me exceptio nally stro ng at close pro ximity to the mo lecule.
This field is respo nsible for energy transfer pro cesses such as the
Fo rster mechanism. The o scillating dipo le, near a surface, stro ngly
po larizes the metal which exerts a field back on the mo lecule, which
further po larizes it. The larger mo lecular dipo le induces additio nal
po larizatio n in the metal and so o n. The net result is a much larger
induced mo lecular dipo le than wo uld be achieved in the absence
of the highly po larizable surface. Such a large o scillating dipo le
scatters much more light which amo unts to a measured enhance-
ment. In mo lecular terms, as will be shown belo w, this self-
po larizing effect means a shift of the mo lecular levels to attain a
state separatio n which is, under certain circumstances, in reso nance
with the incident light. Thus the mo lecule which may be a no rmal
Raman scatterer in so lutio n turns into a reso nance scatterer on the
surface.
The simplest presentatio n of this mechanism starts from an
expressio n which gives the induced dipo le /JL in terms of the to tal
field E
T
o perating on it:
\x = a
0
E
T
(4)
where a
0
is the mo lecular Rayleigh po larizability, in the absence
of the surface. The to tal field is co mpo sed of the incident laser field
(perhaps modified by the surface) E
p
and a field exerted by the
induced po larizatio n in the metal which is pro po rtio nal to the dipo le
mo ment and falls off as the distance to the surface, Z, cubed:
E
T
= E
p
+
yfJ
L/(2Z)
3
(5)
Here y deno tes a metal respo nse functio n and the facto r 2 was
written in o rder to o btain the form of an image interactio n. From
Eqs. (4) and (5) o ne o btains:
M = OL
S
E
P
(6)
with the surface po larizability a
s
given by
<** = o /[l " 7o /(2Z)
3
] (7)
In the absence of the metal, y = 0 and a
s
= a
0
. Ho wever, in its
presence, y may be large so that the who le deno minato r beco mes
very small and the po larizability very large. This is what is generally
called the image mechanism. In this fo rm it amo unts to calculating
y and checking whether it can be large eno ugh and in the appro pri-
ate directio n, y generally has an imaginary part, which remains
even when the deno minato r of Eq. (7) vanishes. This will determine
the maximum value of the surface po larizability. Fo r large enhance-
ments, o ne needs small co ntributio ns of the imaginary part. This
is also a matter of co ncern in all calculatio ns of y.
Befo re discussing calculatio ns of % which is at the co re of this
mechanism, we sho w the equivalence of this mo del to a reso nance
enhancement mechanism. We take a simple fo rm of the mo lecular
po larizability,
a
0
= (fe
2
/m)/(co
2
0
-co
2
- 2icoT) (8)
where / is the o scillato r strength, e the electro nic charge, m the
electro n mass, co
0
a self-frequency of the mo lecule (an electro nic
transitio n frequency in a mo lecule in a quantum-mechanical pic-
ture), F the transitio n width, and to the frequency of the exciting
light. Inserting this expressio n fo r the po larizability into Eq. (7)
o ne o btains
a
s
= (fe
2
/m)/[co
2
-co
2
- 2cob
s
- 2ico(T + T
s
)] (9)
Here we defined the surface shift A
5
and the surface width T
s
as
the real and imaginary parts of (fe
2
/m)y/(2Z)
3
, respectively. In
the absence o f the surface, the reso nance co nditio n is attained fo r
co = COQ. On the surface, the reso nance co nditio n is appro ximately
co = co
0
- A
5
(10)
and the to tal width has increased by T
s
. This establishes the co nnec-
tio n between the "image" mo del and a surface-induced reso nance
Raman pro cess. Incidentally, such a picture was develo ped even
prio r to the disco very of SERS by Philpo tt,
318
and enhancements
were predicted assuming increased widths (no t shifts).
328 S . Efrima
The Raman po larizability will be o btained from a
s
by differen-
tiating with respect to a vibratio nal co o rdinate Q, which gives the
leading term in the scattered intensity
I'D ~ klViD ~ ya
o
/(2Z)
3
f\da
o
/dQ\
2
(11)
Efrima and Metiu,
24
"
26
and King et al.
316
suggested that y co uld
be calculated o n the basis of reflectio n from a plane metal surface.
They find
y = 2(e
M
- e
s
)/(e
M
+ e
s
) (12)
Here e
M
and e
s
are the frequency-dependent dielectric co nstants
of the metal and the so lutio n, respectively. Using kno wn pyridine
po larizability and silver dielectric data,
319
large enhancements co uld
be o btained (up to 10
7
). In terms of the mo lecular picture, a
several-eV decrease of level spacing was invo lved. This shift,
ho wever, stro ngly depends o n the frequency, thro ugh the dielectric
co nstant of the metal. This is a dynamic shift and the reso nance is
really a jo int metal-mo lecule-pho to n excitatio n. This is different
from a shift of levels under static fields. This po int has o ften been
misundersto o d.
The co nsequences of this mo del are:
1. Fo r realistic mo lecular po larizabilities a clo se pro ximity
to the surface is needed. Fo r a no rmal Raman scatterer,
generally o nly first-layer enhancement is expected (as seen
belo w, ro ughness can increase this range to 1-2 nm); fo r
a prereso nance scatterer, the effect can be at lo nger dis-
tances, ho wever, the enhancement will be smaller than for
a NR scatterer.
2. No further enhancement is expected of a mo lecule which
is already in reso nance. This is a co mmo n feature of all
RE mechanisms.
3. Co inage metals will suppo rt SERS at appro priate frequen-
cies, due to their dielectric pro perties. Silver is especially
go o d due to the relatively small imaginary part of the
dielectric co nstant. Other metals may be SERS active, Hg
fo r instance, especially for prereso nance scatterers (i. e. ,
when the po larizability is already relatively large).
4. The excitatio n spectrum sho uld be stro ngly related to the
dielectric respo nse of the metal-mo lecule system. Fo r a
NR scatterer, the maximum of enhancement sho uld appear
o n the lo ng-wavelength side of the metal substrate exci-
tatio n.
5. No direct dependence o n surface ro ughness! (Ho wever,
no te below that ro ughness do es increase the "image" inter-
actio n and changes the dielectric respo nse.)
6. The dependence on electric po tential stems from the
dependence of the dielectric pro perties on it, and it can
be a stro ng dependence as the enhancement is no nlinear
with the dielectric respo nse.
The mo del has the disadvantage (and advantage) of being
extremely simplistic: classical electro dynamics, plane surface, po int
dipo le, etc. , co ncepts are invo lved. From the po int of view of theo ry,
using a classical electro magnetic treatment at a distance of 0.1 nm
from the surface can send shudders do wn the spine of any decent
theo retician. Using a po int-dipo le appro ximatio n do es no t help
either. Hilto n and Oxto by
320
indeed criticized this mo del for the
use of the dipo le appro ximatio n. In a series of papers,
321323
Maniv
and Metiu used a quantum-mechanical RPA (rando m-phase
appro ximatio n), infinite-barrier metho d to investigate the validity
of macro sco pic electro dynamics at the surface (see also Feibel-
man
324
"
326
). They find that the macro sco pic results, the Fresnel
reflectivity, for instance, are exact o utside of the metal electro nic
clo ud, are still reaso nable abo ut halfway between the infinite barrier
and the jellium edge, and for clo ser distances are simply inappli-
cable. Fo r a dipo le near the surface,
327329
they find that the simple
image interactio n is no t a go o d appro ximatio n. Outside the electro n
clo ud, it is to o small, because of "spillo ut" effects (the po larizable
electro ns are clo ser to the mo lecule and the "image plane" is clo ser;
see also Efrima
330
). As the mo lecule penetrates the electro nic clo ud,
stro ng screening sets in and the interactio n beco mes much smaller
than the "image. " Their co nclusio n is that a co rrected image mo del
co uld still pro duce, so mewhat reduced, but still substantial,
enhancements, but only at higher frequencies than tho se predicted
on the basis of the clasical image, pro bably in the blue (for silver).
This mo del still uses the po int-dipo le appro ximatio n and the surface
is taken as flat.
Weber and Fo rd
331
"
333
intro duce finite-size effects and also
clo se-range dispersio n for a ro ugh surface in a classical electro dy-
330 S . E frima
namic mo del. To simulate the size, they perfo rm their calculatio n
for a po larizable sphere, and the dispersio n is intro duced via a
Lindhard dielectric functio n.
334
They find that the "image" enhance-
ment is much reduced, but still co nsiderable,~1000.
Agarwal et al.
335
sho wed, using a po int-dipo le, classical elec-
tro dynamic calculatio n, that the image can be co nsiderable near a
metal sphere (simulating a ro ughness feature) of abo ut 2-3 nm and
with similar mo lecule-sphere distances. At such distances the
appro ximatio ns are to lerable, so that their results are dependable.
The reaso n for the increase in the interactio n is a co upling to the
surface plasmo n (o r shape reso nance), which in the sphere can
o ccur at lo wer frequencies than for a flat surface.
Incidentally, any mechanism which lowers the plasmo n
frequency (by shape effects o r by interactio n between small particles
sustaining the lo cal plasmo n o scillatio ns) will result in a stro nger
"image" interactio n, pro vided dissipatio n do es no t increase to any
large extent. Furthermo re, ro ughness pro mo tes efficient co upling
also by pro viding wavenumber co mpo nents that help in co nserving
mo mentum (i. e. , co nservatio n of "crystal" mo mentum).
Wo o d
336
no tes that the static image interactio n with a sphere
is smaller than with a plane. No te, ho wever, that the co upling at
o ptical frequencies is stro nger due to the effects mentio ned abo ve.
Gersten
337
sho wed that at the tip of a perfect metal ellipso id of
aspect ratio of 10:1 to 50:1 the "image" is small at any reaso nable
distance. Gersten and Nitzan
338
sho w, o n the o ther hand, that at
the tip of an ellipso id co nducto r characterized by silver dielectric
pro perties, the image can be of impo rtance at distances of 0. 1-
0.25 nm. Kerker et al
339
remark that in the limit of the small
spherical particle (particle radius smaller than the wavelength) the
image enhancement is small, but they give no details.
Eesley and Smith
340
have carried o ut a classical electro dynamic
calculatio n, which is essentially an "image" mo del. They also
co nsider the interactio n between neighbo ring mo lecules, using a
dipo le-dipo le co upling including images. The most significant
result they present is a dependence of the scattered intensity on
the second po wer of the incident intensity! No o ther mo del has
this predictio n, and it can easily be checked experimentally. Ano ther
po int of interest is the co verage dependence, at the submo no layer
level. Due to the depo larizing effect of the neighbo ring mo lecules,
the Raman cross sectio n sho uld decrease at co verages higher than
0. 1-0. 3. This effect can also be represented simply by an average
dielectric co nstant of the adso rbed layer, decreasing the field
intensity sensed by the individual mo lecules. Ho wever, an increase
in the dielectric co nstant of the surface layer affects the metal
excitatio ns as well, a facto r which was no t co nsidered in this wo rk.
Arunkumar and Bradley
341
carry o ut a similar calculatio n, but
include the po larizing and depo larizing effect of the o ther mo lecules
and the ro ughness features. They assume that ato mic-scale surface
ro ughness can reflect the near field of the mo lecules that are neigh-
bo rs to the site of the scattering mo lecule. If the po larizing effect
is larger than the depo larizing effect, then enhancements are expec-
ted. Large surface-ro ughness features are fo und to increase the
co ntributio n of the po larizing reflections (pro bably due to allo wing
favo rable mo lecular o rientatio ns with respect to each o ther). The
expected enhancements are >10
5
for the ato mic-scale ro ughened
surface and higher by several o rders of magnitude, when micro -
sco pic features are present.
Li,
342
in a classical treatment based on the Drude equatio n,
co nsiders also no nlinear effects. The mo del is essentially an "image"
mo del.
There are several theo retical mo dels which are essentially
image mo dels, but apply quantum-mechanical treatments. Lee and
Birman
343345
find "co upled-system eigenstates" created from the
electro dynamic interactio n of the mo lecular-induced dipo le and
the po larizable metal medium, which are analo go us to the shifted
mo lecule-metal-pho to n states of the classical treatment. They
include dispersio n, which is impo rtant at sho rt distances, but still
retain a planar surface. No te that they have a sharp bo undary, i.e.,
no allo wance is given to the penetratio n of the po larizable electro n
clo ud o utside the po sitive-charge backgro und of the metal, an effect
which generally increases the interactio n. They find a peaked depen-
dence of the enhancement on the frequency, near the surface-
plasmo n excitatio n o r even o n the sho rt-wavelength side of it, and
a maximum enhancement of a 1000. If surface structure will push
the surface excitatio ns into the visible range, then this calculatio n
predicts "image" enhancements of this o rder of magnitude.
The treatment of Eguiluz
346
for the "image" interactio n strength
also shows that dispersio n tends to decrease it.
332 S . E frima
Ferrell,
347
using a simple quantum-mechanical appro ach to
investigate the case of a mo lecule adso rbed on a small sphere, finds
reno rmalized states, which enable a reso nance pro cess to arise at
lower energies than in the so lutio n. He predicts an enhancement
of 10
4
, but do es no t state at what mo lecule-surface distances it is
calculated, no r whether such distances which cause a reso nance
are realizable.
Arya and Zeyher
348
develo p a general many-bo dy theo ry for
SERS. In the limit of a planar surface and only plasmo n co ntribu-
tio ns to the interactio ns, they find an enhancement of a facto r of
100 for the "reno rmalizatio n" mo del and it is relatively weakly
dependent o n the excitatio n frequency. This is for silver of co urse.
Fo r Cu o r Au, they predict even smaller "image" effects, <10.
To summarize the "reno rmalizatio n," "image" enhancement
mechanism, it is impo rtant to no te that all estimates predict
maximum enhancements ranging from 100-10
8
, lo cated at frequen-
cies close to the metal excitatio ns (plasmo n o r shape reso nances
o r electro n ho le, for that matter). If such excitatio ns are po ssible
in the visible range, then this mechanism sho uld be an impo rtant
co ntributo r to SERS. The "image" mechanism, also , co ntrary to
po pular belief, is sensitive to surface ro ughness, and generally
favorably so . It therefo re can be stro nger at specific SERS-active
"sites" o n the surface. It is also mo lecule sensitive thro ugh the
mo lecular (Rayleigh) po larizability.
(ii) Charge Transfer Models (RE-CT)
Basically, this set of mo dels claims that SERS is a result of a
reso nance Raman pro cess, where the mo lecule avails itself of the
uno ccupied states of the metal, o r vice versa. Thus o ne can envisage
a virtual intermediate transitio n to o ccur no t between pure
mo lecular states, but between a mo lecular and a metal state. This
mo del has the advantage of a clear chemical picture, but it do es
no t easily lend itself to rigo ro us calculatio ns leading to quantitative
predictio ns.
Aussenegg and Lippitsch
349
have explained Raman scattering
enhancements in charge transfer co mplexes as co mpared to the
separate mo lecules, on the basis of this charge transfer. They fo und
enhancement facto rs of abo ut 2, in agreement with experiment.
They suggested that the same mo del is valid for SERS, where due
to the high po larizability of the metal electro ns, large enhancements
are expected. They also predict that the mo lecule-metal vibratio nal
mo de will be exceptio nally intense, as it stro ngly affects the degree
of charge transfer.
King and Schatz
350
investigated the effect of charge transfer
on the transitio n dipo les (o scillato r strengths) determining the
Raman activity. This charge transfer, in their mo del, is pro mo ted
by static electric fields at the surface. Fo r the case of small o scillato r
strengths, a large enhancement is predicted, due to the stro ng
co upling thro ugh the metal states.
Burstein et al.
351
discussed several po ssible mechanism involv-
ing electro n-ho le pairs and charge transfer (CT). They expect a
thresho ld behavio r at a frequency where the pho to n energy plus
the mo lecular gro und-state energy surpass the Fermi level in the
so lid, for a mo lecule-to -metal charge transfer. In the case of metal-
to -mo lecule charge transfer, an o nset sho uld appear at the frequency
that equals the difference between the Fermi level and the lowest
uno ccupied mo lecular state (LUMO).
Gersten et al
352
treat this mo del using an Anderso n mo del.
They no te a thresho ld behavio r, as mentio ned abo ve. A dependence
on the electric po tential is also predicted. When the virtual excited
state resides on the mo lecule (metal-mo lecule CT), then mo re
po sitive po tentials will require higher excitatio n frequencies. Fo r
mo lecule-to -metal CT, mo re po sitive po tentials sho uld be asso ci-
ated with lo wer frequencies for SERS. The CT mo del also ratio nal-
izes the co ntinuum backgro und as real transitio ns which o ccurred
and had suffered some decay in the metal.
Ueba et al
353 35S
have presented a co mprehensive treatment
of the CT mo del. Based o n a Fano -type formalism they predict an
enhancement of ~ 100 for pyridine on smo o th silver. When ro ugh-
ness is added, in the form of ad-ato ms, the enhancement increases
to 1000. The excitatio n profile exhibits a reso nance shape, no t an
o nset. Ueba
359
'
360
applied his mo del to the Raman scattering of
mo lecules adso rbed on semico nducto rs and interacting with them
via the excito nic states. Persso n
361
and Kirtley et al
362
using similar
but no t identical mo dels predict the same o rder of magnitude of
CT enhancements, ~ 100. Adrian
363
calculated enhancements of
10-1000, again, pro vided the thresho ld co nditio ns discussed abo ve
334 S . E frima
are attained. Ro binso n,
364
'
365
invo king "exchange dipo le interac-
tio ns," predicts enhancements of 10
9
-10
13
and a distance depen-
dence of R~
12
. He finds that particles smaller than ~50 nm are no t
expected to give enhancements. A relatively flat excitatio n
frequency dependence is predicted. The reader is referred to these
papers for full details.
To summarize the CT mo del calculatio ns:
1. Most predict maximum enhancements of abo ut a 100.
2. The excitatio n frequency is related to the energy difference
between the metal Fermi level and the mo lecular LUMO
and HOMO, i.e., these mo dels are mo lecule sensitive.
3. A thresho ld excitatio n frequency is predicted or a reso -
nance shape.
4. The co ntinuum backgro und is explained.
5. Ro ughness of ato mic scale favors e-h (electro n-ho le)
co upling and o rbital o verlap.
6. SERS-active sites are tho se lo catio ns on the surface that
have ato mic-scale ro ughness features. Thus the apparent
enhancement will co nsist of an average over the (small?
number of) enhanced scatterers at the active sites and the
(large number of) mo lecules adso rbed at smo o ther parts
of the surface, and which do no t co ntribute much to the
to tal signal. The net result sho uld be apparent enhance-
ments that are much smaller than the enhancement per
site. This remark is valid for any o ther mo del which calls
for a limited number of active sites.
7. The dependence on the electric po tential is a result of the
change in mo lecule-metal relative energy separatio n.
(III) Raman Reflectivity (RE-RF)
The "image" mo dels describe SERS in terms of mo lecular
states modified by the surface. The CT mo del focused on jo int
mo lecule-metal states. The Raman reflectivity envisages the scatter-
ing as co ming from the metal, modified by the presence of the
mo lecule, and its internal vibratio ns.
Metals, and especially at frequencies near a metal excitatio n,
are stro ng reflectors and exhibit high luminescence. If the presence
of the mo lecule can mo dulate any metal pro perty, or accept energy
from the metal into its vibratio nal mo des, then a Raman branch of
this emissio n will be detected. The mo dulatio n can be bro ught
abo ut by several mechanisms: van der Waals-type interactio ns,
charge transfer, density fluctuatio ns in the so lid due to electro dy-
namic interactio ns, etc.
Otto
366
'
367
suggested that, as in electro reflectance, where
changes in the structure of the interface cause changes in the
reflectance, mo dulatio ns of the interface by the mo lecular vibratio ns
can change it as well. Thus, the reflectivity R is given by
* = A2(l + 2/
ER
AJ5
II
) (13)
where A
o
is the amplitude of the incident field; /
ER
is an electro re-
flectance coefficient, which can be o btained from independent
measurements; and A
n
is the change in the no rmal co mpo nent of
the field. Otto calculated A
n
from a mo del of a layer of o scillating
mo lecules, and from that estimated the SERS enhancement to be
>10
3
. The basic implicit assumptio n here is that the vibratio ns are
co rrelated in SERS as they are when excited in the infrared. Thus,
all mo lecules within the co herence distance will pro duce reflectivity
changes in the same directio n, thus enfo rcing each o ther's effect.
Ho wever, such an assumptio n is inappro priate for the o ptical
frequencies of SERS, where the electro nic po larizability is driven
and there is no phase co rrelatio n between the vibratio ns of different
mo lecules. Co nsequently, the mo lecules wo uld mo dulate the inter-
face at rando m, resulting in a smaller effect than that estimated
abo ve. Otto also mentio ns that this mo del canno t explain the special
ro le of silver in SERS.
McCall and Platzman
368
suggest that charge transfer between
the metal and the chemiso rbed mo lecule mo dulates the dielectric
pro perties of the metal and thus its reflectance. A similar mo del
was presented by Mal'shuko v.
369
Burstein et al?
51
discuss mechanisms by which electro n-ho le
pairs (e-h) are generated and, by interactio n with the adso rbed
mo lecule, lo se energy to it, while the rest is emitted (some also
dissipates as heat and some gives the elastic emissio n and the
co ntinuum backgro und). They envisage the e-h excitatio ns to be
reso nant with the incident light, the ro ughness relaxing the mo men-
tum co nservatio n requirements. An e-h excitatio n can be transferred
to the mo lecule by co ulo mbic interactio ns, and then either emitted
336 S . Efrima
directly from the mo lecule, o r transferred back to an e-h excitatio n
in the metal and then emitted, in bo th cases the mo lecule retaining
the vibratio nal quantum. Ano ther po ssibility is similar to the abo ve,
except that the co upling to the mo lecule o ccurs thro ugh wave-
functio n o verlap. In the case of stro ng interactio ns between the e-h
pairs and the mo lecular vibratio ns, o ne can envisage a direct inelas-
tic scattering of the incident light off "e-h po larito ns," i.e., dressed
e-h excitatio ns.
Maniv and Metiu
370
and Maniv
371
have co nsidered the co ulo m-
bic co upling mechanisms and find, under RPA and infinite-barrier
appro ximatio ns, a large enhancement of the Raman scattering, of
up to 10
4
. Ho wever, that is o btained only for unreaso nable distances
of the mo lecule from the surface (0.05 nm from the jellium edge).
Intro ducing ro ughness may increase the range. Maniv
496
has sum-
marized the results and sho wed large effects inside the metal electro n
clo ud.
To summarize this part, o ne might say that the Raman reflec-
tivity mo dels, tho ugh po ssible in principle, still need mo re theo reti-
cal substantiatio n befo re o ne can decide regarding their impo rtance
in SERS. Certainly, these mechanisms canno t be the who le sto ry.
3. E lectric Field and E mission E nhancement M echanisms (L FE )
In this sectio n, we discuss the theo retical mo dels that asso ciate the
SERS mechanism with the enhancement of the electric field sensed
by the mo lecule and the amplificatio n of the fields emitted by it.
The key wo rds here will be "surface plasmo ns. " These are co llective
excitatio ns of the electro ns o n a nearly free-electro n metal. There
are bulk plasmo ns, which are generally very high in energy, com-
pared to pho to n energies of 1.5-3 eV, which are of interest in the
co ntext of SERS. There are also surface plasmo ns, which are
confined to the regio n of the surface and decay expo nentially away
from it. Their characteristic frequencies are lower than the bulk
plasmo ns and can be bro ught into the visible range by confining
them in "bumps," i.e., metal particles with sizes ranging between
a few nm and hundreds of nm. The characteristic frequencies can
be affected also by the interactio n between several of these "bumps. "
Fo r a co mprehensive review, the reader is referred to Raether.
372
'
373
The theo ries which center on the ro le of plasmo ns auto matically
give special impo rtance to the co inage metals, due to their relatively
low-frequency plasmo ns o r o ther dielectric excitatio ns.
() The Lightening Rod Effect
Gersten
337
suggested that the stro ng electric fields pro duced
near sharp metallic tips may cause some of the Raman enhancement.
Fo r an ellipso id perfect co nducto r, the field at its tip can be even
10
3
times larger than the external electric field pro ducing it. This
was calculated for a po int lo cated 0.1 nm from the tip of an ellipso id
with a major axis of 50 nm and a mino r axis of 2.5 nm. Lio and
Wo kaun
374
o btain 10
4
Raman enhancement due to these effects at
the tip of an ellipso id of 3:1 axial ratio . At o ther po ints, on o r near
the ellipso id, they find the electric field greatly reduced.
These tips are suggested as simulatio ns of the ro ughness on
the SERS-active surfaces. On the average (co nsidering the
mo lecules distributed over the entire surface of the ellipso id) large
enhancements are no t expected from this mo del. There is also
no thing special abo ut silver in this respect, and all mo lecules sho uld
exhibit this kind of enhancement, if it is really significant.
(ii) Surface Electromagnetic Wave Enhancement
The po ssibility of utilizing the surface electro magnetic field to
enhance the Raman scattering from o verlayers on metals in an ATR
co nfiguratio n was pro po sed befo re the SERS "era" by Chen, et
a
j 375,376 Thgy predicted, for silver, enhancements of abo ut 300 when
bo th the excitatio n and emissio n were carried o ut thro ugh the
co upling prism, and a facto r of ~ 100 when o nly the excitatio n was
thus co upled. Indeed, they repo rted
376
a 75-fold enhancement of
benzene o n a silver film. These ideas were used by Chen and
Burstein
377
to suggest that SERS o n silver islands was due to the
excitatio n of transverse co llective electro n reso nances, which caused
large electric fields and amplified the emissio n. Their estimate of
the enhancement was abo ut 10
6
, which they reduced to abo ut 10
4
,
co nsidering inho mo geneo us bro adening.
Gersten and Nitzan
338
have presented a co mprehensive treat-
ment of the electric field and emissio n enhancement mechanism.
In o rder to illustrate the main physical features of this mechanism
a simple mo del, following Gersten and Nitzan,
338
will be given here.
338 S . Efrima
Let the system co nsist of a mo lecule with (Rayleigh) po lariza-
bility a
u
and a metallic bo dy with the po larizability a
2
. Let the
external field be E
o
. The mo ments of the induced dipo les, in the
mo lecule /xj and in the metal fi
2
, are given by the pro duct of the
po larizability and the to tal field o perating o n each mo iety. Here
o ne assumes the particles to be much smaller than the wavelength
and, for simplicity, the tenso rial pro perties are dro pped. Thus,
(14)
(15)
where M is the scalar form for the dipo lar field function
3
(16)
d is the distance between the two (po int) dipo les and n is the
directio n of the radius vecto r. In Eqs. (14) and (15) the to tal field
is co mpo sed of the incident field and the po larizatio n field exerted
by the o ther particle.
Solving these linear equatio ns and summing the to tal induced
dipo le in the system, gives an effective po larizability
a
T
= (1 - a
x
Ma
2
M)-\a
x
{\ + Ma
2
) + a
2
(l + Ma,)] (17)
Tho ugh written in scalar form, the tenso r structure of the equatio n
was retained.
The Raman po larizability of the system is o btained by differen-
tiating Eq. (17) with respect to a mo lecular vibratio nal co o rdinate
Q and multiplying by its displacement AQ. If o ne neglects the
image term, which is the first term in Eq. (17), then o ne o btains
for the Raman po larizability of the system:
AQa' = AQ[a[ + ot\Ma
2
+ a
2
Ma[] (18)
where the differentiatio n with respect to the vibratio nal co o rdinate
is deno ted by the prime. It is assumed here that the only vibratio n-
dependent quantity is the mo lecular po larizability. One co uld
include the Raman reflectivity mo del by allo wing a
2
to be dependent
on the vibratio n. Also o ne co uld co nsider the dependence of the
co upling matrix M on the vibratio nal co o rdinate. M depends on
the metal-mo lecule distance, which certainly varies with the vibra-
tio n of the mo lecule against the metal. This term was co nsidered
also by Eesley and Smith
340
and predicts a special dependence of
the mo lecule-metal-"bo nd" Raman scattering.
The three terms of Eq. (18) stand fo r three distinct pro cesses.
The first is the usual scattering of the iso lated mo lecule. The seco nd
co rrespo nds to the additio nal Raman scattering by the mo lecule
due to the lo cal field induced by the po larizable metal. The third
term is a Raman reflectivity, where the co upling mechanism is the
co ulo mbic interactio n [see Sectio n III. 2(iii)]. If the term Ma
x
is
1, then enhancements of the Raman scattering are expected.
A further enhancement is expected if o ne co nsiders the
emissio n pro cess. The Raman-shifted mo lecular dipo le mo ment n"
is given by
(19)
where
/itfo = (A(?I + AQa[Ma
2
)E
0
(20)
and that of the metal "bump" is given similarly by
At2 = At2o +
2
A^r (21)
with
0
(22)
We have, fo r simplicity, assumed that the Rayleigh po larizability
at the Raman-shifted frequency is equal to the po larizability at the
incident frequency. This appro ximatio n can be easily remo ved. It
is impo rtant to do so for large Raman shifts, and this predicts
smaller maximum enhancements for high wavenumber vibratio ns
than for small wavenumber mo des.
Co mbining Eqs. (19)-(22) gives, for the to tal Raman-shifted
dipo le,
Mr = (1 - ^ M^ Mr Vi ' o U + <*
2
M) + fi"
20
(l + a,Af)] (23)
Once again an image term is apparent (rigo ro usly at the Raman-
shifted frequency). In additio n, the mo lecular "Raman" dipo le is
amplified by the facto r a
2
M, and to that is added the Raman-shifted
scattering of the metal with its "reflectio n" in the mo lecule. This
co nstitutes the emissio n enhancement. The relatio n between the
340 S . E frima
field enhancement and the emissio n amplificatio n is o bvio us. They
arise from the same type of interactio n and have the same form,
but quantitatively may be different as they are to be evaluated at
different frequencies. Recall that the detected intensity is pro po r-
tio nal to the square of the Raman-shifted to tal dipo le mo ment.
Gersten and Nitzan
338
investigated the case of metal ellipso ids
and spheres, using classical electro dynamics. They find that at the
tip of the ellipso id large enhancements can o ccur due to the LFE
mechanism. They also find that the largest enhancement o ccurs at
the plasmo n frequency of the particle, which is size (and shape
378
)
dependent. This co nditio n is the o ne that maximizes a
2
. They find
that relatively large particles (several tens of nm) can be SERS
active. Larger particles wo uld intro duce retardatio n effects, which
wo uld adversely affect the enhancement, mainly due to unco rrelated
phases of effects from different parts of the particle, and also
radiatio n damping. The preferred aspect ratio , for silver, is abo ut
1:3. Fo r a sphere of co mparable dimensio ns, the calculated
enhancements are abo ut two o rders of magnitude lower than for
an o ptimized ellipso id. The range of the enhancement, in terms of
distance from the surface, depends stro ngly o n the shape. The larger
is the aspect ratio , the sho rter range is the effect. Fo r a sphere, the
range of enhancement is several nm, as is the case for low aspect
ratio s. Fo r an aspect ratio of 10, the range is extremely sho rt and
the enhancement is to a large degree co ntributed by the image term.
There are many o ther interesting aspects discussed in this classic
paper and the reader sho uld refer to it.
Several appro ximatio ns and assumptio ns in these calculatio ns
are wo rth mentio ning. The enhancement facto rs which were calcu-
lated are for a mo lecule lo cated at the tip of the metal ro ughness
feature. The autho rs argue that due to the large (static) fields at
tips the mo lecules will tend to co ncentrate there. Even if that was
true, then for full co verage still, an average over the pro tusio n area
sho uld be carried o ut to o btain the apparent enhancement facto r.
Wo kaun et al
319
estimate the reductio n in intensity due to this effect
to be a facto r of 43, for an ellipso id with the favo rable aspect ratio
of 3:1. Also Ko tler and Nitzan
380
found co nsiderable reductio ns
of the average lo cal intensity in a film. Furthermo re, at ro o m
temperature there is no preference for adso rptio n at the tips, as the
thermal energy is co mparable to , or higher than, the energy gain
by a mo lecule with a static po larizability of 10~
2
nm
3
and sitting at
a site of an extremely high field, 10
7
Vcm"
1
.
Ano ther matter to co nsider is radiatio n damping, i.e., self-
induced emissio n. Wo kaun et al.
379
find that this effect limits the
po ssible enhancement and they calculate a reductio n of five orders
of magnitude of their calculated enhancement of 10
11
witho ut the
damping. Similarly, Mills and Weber
381
find, near a grating, that
the fields are enhanced o nly by a facto r of 5 (i.e., a facto r of, at
mo st, 600 for the LFE Raman enhancement). They estimate that
these effects start to be impo rtant for typical sizes of 12.5 nm.
This is confirmed by calculatio ns of Kerker et a/.,
339
who find
significant enhancements o nly for particles smaller than 5 nm.
At the small-particle limit, where retardatio n is unimpo rtant,
the LFE enhancement is limited by surface scattering. This means
that the dielectric coefficient of the bulk metal is no t valid for the
small particle. The co llisio ns of the electro ns in the small particle
with the wall causes dissipatio n, that is, bro adening of the plasmo n
spectrum. Co nsequently, the particle excitatio ns are less efficient
in pro ducing the large fields needed for LFE enhancement. The
pro cess is damped by the surface scattering. Surface scattering starts
to be impo rtant when the particle size is smaller than the mean free
path of an electro n in silver, abo ut 10 nm. Wo kaun et al
319
find
that the scattering affects the LFE enhancement significantly already
at 20 nm. Fo r a silver ellipso id of abo ut 10-nm average axis size,
the amplificatio n of the square of the electric field is reduced by
facto rs ranging from 10 to 100. Thus the LFE SERS enhancement
would be reduced by two to fo ur o rders of magnitude; this is o ut
of 10
5
-10
n
facto rs they calculate for the to tal enhancement at the
tip.
Ano ther po int which is impo rtant to remember when evaluating
the LFE is its sensitivity to geo metrical facto rs of the metal
"bumps. " Fo r example, Gersten and Nitzan
338
show that for a silver
ellipso id with an adso rbed mo lecule po sitio ned alo ng the major
axis, 1 nm away from the surface, the enhancement changes from
~200 for bo th axes of 50 nm to abo ut 8 x 10
4
for a major axis of
50 nm and an aspect ratio of 5:1. In most of the SERS experiments,
the ro ughness is no t unifo rm. Therefo re, averaging over the distri-
butio n of pro tusio ns sho uld be carried o ut, which certainly
decreases the expected LFE enhancement even further. Ano ther
342 S . E frima
effect this averaging will have is a bro adening of the excitatio n
pro file, from a sharp reso nance spectrum. McCall et a/.
382
have
treated the case of a small sphere. They simulated the distributio n
of the "bumps" by assuming a distributio n of reso nant frequencies.
Lao r and Schatz
383
'
384
co nsidered a distributio n of hemi-
sphero ids o n a flat perfect co nducto r. The interactio ns are taken
as the dipo le co upling of the "bumps," which is valid for a low-
density case. They find for silver (no t including retardatio n and
wall scattering) a flat variatio n with frequency with a dro p at
300 nm. The to tal enhancement is <100. This includes a factor
of 16 with which they multiplied to acco unt for simple reflectivity
from a smo o th surface. They did no t, ho wever, include emission
enhancement (except the trivial reflection facto r), arguing that
rarely will the incident frequency and the Raman-shifted emissio n
be simultaneo usly in reso nance with the plasmo ns. If we add the
maximum value of such an emission enhancement to their evalu-
atio n, we find a to tal ideal enhancement of 500. Similar results,
tho ugh with so mewhat smaller values, are calculated for Cu, Au,
Hg, and Pt.
Arya et a/.
385
co nsider a rando mly ro ugh metal surface and
find a maximum enhancement for silver of 1000 at 400 nm. In the
visible the enhancement is smaller (abo ut 100).
Ano ther po int wo rth mentio ning is the use of the metal lo ng-
wavelength dielectric functio n. No dispersio n was allo wed in the
mo del. The wave-vecto r dependence of the dielectric co nstant is
impo rtant at close pro ximity to the surface as was already remarked
in the co ntext of the image calculatio ns. This appro ximatio n may
be reaso nable away from the surface, distances for which the LFE
is most appro priate.
Fo rd and Weber
331
'
332
included the effect of dispersio n by using
a Lindhard fo rmula for the dielectric co nstant, and included also
a co nstant term to acco unt for the bo und-electro n co ntributio n.
They find that the LFE enhancement is <1000 and po int o ut the
impo rtance of the co upling to e-h.
A further po int is neglect of the interactio n between the ro ugh-
ness features on the surface. This electro magnetic interactio n causes
dissipatio n and bro adening of the plasmo n excitatio ns, with an
adverse effect on the enhancements. Aravind et a/.
386
investigated
the case of two metal spheres. They fo und that the enhancement
is smaller than for a single sphere, except at co nfiguratio ns which
mo nito r the regio n between the two spheres.
Yamaguchi, et al
387
have sho wn that in additio n to bro adening
due to dipo le-dipo le interactio ns between silver particles, addi-
tio nal bro adening is bro ught abo ut by pro per treatment of the
retardatio n, beyo nd the static limit.
The effect of the appro ximatio ns discussed abo ve, or at least
some of them was shown in the work of Mo reland et a/.
388
They
demo nstrated that the efficiency of light emissio n from silver sur-
faces excited by ATR was typically small: abo ut 5% for a silver
island film, 9% for a calcium fluo ride ro ughened layer, and up to
80% for a silver film evapo rated o n a ho lo graphic grating.
Several o ther gro ups have co nsidered the LFE mechanism in
a variety of systems with similar mo dels. Aravind and Metiu
389
have
studied the case of a sphere extended abo ve a flat metal substrate.
They find exceptio nally high enhancements in the regio n between
the two bo dies. Aravind and Metiu
390
discuss the ro le of emissio n
enhancement due to rando m ro ughness characterized by a co rrela-
tio n length. They find a maximum enhancement of a 100 for silver,
but that is at the plasmo n frequency, 3.5 eV. In the visible the
enhancement due to this mo del is <10. Fo r co rrelatio n lengths
>15nm, there is an attenuatio n instead of an enhancement.
Adrian
391
calculated the LFE enhancement for a mo derately pro late
sphero id in the electro static limit. He finds up to 10
7
enhancement
for a mo lecule sitting alo ng the major axis. It is very slightly distance
dependent. Rupin
392
calculated the electric field enhancement near
a hemisphero id o n a flat surface. Both have "real" dielectric pro per-
ties (no t perfect co nducto rs). He further assumes the emissio n
enhancement to be equal to the field facto r. He finds maximum
enhancements of 10
7
alo ng the no rmal to the flat surface, at the
plasmo n frequency. Off the plasmo n reso nance, the to tal enhance-
ment is typically 1000. The distance dependence is again weak. Fo r
a 10-nm bump, the enhancement decreases by a facto r of 10 go ing
from the first to the third pyridine layer. Messinger et al
393
co n-
sidered o nly the field enhancement and find that the multipo lar
excitatio ns can be impo rtant and will suppo rt reso nances at frequen-
cies lower than the dipo lar reso nance frequency. Additio nal calcula-
tio ns have been made by Go ro bei et al.
394
Ohtaka and Ino ue,
395
Numata,
396
Agarwal, et al
335
Sako da et al
397
Arya and Zeyher,
348
344 S . Efrima
Brodsky and Urbakh,
398
Barber et al,
399
Garcia,
400
'
401
and Kirtley
et a/.
402
'
403
Regretfully, these papers canno t be discussed in detail
here and the reader sho uld refer to the o riginal articles quo ted
abo ve.
As mentio ned abo ve, Kerker et a/.
339
-
404
-
407
have carried o ut a
rigo ro us calculatio n in the classical limit for metal spheres,
sphero ids, and covered spheres suspended in a liquid suppo rt
(co llo id). They no ticed that large particles (>5 nm) exhibit reduced
enhancements, pro bably due to the retardatio n and radiatio n damp-
ing. Fo r the small particles they find large enhancements (~10
5
),
but only at the maximum of the excitatio n spectrum, which sho uld
be for their co llo ids (silver citrate) at ~400 nm, and no t in the visible.
Finally, Weber and Fo rd
408
estimate an upper limit of the field
enhancement o n the basis of co nservatio n-o f-energy co nsideratio ns.
They find for silver and a perfect co upler between the radiatio n
and the metal excitatio ns (a grating or a prism) that the maximum
enhancement of the square of the field is appro ximately 300. This
is pro bably the average quantity. Fo r a ro ugh surface they estimate
an enhancement on the o rder of magnitude of unity!
4. Dyes in S E R S T heory
In this sectio n the behavio r of dyes, i.e., mo lecules that are in
reso nance with the incident light befo re adso rptio n on the surface,
will be discussed from the theo retical po int of view. It is of interest
to see whether the study of dyes may no t help discriminate between
the vario us mechanisms. Perhaps, this may have also some value
for the utilizatio n of SERS.
The stro ng reso nance behavio r of dyes may interact with the
metal substrate reso nances and bring abo ut a behavio r which is
no t a simple superpo sitio n of either of the two . Po ckrand et al
409
have sho wn the o rienting effect of a surface on the o rganizatio n in
the dye layer, which affected the fo rmatio n of dimers o r mo no mers,
and also the po larizatio n pro perties of the dye abso rptio n. In this
case, due to the wide abso rptio n bands of the dyes, no reso nance-
reso nance effects were seen.
Glass et al.
410
and Craighead and Olso n
411
have shown experi-
mentally that the reso nance of rho damine 6G (R6G), at abo ut
570 nm, interacts stro ngly with the excitatio n reso nance of silver
island films (asso ciated with plasmo nlike excitatio ns). A do uble-
peak abso rbance develo ps, with the high-energy peak at energies
greater than that of the iso lated silver film and the lo wer-energy
peak is red shifted co mpared to that of the dye alo ne. Fo r silver
film thicknesses such that the film is co ntinuo us, the R6G spectrum
reappears. Similar results were o btained also for rho damine B and
Nile Blue. The luminescence intensity was also measured as func-
tio n of average film thickness. It was fo und that the intensity
generally peaks at a thickness for which the plasmo n reso nance of
the bare silver co incides in frequency with that of the dye. The
luminescence intensity changed by as much as a facto r of 20. It
was no t co rrected for the surface co verage which may also change
in a peaked waya small amo unt of adso rbed material for the
lo w-thickness, low silver-particle density as for the relatively smo o th
thick films, and in between, the largest adso rbed amo unt o n the
ro ugh and dense silver island film. The excitatio n spectrum (for
luminescence) or rho damine B o n a silver film co incided with that
measured when this dye was adso rbed o n glass.
Garoff et al
412
fo und similar results for R6G o n silver films.
They study the o ptical density of the dye-co ated films as a functio n
of dye co ncentratio n (in the so lutio n from which it is adso rbed o n
the silver) and as a functio n of film thickness. The do uble peaks
appeared and were explained o n the basis of Mie fo rmalism. No te
that significant changes in the spectrum shape appear only from a
co ncentratio n of 2.8 x 10~
4
M. Also no determinatio n of the amo unt
adso rbed o n the surface is repo rted.
Wang and Kerker
413
and Chew and Wang
414
have presented
a theo retical treatment, based on the electro dynamic appro aches
used for the SERS pro blem, and pro vide a full descriptio n of the
extinctio n of the dye-co ated sphero ids. They also calculated the
luminescence enhancement, and find it to be up to 10
4
o n silver
for o ptimal wavelengths and particle shapes.
Ko tler and Nitzan
415
applied the electro static limit to a silver
sphere co ated with a dye. They fo und also in this case a do uble-peak
behavio r, under certain circumstances. No tewo rthy, are the
enhancements of the Raman scattering of up to ~10
4
, near the
particle plasmo n reso nance. (Fo r their mo del of a sphere it is at
3.5 eV but for o ther shapes it can be bro ught into the visible range).
The enhancement is very weakly dependent on the distance from
346 S . E frima
the surface, decreasing by an o rder of magnitude for a layer of
8 nm (for a particle of radius of 10 nm).
Ho wever, changes in the abso rptio n spectrum are no t the only
effects expected and seen in the behavio r of dyes on metallic (silver)
surfaces. It has been kno wn for some time now that pro ximity to
a silver surface brings abo ut major changes in the lifetimes and
quantum yields for fluo rescence of mo lecules. Fo r an early work
in that field, see Kuhn
416
and for a excellent theo retical treatment,
Chance et al
417
Within the framework of classical electro dynamics,
it was sho wn that the metal o pens dissipative channels into which
the excited mo lecule can discharge its energy. The theo retically
calculated lifetimes fully agreed with tho se measured, up to dis-
tances of abo ut 10 nm from the surface.
Ro ssetti and Brus
418
fo und, for pyrazine o n silver, that the
classical electro dynamic theo ry indeed agrees well with the
measured decrease of lifetimes. Ho wever, at sho rter distances the
change in lifetime was much mo re gradual and did no t follow the
theo ry. Campio n et al.
419
and Whitmo re et al
420
fo und, for the same
mo lecule, that the classical theo ry wo rked agreeably all the way
do wn to 0.5 nm away from the surface, where the lifetime has
decreased by a facto r of ~1000 as co mpared to the lifetime of the
iso lated mo lecule.
Po ckrand et al
421
also find that the decay into the surface
plasmo ns beco mes inefficient at distances smaller than 18 nm, when
the dye is no t in reso nance with the plasmo n frequency.
Weitz et al
422
*
423
studied the fluo rescence of euro pium io ns
adso rbed o n silver islands. They find the lifetime to be abo ut three
o rders of magnitude sho rter than on a bare silica substrate. The
emissio n in this case is reso nant with the silver islands at 613 nm.
Gersten and Nitzan
424
develo ped the theo ry of lifetimes and
quantum yields near metal sphero ids. They showed that at sho rt
distances the expected change in lifetimes sho uld be larger than
near a flat surface by several o rders of magnitude, when in reso nance
with the plasmo n of the sphero id. When o ut of reso nance, the effect
is limited to a facto r of abo ut 10. Thus a to tal of lifetime sho rtening
of abo ut 10
3
is expected.
The two effects discussed abovethe enhancement of the fields
(and emissio n) and the sho rtening of lifetimeswere co mbined by
Weitz et al
240
to describe SERS behavio r of dyes. The basic claim
is that the LFE mechanism enhances the Raman scattering of the
dye, just as it wo uld that of a no rmal Raman scatterer, i.e., by
facto rs of abo ut 10
5
-10
6
. Ho wever, they co ntinue, due to the sho rter
lifetimes near the surface, the reso nance of the dye is bro adened,
and a less efficient scattering is exhibited. The net effect wo uld be
an enhancement two to three o rders of magnitude lower than that
for a no rmal scatterer.
Ho wever, the latter argument is no t valid for the following
reaso n: typical lifetimes of high-quantum-yield mo lecules are 10 n.
Fo r a surface effect of even 10
4
(which is a higher facto r than that
measured o n island films), the surface lifetime beco mes ~l ps ,
which is 3 cm"
1
. This is clo se to the linewidths asso ciated with
vibratio nal, no nradiative decay rates. Thus, the reso nance Raman
intensity which is determined by the shortest lifetime will not change
to any significant degree. The vibrational lifetimes are clearly no t
changed to any large degree, as the SERS vibratio nal bands are
only slightly bro ader than in so lutio n (up to a facto r of 2) and part
of that is due to inho mo geneo us bro adening. It must be mentio ned
that there are claims for larger lifetime changes in several systems,
bo th for electro nic and vibratio nal degrees of freedom (see, for
instance, Persso n
425
and Demuth and Avo uris
297
'
426
), but that is a
separate sto ry. Anyway, in o rder to affect the reso nance Raman
intensity to any significant degree, the bro adening sho uld be as
large as the electro nic abso rptio n envelo pe itself. Champio n and
Albrecht
427
show that there is no difference in the Raman scattering
intensity for widths of 10 o r 100 cm"
1
. If indeed the bro adenings
due to the surface are as large as the abso rptio n band itself, then
no typical reso nance structure of the SER spectrum of the dye
sho uld appear. Thus o ne wo uld expect the SER spectrum to maxim-
ize at the same wavelengths as tho se for which the SERS of no rmal
scatterers is a maximum (especially if the dye and the no rmal
Raman scatterer are co adso rbed).
Thus, in summary, it appears that the LFE mechanism predicts
that for dyes in reso nance the Raman spectrum will be enhanced
to the same degree as no rmal scatterers, except when a typical
reso nance excitatio n profile is no t o bserved. This co nclusio n is in
co ntradictio n to that expressed in Reference 240. The excessive
sensitivity of the mo del presented there to lifetime changes is, to a
large part, due to the simple two -state descriptio n of the excited
348 S . E frima
mo lecule. One sho uld keep in mind that, on the surface, there may
be shifts of the spectra. That still wo uld require the usual large
SERS enhancements acco rding to the LFE. A mo re detailed analysis
is given elsewhere.
497
The reso nance mechanisms, by virtue of all of them having a
ceiling enhancement determined by the pro perties of the enhanced
mo iety, predict that the enhancement effect with dyes in SERS will
be o rders of magnitude smaller than for a no rmal scatterer. As a
ro ugh rule of thumb, the enhancement will be smaller by a facto r
co mparable to the ratio of the scattering intensity of the dye and
no rmal scatterer in so lutio n.
Thus, study of the surface Raman scattering of dyes can be
helpful in pinning down the SERS enhancement mechanism.
I V. W H A T I S " T H E " S E R S M E C H A N I S M ?
1. General
The po ints to be co nsidered when analyzing the vario us theo retical
mo dels in the light of the available experimental evidence are the
fo llo wing:
1. Can the theo retical mo del explain apparent enhancements
>10
4
and as high as 10
7
? This evaluatio n sho uld have
been do ne after co nsidering the appro ximatio ns in the
mo dels and the effect the remo val of these appro ximatio ns
may have on the calculated enhancement.
2. Is the surface mo rpho lo gy required by the mo del shown
to be unquestio nably present in the experimental setups?
3. Can the mo del explain the dependence on the metal
substrate?
4. Can the mo del explain the electric po tential dependence?
5. How do es the predicted excitatio n profile agree with the
experimental o ne?
6. Regarding the distance dependence, how do es theo ry
co mpare with experiment?
7. What is the dependence on the mo lecule?
8. What is expected of the behavio r of two different
mo lecules co adso rbed, in terms of intensities and
frequency dependence, and what is seen?
9. How are "dye" mo lecules expected to behave, especially
co mpared to (co adso rbed) no rmal scatterers?
10. How do es the SERS depend o n the "so lvent," especially
as regards the excitatio n spectrum?
11. What is the dependence of SERS of o ne mo lecule on the
co ncentratio n of o ther chemical species present?
12. What sho uld be the effect of temperature annealing, and
how do es it co rrelate with irreversible behavio r under
electric po tential changes?
13. Regarding the dependence of SERS on the Raman shift,
how do es the SERS of the vario us mo des in the same
mo lecule co mpare?
14. How is the dependence of the excitatio n maximum on
the electric po tential explained, especially as regards the
magnitude of the shift?
Most of these po ints were addressed in this review, bo th from the
experimental side and the theo retical aspect.
There are several o ther criteria which we have no t mentio ned
here, o r discussed in the main bo dy of this review, such as the
po larizatio n dependence, angular dependence, selectio n rules, the
appearance of a co ntinuum, and the dependence on intensity. These
to pics were no t discussed here due to space limitatio ns. It seems
that the po larizatio n characteristics, the angular dependence, and
the selectio n rules are less mo del sensitive and depend mo re stro ngly
on the metal dielectric pro perties and the adso rptio n fo rmatio n
than on the specific enhancement mechanism. The co ntinuum back-
gro und, which appears in mo st SERS studies, is perhaps mo re
indicative of the enhancement mechanism, o r parallel pro cesses at
the surface.
Ano ther to pic which was no t discussed in this review is the
ro le of graphitic layers in the pro mo tio n of SERS. A sho rt expo sitio n
will be given in Sectio n V.
This is an appro priate place to ackno wledge the co ntributio ns
of the large number of researchers to the advancement of the
understanding of SERS, and to apo lo gize to tho se whose work has
no t been adequately co vered in this review, as it certainly deserves.
2. "T he" S E R S M echanism
This sectio n is left for the reader to fill in!
The experimental facts (and myths) were critically reviewed
and expo sed here. The theo retical mo dels were discussed.
350 S . E frima
The present autho r can only reiterate his co nclusio n, stated in
the Intro ductio n, based o n the evaluatio n of theo ry and experiment
as given abo ve: "There is no 'o ne' mechanism at the ro o t of SERS;
ho wever, there is a mechanism which, in the large majority of
systems, is the main co ntributo r to the surface enhancement effect.
That mechanism is a reso nance mechanism. It is felt there is no t
eno ugh evidence, yet, to determine which of the mechanisms
belo nging to this gro up is the impo rtant o ne, o r which can be ruled
o ut. The LFE mechanism certainly has a ro le, but a mo re mino r
o ne. No te, ho wever, that a mino r facto r in SERS is a facto r of a
100 o r so , which may be the difference between a detectable and
a no ndetectable signal!"
V. S E R S A US E FUL T O O L
It is appro priate to begin this last sectio n by quo ting Furtak,
138
in
o ne of the early SERS papers: 'The lo ng so ught for experimental
to o l for detailed chemical characterizatio n of the so lid-aqueo us
electro lyte interface may have at last been fo und. " This was the
general feeling o r at least the general wish. Has it been realized?
What do es the future ho ld for it?
As was shown in this review, the major effort in SERS studies
was directed to ward understanding this pheno meno n, and generally
no t to ward its applicatio n and utilizatio n. Nevertheless, some very
interesting info rmatio n was acquired alo ng the way, regarding
interfaces and mo lecules at interfaces, as can be seen from the
repo rts reviewed thro ugh this review. An increasing number of
studies is carried o ut now to use SERS as a to o l and the pro po rtio n
can be expected to increase further.
In this sectio n a brief summary of representative studies, which
have used SERS for surface studies, is given.
SERS is no t the only metho d to apply Raman techniques to
surfaces. There are several o ther ways of increasing the sensitivity
of the Raman technique, and all work to gether to offer a versatile
and powerful instrument. No wadays, Raman measurements can be
perfo rmed with the high sensitivity of OMA techniques, which po se
no special restrictio ns on the systems investigated (no specific metal
o r surface preparatio n).
28110
'
428
An alternative is using metal grating surfaces.
110
'
170
'
175
'
281
'
429
'
430
Such surfaces can exhibit enhancements up to two o rders o f magni-
tude. Also ATR co nfiguratio ns can be used o n a variety o f sur-
faces.
94
'
177
'
431
"
435
Interference techniques can be applied
436
as well
as waveguide techniques in 100-nm films.
437
"
439
New geo metries fo r
surface enhancement were suggested, fo r instance by Aravind et
al
440
An interesting po ssibility is inducing SERS activity, in a no n-
SERS-active substrate, by depo siting submo no layer quantities of
silver on its surface. Van Duyne and Haushalter
225
used this metho d
to measure Raman scattering from a GaAs semico nducto r interface.
There was also an experiment to use a silver underlayer to induce
SERS in a layer co vering it.
256
A very impo rtant feature of SERS is that it works in "dirty"
ro ugh-surface systems, and is relatively insensitive to the phase
adjacent to the metal. This allo ws its use in "real" systems of
interest, for instance, to the study of abso rptio n in catalysis.
Ano ther interesting characteristic of SERS is that, as was shown
abo ve, in many systems special sites are mo st efficient in pro mo ting
it. Thus, generally, SERS do es no t "see" all the mo lecules, but
mainly tho se adso rbed near surface defects. But these same defects
and sites may be the center of the chemical activity of the surface.
It wo uld be of extreme impo rtance if such a co nnectio n co uld be
made, and future research in this directio n may pro ve very fruitful.
Kno ll et al
156
have sho wn that IR and SERS are sensitive to
mo lecules in different enviro nments o n the same system. Also ,
Yamada et al.
277
fo und for CO o n silver that the IR exhibited a
band'at 1940 cm"
1
, while in SERS a band at 2112 cm"
1
was o bserved.
Co nsequently, these two metho ds are co mplementary also o n the
surface.
SERS pro vides a means to study adso rbed mo lecules thro ugh
their vibratio nal structure. Ho wever, a simple co mpariso n is, alas,
no t straightfo rward in mo st cases. Besides the chemical changes
which can o ccur, we still do no t know in what way the enhancement
mechanism affects the vario us vibratio nal bands, shifts them, and
changes their relative intensities. It is established that the selectio n
rules on the surface are different than tho se which pertain to a bulk
situatio n. Hexter and Albrecht
89
have analyzed the selectio n rules
by assuming that the metal surface is appro ximately a perfect mirro r,
352 S . E frima
which adds a symmetry element, impo sing some restrictio ns on
the appearance of vibratio nal bands. Ho wever, real (SERS-
active) metals at o ptical frequencies are no t perfect co nducto rs
and o ne wo uld no t expect a co mplete disappearance of mo des
which are parallel to the surface. Furthermo re, in Raman scat-
tering the directio n of change of the po larizability is the impo r-
tant directio n and no t that of the vibratio nal transitio n dipo le,
which co mplicates the analysis even further. Erdheim et al
51
have
fo und that the SERS of pyrazine exhibited asymmetric bands,
which in so lutio n are Raman fo rbidden. Kunz et al
120
have dem-
o nstrated that azide io n adso rbed on silver exhibits SERS of IR-
allo wed-Raman-fo rbidden bands. Mo sko vits and DiLella
105
'
441
find similar behavio r. Mo sko vits et al
442444
analyze this in
terms of the existence of electric field gradients at the surface.
They show that the bands that appear have the pro per symmetry
to be explained by this assumptio n. The po ssibility of the lower-
ing of the symmetry upo n adso rptio n in a site of a specific sym-
metry, was also mentio ned by them and further discussed by
Do rnhaus.
55
The vibratio nal analysis of the SERS spectrum can be further
co mplicated by the appearance of o verto nes.
445
The net result is
that extreme care sho uld be exercised when trying to use the
vibratio nal shifts and relative intensities to infer the identity of a
surface species and its immediate enviro nment. Nevertheless, such
analyses were carried o ut in the past, and will co ntinue to be
perfo rmed also in the future, until we have a better understanding
of the surface co ntributio ns invo lved.
Allen and Van Duyne
446
have co rrelated the Raman intensity
for the cyano gro up in 2-, 3-, and 4-cyano pyridine to its directio n
with respect to the surface. They found that the mo lecule for which
this gro up is parallel to the surface exhibits the weakest signal.
Creighto n
447
discussed the po ssibility of determining adso rbate
o rientatio n from SERS relative intensities. The co nclusio n is that
it is feasible, unless chemical changes are invo lved.
SERS was used to determine the structure of adso rbed
mo lecules. Many examples were cited in the vario us sectio ns of
this review, such as the study of adso rbed water, and will no t be
repeated here. We give here only a few additio nal examples, most
of them very recent.
Fleischmann et a/.
209
'
448
discuss the structure of water in the
do uble layer and adso rbed o n a ro ugh silver electro de. They find
several bands indicating different forms of water. These are asso ci-
ated with so lvated catio ns. The effect of anio ns is also studied and
it was fo und that they are co adso rbed with the water. Fleischmann
et al.,
449
in a separate sutdy, have inferred from the SERS spectra
that quino line and iso quino line io ns adso rbed as io n pairs when
adso rbed from an acidic medium. Bunding and Bell
450
infer selective
hydratio n of pyridine carbo xaldehydes pro ducing carbino ls, for the
para and o rtho derivatives but no t for the meta. Po ckrand et al
451
identify two forms of acetylene o n a silver film. They canno t assign
the bands seen to any specific fo rm. Sandroff et al
452
use tetrathiaful-
valene to pro be the charge transfer to silver and go ld surfaces,
mo nito red by the po sitio n and intensity of the vibratio nal bands.
The po ssibility of detecting a vibratio nal band asso ciated with
a surface-mo lecule bo nd was already discussed. In this co ntext we
mentio n the silver-thio urea bo nd seen by Maco mber and Furtak
57
and the co pper-N vibratio ns seen on co pper co llo ids.
36
Several mo lecules were investigated because of the applicabil-
ity in a system of interest. Silver o xide was investigated by Kotz
and Yeager
453
for the significance of the silver/silver o xide electro de
as a catho de in batteries and as a catalyst for oxygen reductio n.
Mercapto benzo thiazo le was studied
454
for its ro le as a co rro sio n
inhibito r for several metals. Von Raben et a/.
455
'
456
co uld follow
the adso rptio n of sulphates and nitrates on a silver po wder in the
co ntext of catalysis. Sandroff and Herschbach
56
showed that several
disulfides disso ciate to the sulfides when adso rbed on silver. This
was discussed in relatio n to lubricatio n pro blems. Sandroff et al
457
investigated the surface co nfo rmatio ns of hexadecane thio l as a
functio n of the so lvent in co ntact with silver. This mo lecule is an
amphiphile, of interest in wettability pro blems.
Reactio ns were also mo nito red by SERS. Yamada et al
45S
discussed the reactio n of ro se bengal adso rbed on a ZnO electro de.
This is an example of the use of the reso nance enhancement to
gain eno ugh sensitivity. Billmann et al
92
followed the chemiso rptio n
of cyanide o n silver, and detected the fo rmatio n of the vario us
cyanides o n the surface. Similarly, Lo o
190
investigated halide com-
plexes on a go ld electro de. Pemberto n and Buck
214
used SERS to
see the adso rptio n of diphenylthio carbazo ne and its o xidatio n into
354 S . E frima
a disulfide. Itabashi et al
222
lo o ked at the disso ciatio n of po r-
phyrin into its mo no mers and silver inco rpo ratio n into the ring.
Fleischmann et al
459
investigated the electro po lymerizatio n of
pheno l o n silver.
SERS is impo rtant also in the study of catalysis. Here silver
itself is of interest such as for the ethylene epo xidatio n reactio n.
460
Mo sko vits et a/.
46
-
50
-
106
sho wed the usefulness of SERS for the study
of the adso rptio n of simple alkenes o n silver. Do rain et al
461
fo und,
using SERS, catalytic fo rmatio n of sulfites from sulfur dio xide on
silver po wder, and followed the o xidatio n by oxygen to sulfates.
Pettenko fer et al
462
repo rt the detectio n of pero xides and super-
o xides o n silver.
SERS has been used also under high-pressure co nditio ns by
Po dini and Schnur
463
who discuss the reliability of the measured
parameters. Sandroff et al
464
have used high-pressure chambers,
to o .
Suh et al
97
demo nstrated that SERS co uld be used to detect
"two -dimensio nal" phase equilibrium between a gaslike phase
and a so lidlike phase, for /7-aminobenzoic acid adso rbed on
silver.
Co mpetitio n over surface sites and surface displacement of
adso rbates was o bserved by Garrell et al,
192
who detected replace-
ment of chlo ride by bro mide o n a silver co llo id. Owen et al
465
repo rt similar displacements on a silver electro de. Bachackashvilli
et
a
i
49
>
229
>
230
have mo nito red co mpetitio n of pyridine and several
azo dyes o ver the surface of a silver co llo id.
Kinetics of adso rptio n were investigated by Pemberto n and
Buck,
466
who followed the adso rptio n of dithizo ne on a ro tating-disk
silver electro de, on the time scale of a few seco nds. Dendramis et
al
461
repo rted adso rptio n of cetyltriammo nium on co pper in the
minute time scale.
An interesting applicatio n of SERS was repo rted by Farquhar-
so n et al
46S
They determined the reversible redo x po tential of
osmium io ns by mo nito ring their relative surface co ncentratio ns as
a functio n of electric po tential.
The investigatio n of dye mo lecules o r o ther highly fluorescing
mo lecules can be facilitated by the quenching of the fluo rescence
by the surface, as no ted by Nimmo et al
241
A go o d example can
be seen in References 59 and 227.
SERS has been used for the study of mo lecules of bio lo gical
impo rtance, such as nucleic acid co mpo nents.
469
'
470
The adso rptio n
on a silver electro de was co nsidered in some way similar to the
adso rptio n to the charged membranes in bio lo gical systems. The
adso rptio n of a nucleic acid itself was also studied with SERS.
471
We have already discussed the work of Co tto n et a/.
218
'
219
'
221
who studied Cyto chro me C and myo glo bin. SERS requires o nly
small quantities of material, which is very suitable for bio lo gical
studies.
Special mentio n must be made of SERS studies of carbo nates,
carbo n, and graphitic layers o n surfaces. Co o ney et al
131
'
412
'
415
have repo rted the appearance of Raman vibratio nal structures
asso ciated with the presence of carbo n species o n the SERS-active
surfaces, in electro chemical systems. They even suggest that a
graphitic layer formed o n the surface is respo nsible for the SERS
pheno meno n itself. Tsang et al
416
also discuss the bro ad bands
seen in SERS at 1350 and 1550 cm"
1
in terms of amo rpho us carbo n.
In the UHV systems, Po ckrand and Otto
69
repo rt carbo nate
impurities exhibiting enhanced Raman scattering. They find that
these impurities are inco rpo rated into the sample belo w the surface.
DelPrio re et al.
166
find by XPS several layers of carbo n and oxygen
on SERS-active vapo r-depo sited surfaces in the UHV.
Very recently, Efrima
477
suggested a co mbinatio n of SERS and
o ptical-activity measurements. Pro vided large field gradients are
present near the metal surfaces, o ne sho uld measure very large
effects. This may pro vide an easy way to extract chiral info rmatio n.
Besides the direct utility of SERS and the impact it had had
on the way we think abo ut metal interfaces, SERS and the SERS
mechanisms have suggested many o ther effects, some of which have
already been put to trial. This review wo uld no t be co mplete witho ut
mentio ning them.
Nitzan and Brus
478
'
479
have pro po sed that pho to chemical reac-
tio ns on SERS-active substrates may be also enhanced. Go ncher
and Harris
480
repo rted pho to fragmentatio n of several mo lecules
adso rbed o n a silver surface, with an incident wavelength of
363.8 nm(!). They attribute the reactio n to enhanced singlet-triplet
transitio ns o r to multipho to n pro cesses. Chen and Osgo o d
481
repo r-
ted enhanced pho to depo sitio n o n several metals, but no t on go ld,
at 257 nm.
356 S . E frima
Garoff et al
226
repo rt co ntrary behavio r. They no ticed slower
rates of pho to fragmentatio n on silver islands as co mpared to an
o xide substrate. This is pro bably due to the efficient dissipative
channel for transfer of excess energy of the mo lecule to the metal,
which arises upo n adso rptio n.
Weitz et al
240
also no ted an effect of SERS-active systems on
the fluo rescence of mo lecules. Fo r the mo lecules they studied, a
low quantum yield in the bulk was asso ciated with higher fluo res-
cence on the surface, while efficient emitters exhibited a quenched
fluo rescence.
Chuang
482
and Chuang and Seki
483
'
484
repo rted enhanced
deso rptio n rates of pyridine from silver when illuminated in the IR
near a pyridine vibratio nal frequency. The rate was no nlinear in
the laser intensity and exhibited a definite reso nance behavio r
aro und the breathing mo de of pyridine. Pyridine on KC1 gave
essentially similar results. It seems that lo cal heating due to the
abso rbance of the pyridine is impo rtant here.
Ano ther pheno meno n related to SERS and suppo sed to be
affected by the same mechanisms, is seco nd harmo nic generatio n
(SHG). This was seen a lo ng time ago by Lee et a/.
485
In a series
of papers, Chen et
a
/.
95
-
486
-
489
repo rted enhanced SHG with
enhancement facto rs ranging from 100 to 10
4
. These results have
an immediate impact o n the validity of the LFE mechanism.
Ho wever, the ro le of field gradients has no t beeen co nsidered. SHG
was used to mo nito r changes o n a silver electro de during electric
po tential cycling.
490
Also co herent anti-Sto kes Raman scattering (CARS) was tried
in SERS-active systems. Schneider
491
measured the CARS of ben-
zene on a silver film. The degree of enhancement (if any) is no t
given. Chew et al
492
have presented a theo retical discussio n of the
CARS o n co llo ids. Schneider
491
repo rted that CARS was no t seen
on co llo ids, due to a small interactio n zo ne.
Finally, Glass et al
493
investigated two -pho to n fluo rescence of
mo lecules adso rbed o n silver surfaces, and fo und an enhancement
facto r of -150.
Examples of several of the ways SERS has been utilized were
quo ted here in o rder to show the directio ns of research and applica-
tio n. The validity of the vario us applicatio ns and their results are
still an o pen questio n, and hopefully will be investigated in future
experiments.
As a final no te, it is useful to quo te Furtak
138
o nce again: "We
have sho wn in this repo rt, given the state of understanding as it
now exists, that so me. . . systems can already be studied in detail
using enhanced Raman scattering. If we can develo p the technique
to its po tential, as Auger spectro sco py has been develo ped in
surface-vacuum characterizatio n, understanding of the metal-elec-
tro lyte interface will be pro pelled by a genuine breakthro ugh. " This
ho lds true to day, five years later. The if is perhaps smaller, but it
is still there!
A C K N O W L E DGM E N T S
I wish to thank Mr. Hai Co hen for his invaluable help in assembling
and catalo guing the extensive literature.
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B atteries for Vehicular P ropulsion
Halina S. Wro blo wa
Ford Motor Company, Scientific Research Laboratory, Dearborn, Michigan 48121
1. General R emarks
The key part of an electric vehicle (EV) is its po wer plant. Within
10 years of the inventio n of the lead/acid battery (Plante, 1860) an
electric carriage appeared in England, followed 10 years later by
an electric tricycle in France. In America the first electric two -seater
was co nstructed in 1891, and in 1899 electric vehicles captured 60%
of the emerging U.S. auto mo bile market. The nickel-iro n battery
invented by Ediso n to pro vide cars with lo nger range between
recharges failed to prevent, ho wever, an early demise of the EV
market share. Its abrupt decrease was a result of the inventio n of
the electric self-starter for internal co mbustio n engine vehicles
(ICEV) and their impro ved reliability. A few years after the
intro ductio n of the Fo rd Mo del K car, the market share of EVs
dwindled to some 3%. Abo ut the same time, small fleets of electric
buses, delivery vans, and cars appeared in Germany. They were
po wered by so mewhat impro ved versio ns of the lead-acid system
(18 Whkg"
1
). Over 20,000 electric trucks were on German ro ads
until the middle 1930s to reappear for abo ut a decade after World
War II.
1
Over 200 battery-po wered railcars are in o peratio n each
day in West Germany.
2
In Great Britain, fleets of delivery vans
(presently o ver 55,000 units) have been on the ro ad co ntinuo usly
371
372 H alina S . W roblowa
for the last 70 years. The energy and maintenance co sts of electric
vans were sho wn to be 45-60% of their gaso line and diesel-po wered
analo gues.
3
'
4
Small fleets of electric buses are in o peratio n in Aus-
tralia, England, France, Germany, and Japan.
4
'
5
Fo r specialized
purpo ses (e.g., indo o r, undergro und, and airpo rt transpo rt of peo ple
and cargo ; golf carts; forklifts) lead/acid tractio n batteries are
widely used. Only in the USSR they have no t co mpletely displaced
nickel-iro n batteries.
Electric passenger cars canno t presently co mpete with ICEVs,
neither eco no mically no r in terms of user's co nvenience. Therefo re,
only a very limited number of two - and fo ur-seater lead/acid-
po wered passenger EVs have as yet been co nstructed.
2
'
4
In the 1960s the interest in electric carsas a remedy against
urban po llutio nwas revived and strengthened in the 1970s by the
realizatio n that foreign oil so urces can be abruptly shut off, oil
supplies will be exhausted in the no t-to o -distant future, and indeed
all fossil-fuel supplies are finite. Intensified research in the area of
battery systems, which (at least in the USA) seems to have peaked
in terms of funding aro und 1980, resulted in co nsiderable impro ve-
ments of previo usly available systems and in wo rldwide efforts to
develo p new batteries better suited for EV applicatio ns than lead-
acid. The latter still remains the only battery co mmercially used
for specialized tractio n purpo ses, while o ther systems are now at
vario us stages of develo pment. The decrease in the EV battery R&D
effort can be related, on the o ne hand, to the tempo rary "o il glut"
and, on the o ther, to the inherent range limitatio n of cars po wered
by seco ndary batteries and severe technical difficulties co nnected
with the necessity of simultaneous o ptimizatio n of several battery
attributes which are desirable for EV applicatio ns. The required
battery attributes are closely linked to gether and impro vement of
o ne feature usually has an adverse effect on o ther pro perties.
2. B attery C lassification
Among rechargeable batteries co mmercially available to day (Table
1), only the lead/acid (Pb-A) and Ni-Fe systems can be co nsidered
as po tential EV po wer plants because of the cost and scarcity of
materials used in o ther batteries. The perfo rmance of the Pb-A and
Ni-Fe systems is, ho wever, inherently limited by their low-energy
B atteries for Vehicular P ropulsion 373
T able 1
C ommercially A vailable R echargeable B atteries
Name System Applicatio ns
Lead-Acid (SOA) Pb-H
2
SO
4
-PbO
2
Automotive SLI; tractio n
(specialized vehicles);
emergency power
Nickel-Iro n (SOA) Fe-KOH-NiOOH Tractio n and lighting of trains
(predo minantly in USSR)
Nickel-Cadmium Cd-KOH-NiOOH Small-size po rtable po wer
Silver-Cadmium Cd-KOH-Ag
2
O
2
Aero space applicatio ns requiring
no nmagnetic co mpo nents
Silver-Zinc Zn-KOH-Ag
2
O
2
Military; aero space
sto rage capability. Attempts to pro vide EVs with a range (between
recharges) exceeding that of the SOA (state of art) Pb-A tractio n
batteries has led to co nsiderable impro vements in the techno lo gy
of Pb-A ISOA ("Impro ved" SOA) battery pro to types, "advanced"
Pb-A cells, and Ni-Fe batteries, as well as to the emergence of
several new systems expected to have a mo re acceptable range on
the basis of their higher theo retical specific energies. With the
exceptio n of a few primary batteries (metal fuel cells), the candidate
systems are electrically rechargeable. They can be classified in a
number of ways, e.g., acco rding to the o perating temperature
(ambient o r high), type of electro lyte (aqueo us, o rganic liquid,
mo lten salt, so lid; flo wing o r statio nary), o r their relative stage of
develo pment. The latter classificatio n, so mewhat subjective and
labile, divides the candidate systems into three gro ups: near term,
advanced, and explo rato ry. Very ro ughly, the develo pment of near-
term systems has reached the pro to type EV battery stage; of
advanced systems, the battery pro to type o r mo dule stage; and of
explo rato ry systems, the small-mo dule, or cell stage. The list and
basic characteristics of near-term and advanced batteries is given
in Table 2, alo ng with data pertaining to some explo rato ry systems.
I I . EV B A T T E R Y R E QUI R E M E N T S
Battery characteristics can be described in terms of the desired EV's
performance-, cost-, and safety-related facto rs, as listed in Table 3.
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T able 3
C orrespondence between the Vehicle and EV B attery C haracteristics
EV parameters Battery parameters
1. Performance
Range between recharges
Daily range
Acceleratio n capability
Climbing speed
Reliability
2. Cost
3. Safety and enviro nmental
aspects
Specific energy (Wh kg
l
)
Energy density (Wh liter"
1
)
Self-discharge rate (percent per day)
Charging time (h/C)
Specific peak po wer (Wkg"
1
)
Peak-power density (W liter"
1
)
Specific sustained po wer (Wkg"
1
)
Ruggedness
Insensitivity to ambient co nditio ns, o vercharge,
o verdischarge, sho ck, vibratio n, etc.
Lack of complexity
Materials
Fundamental reso urce limitatio ns
Recycleability
Geo po litical distributio n
Manufacturing, R&D
Cycle life
Overall energy efficiency
Maintenance
Statio nary failure modes
Impact failure modes
Fire and/o r explo sio n hazard
Reactive and/o r to xic material release
Enviro nmental impact
Po llutio n
Mining and pro cessing effects
1. P erformance-R elated R equirements
(i) Range between Recharges
EV range depends primarily o n the amo unt of effective energy
sto red per unit weight or vo lume of the battery. The specific energy
(Wh kg"
1
) of seco ndary batteries delivered to EV wheels is appro xi-
mately 2-5% of that of gaso line. Vo lumetrically, the situatio n is
no t much better, the energy density being within 3-7% of the
gaso line value. This explains the inherent gap in the vehicle range
between "refueling" of battery- and ICE-po wered cars, a gap which
canno t be bridged by simply increasing the battery weight. The
battery fractio n (battery weight/vehicle curb weight) sho uld no t
exceed ~ | to ensure mechanical stability and to avoid the excessive
waste of energy spent on pro pelling the battery itself.
(a) Specific energy
The energy available for driving purpo ses is often so mewhat
lower than the energy deliverable by the battery. The lo sses may
be due, e.g., to the o peratio n of battery auxiliaries (pumps in flo w
batteries, shunt-current pro tectio n, etc.) The translatio n of the avail-
able specific energy into the EV's range must take into acco unt the
vehicle characteristics including its weight, wind and ro lling resist-
ance, and the driving pro file
6
determined by the vehicle's end use
as shown in Fig. 1, based on the average perfo rmance of Pb-A-
po wered vehicles driven in Germany.
7
The trend shown can be
ratio nalized in terms of slower speeds and acceleratio n (energy
lo sses are pro po rtio nal to the square of velo city) of larger German
vehicles driven with vario us driving pro files, depending on their
missio n. Also the drag due to the fro ntal wind resistance do es no t
decrease linearly with decreasing vehicle vo lume. The o rdinate
values can vary co nsiderably from tho se sho wn in Fig. 1. Thus,
I PASSENGER
250 i
CARS
TRUCKS
BUS
170
v.
i
130
VANS
210
i i
I I I n I
2 4 6 ^
T 0 N
20
Figure 1. Specific energy o f vario us types o f EVs.
377
e.g., a 1500-kg co mpact-type EV with ~ | battery fractio n, driven
under urban co nditio ns, as simulated by the U.S. Federal Urban
Driving Schedule,
6
requires only 250 Wh mile"
1
, o r ~ 170 Wh t o n
1
mile"
1
.
8
The trend, ho wever, co rrectly indicates that the most
demanding is a small passenger car. The packaging co nstraints are
co mpo unded by size effects of the battery itself. Scaling do wn
battery capacity results in a lo ss of effective specific energy, which
is relatively small for simple, ambient-temperature systems and
beco mes pro gressively larger with the degree of co mplexity and
number of auxiliary subsystems in flo w- and high-temperature
batteries. As shown in Fig. 2, the specific energy of complex batteries
is severely impaired in the regio n of 20-30 kWh suitable for small
urban cars. The latter require ~60Whkg~
1
to attain a 100-mile
range.
8
This might indicate that, in spite of some mo re o ptimistic
pro jectio ns, only simpler systems may pro ve co mpatible with com-
pact EVs, while mo re co mplex batteries wo uld be mo re suitable
for large family cars, vans, etc.
The effective specific energy of vario us batteries amo unts
presently to some 10-25% of theo retical specific energy (defined
as the reversible work of the cell reactio n per unit weight of reactive
electro de materials). The extent of departure from the theo retical
value depends o n: (1) the weight of no nactive battery co mpo nents;
I I
1
Figure 2. System size effects o n
specific energy.
9
40 80 120
BATTERY CAPACITY, KWH
(2) reactant utilizatio n; (3) discharge o vervo ltage (determined
primarily by o hmic lo sses); (4) co ulo mbic lo sses due to parasitic
reactio ns, self-discharge, and/o r shunt currents in series-co nnected
cells with a common electro lyte; and (4) lo sses co nnected with
o peratio n of auxilaries.
Efforts to impro ve the ratio of effective to theo retical specific
energy invo lve, in general: (1) replacement, where po ssible, of inert
grid, co ntainer, co nnecto r, and current co llecto r materials by light-
weight substances; (2) increase of utilizatio n of active materials by
impro ved cell design and/o r use of special additives; (3) careful
mo deling and o ptimizatio n of current co llectio n; and (4) use of
bipo lar electro des.
Altho ugh the individual mechanism may differ, the specific
energy of batteries decreases, in general, with increasing rate of
discharge. Fo r example, the specific energy of a certain SOA Pb-A
tractio n battery varies between 34 and 22 wHkg"
1
when discharged
within 5 and 1 h, respectively.
1
The capacity C
{
available at the
given discharge current / is often represented for po ro us-plate
simple batteries by the empirical Peukert equatio n:
Cj = KT
n
where K and n are coefficients characteristic for the given battery.
Any co mpariso ns of battery specific energy o r ranges have sense
only if the latter are measured for the same value of C/h, where
C deno tes the rated capacity of the battery and hthe number of
ho urs of discharge.
The EV range is affected by the self-discharge which may o ccur
bo th during rest and o perating perio ds of the battery. The self-
discharge rate depends on the individual battery characteristics,
ranging from zero for batteries with so lid electro lytes (e.g., Na-S)
to co nsiderable values for batteries o perated witho ut separato rs
(e.g., zinc-chlo rine hydrate). In batteries with separato rs, self-
discharge is determined by the rate of io n transpo rt thro ugh the
membrane. The most efficiention-exchange membranesare
usually to o expensive for practical purpo ses and micro po ro us
separato rs are co mmo nly used.
The EV's range can be so mewhat extended by the battery's
capability of accepting charge pulses during regenerative braking.
Depending on the battery and driving pro file, such reco very may
increase the range by so me 15-25%.
10
(b) The volumetric energy density
This defines the packaging requirements for the given EV range.
Fo r simple, ambient-temperature systems, its numerical value is
abo ut do uble the battery's specific energy. This ratio decreases with
increasing vo lume of auxiliaries, and, for smaller cars, vo lumetric
co nsideratio ns may beco me range limiting for rather than the
gravimetric effective energy sto rage capability. This limitatio n may
pertain particularly to bulky batteries which canno t be spatially
distributed in the car being designed as a single package (e.g.,
high-temperature systems envelo ped in a vacuum insulatio n).
Optimal packaging of batteries will require vehicles specially
designed to acco mmo date the given battery.
(11) Daily Range
In general, fast recharge decreases the energy efficiency (unless
the self-discharge rate during charge is co nsiderable, as in the case
of the Zn-Br
2
battery) and may cause severe cell damage owing to
temperature increases which acco mpany high charging currents.
Therefo re, recharging to full capacity requires 6-10 h for most
systems and the range between recharges usually defines the daily
mileage allo wable. Some systems are claimed by their develo pers
to be capable of a 0.5-h recharge to some fractio n (e.g., 50%) of
the rated capacity. If indeed, the high charging rates wo uld no t
affect the battery reliability and cycle life, the daily mileage of EVs
co uld be extended to mo re co nvenient distances. The demands on
the infrastructure of electric utilities wo uld be in this case mo re
severe (altho ugh pro bably no t pro hibitive) than tho se anticipated
for o vernight recharge.
(MI) Acceleration
Specific peak po wer (W kg"
1
) of the battery determines the EV
acceleratio n capability. No t o nly the energy sto rage but also the
po wer/weight ratio co mpariso ns with ICEs are no t favo rable for
380 Halina S. Wroblowa
electro chemical po wer plants. The o bvio us reaso n is the
tridimensio nal character of ho t co mbustio n which o ccurs in the
reacto r's vo lume, as o ppo sed to the two -dimensio nal characteristics
of the interfacial electro chemical energy co nversio n. In spite of the
po o r po wer/weight ratio , acceptable acceleratio n of EVs is mo re
easily attainable than the desirable range.
The specific po wer passes thro ugh a maximum at a vo ltage
co rrespo nding to 50% of the o pen-circuit value (OCV). The
usable peak po wer, ho wever, limited in practice to 85% of the
maximum value, is attainable at vo ltages some 30% lo wer than
OCV. (Higher-vo ltage departures would severely affect the cost of
the present dc mo to rs o r ac co ntro llers.) Available data usually
refer to the maximum po wer. Also , published data often refer to
peak po wer averaged over a 15-s pulse, while actually the value of
peak po wer during the next 5 s is as impo rtant for EV acceleratio n.
In general, the specific peak po wer decreases with the depth
of discharge (DOD) (cf. Fig. 3). Therefo re, EV battery specification
with respect to range and allo wable depth of discharge limit sho uld
pertain to (whichever comes first) DOD values at which EV beco mes
incapable of the demanded acceleratio n, o r to which the system
50
Power kW
40
30
20 40
% DOD
60 80
Figure 3. Specific peak-po wer, averaged over the last 10 s of a 20-s
pulse, as a function of the depth of discharge for Lucas-Chlo ride,
-535 kg, 192-V ISDA tubular Pb-A batteries. EV po wer-train con-
straints impo sed. (Courtesy of Lucas Chlo ride EV Systems, 1984.)
can be safely discharged witho ut impairing its reliability and life-
time (often 80% of the rated capacity is required as a limit).
The EV po wer requirements depend o n the car's end use and
assumed acceleratio n demands. Fo r example, the specificatio ns for
safe driving in a mixed ICEV and EV urban traffic of a small
co mpact-type EV have been defined as acceleratio n from 0 to
50 mph in <20 s.
8
The specific peak-po wer co rrespo nding to these
demands has been calculated as 80-90 wkg"
1
for co nditio ns of
o ptimum use of the AC po wer train (i.e., for co nstant-po wer acceler-
atio n following the initial perio d in which the peak-po wer is attained
at the maximum tractive effo rt
8
). The majo rity of near-term and
advanced batteries co uld, at least po tentially, meet these demands.
The difference between pro jected and actual perfo rmance of
the present pro to types is often very high. Thus, e.g., the po tentially
"best" perfo rmance of the LiAl/FeS battery (Argo nne Natio nal
Labo rato ry) is co mpro mised at present, primarily by the inadequate
current co llectio n which causes substantial po wer lo sses due to the
high internal resistance.
(it;) Specific Energy-Peak power Tradeoffs
The specific energy to peak po wer ratio is a key battery-design
parameter. Since bo th canno t be simultaneo usly increased, the given
system can be designed for maximum range at some loss of peak-
po wer capability, o r for high-po wer o peratio n at some loss of the
achievable range. The sensitivity of the given system to the po wer
demands is sho wn in Rago ne plo ts exemplified
9
in Fig. 4 for
pro jected perfo rmance of a number of battery systems. (It sho uld
be kept in mind that the data in Fig. 4 differ co nsiderably from
tho se presently attainable and are of co mparative rather than
abso lute value). Rago ne plo ts map the specific energy available
from the battery for values of the specific po wer at which the battery
is discharged. The energy/po wer relatio ns determined in labo rato ry
tests have been successfully used to pro ject EV's perfo rmance. An
agreement of 5% has been repo rted for a number of near-term
batteries
10
between the pro jectio ns based o n Rago ne plo ts o btained
for small (6-12 V) mo dules at the Argo nne Natio nal Labo rato ry
and vehicle ranges o btainable under co nditio ns of urban driving
cycle as tested at the Jet Pro pulsio n Labo rato ry.
100
a:
hi
I
CO
50
Pb/acid
0 50 100 150
SPECIFIC ENERGY, Wh/kg
Figure 4. Ragone plo ts. Characteristics expected for 1990s. Specific power data
for 80% DO D.
9
It wo uld seem that battery-battery hybrids might pro vide better
simultaneo us o ptimizatio n of range and acceleratio n. Ho wever, the
o verall specific-energy and efficiency lo sses, co st, and co mplexity
of the hybrid systems seem to militate, at present, against this
so lutio n.
(v) Reliability
The pro bability that a battery will functio n pro perly under
vario us kinds of driving and enviro nmental co nditio ns determines
its reliability. The latter is an extremely impo rtant parameter which
may adversely affect public acceptance of electric cars to an even
greater extent than their limited range. At present, little is known
abo ut the reliability of full systems o ther than a number of lead/acid
tractio n batteries which are highly reliable. (Thus, e.g., batteries
for delivery vans pro duced by Lucas Chlo ride EV Systems are
presently so ld in England with a two -year unco nditio nal and two -
year co nditio nal warranty. ) Data for o ther batteries are largely
absent since very few have been sufficiently tested even at the
mo dule o r cell level and hardly any info rmatio n exists co ncerning
effects of actual driving co nditio ns.
B atteries fo r Vehicular Pro pulsio n 383
Reliability pro jectio ns are often based o n the pro bablity theo ry
which relates the reliability of the battery with that of the single cell:
where P
B
F and P
CF
are the pro babilities of battery and cell failure,
respectively; n is the number of cells; and 1 - P
CF
=
e
^
c
/
MCBF
\
where MCBF is the mean number of cycles befo re cell failure. This
appro ach assumes that a multico mpo nent system do es no t intro duce
additio nal failure pro bability due to the interco nnectio n of cells
and the influence of their electro chemical behavio r on neighbo ring
elements. Physically this assumptio n co rrespo nds to a situatio n in
which each cell is separately mo nito red and prevented from over-
charge, undercharge, o r o verdischarge abuse. It is no t clear, at
present, whether this type of co ntro l wo uld be eco no mically viable.
In additio n, the presence of auxiliaries may adversely affect
the full system's reliability. Simple, ambient-temperature batteries
may require little mo re than some thermal management in the form
of free o r forced co nvective air co o ling and some insulatio n. Other
systems may involve mo re extensive thermal management and/o r
a flowing electro lyte subsystem(s), e.g., the Westingho use Ni-Fe
battery
12
(cf. Section III, Fig. 8) o r the Exxo n Zn-Br
2
battery
13
(cf.
Sectio n III, Fig. 11); vacuum insulatio n for high-temperature
batteries;
14
o peratio n of a co mplex chemical plant relying on inter-
nal feedback co ntro ls of flow rates and the refrigeratio n subsystem
the EDA zinc-chlo rine hydrate battery
15
shown in Figure 10 (Sec-
tio n III); o r o peratio n of an even mo re co mplex, Lawrence Liver-
mo re Labo rato ry primary aluminum-air battery with five subsys-
tems (cf. Sectio n III, Fig. 14).
Facto rs affecting the reliability of cells are discussed in Sectio n
II. 2(ii)(a) to gether with the cycle life, since bo th parameters are
closely interrelated.
Statistically meaningful data require pro lo nged cycling of large
numbers of (co nnected) cells. It sho uld be kept in mind that EV
techno lo gy is at a very immature stage, perhaps co mparable to that
of the internal co mbustio n engine at the beginning of the century.
Attempts are being made to help design appro priate testing metho ds
and achieve high reliability by intro ducing pro per switching
metho ds and sufficient redundancy.
16
2. C ost-R elated R equirements
Data co ncerning battery cost have to be treated with co nsiderable
cautio n. The uncertainty is bo th objective (changing co mmo dity
and labo r co sts; unkno wn price of undevelo ped co mpo nents, mass
pro ductio n, recycling, etc.) and subjective (the enthusiasm of bat-
tery develo pers).
Some of the values pro jected for mass pro ductio n are repo rted
in Sectio n IV (cf. Table 6). Most of them are close to $100 per
kilo watt-ho ur, po ssibly because of the develo pment targets set by
R&D funding institutio ns. Some zinc-based batteries are pro jected
as least expensive
131517
when fully develo ped. It seems unlikely
that the pro jected costs of nickel-co ntaining systems will be met in
the fo reseeable future, altho ugh in the case of Ni-Fe the high initial
cost may be co mpensated by low cost per mile due to the anticipated
lo ng cycle life and high reliability of the battery. At present, it
appears that o nly the impro ved Pb-A battery may be available at
a cost less than $100 per kilo watt-ho ur within the 1980s.
(i) Initial Cost
Battery price is calculated on the basis of the material and
manufacturing co sts. The cost of the active materials is directly
related to their availability. With the exceptio n of Na-S, Fe-air,
and a few o ther explo rato ry systems, all EV battery candidates are
based o n materials whch are either no t to o abundant wo rldwide,
reside in diluted o res, o r can be extracted viably only from o res
lo cated geo graphically in a few areas. The impo rts may be subject
to po litically induced sho rtages o r sto ppages, in analo gy to the
gaso line situatio n. In some cases, even the do mestic reso urce utiliz-
atio n may beco me pro hibitive because of the enviro nmental impact.
Material availability co uld beco me a serio us pro blem if o ne
thinks in terms of to tal co nversio n to electric cars. On the o ther
hand, a 10% incremental demand on the reserves co uld suppo rt
the pro ductio n of 10
5
-10
7
batteries per year of each kind listed
in Table 4.
18
The po tential availability pro blem might be substantially
relieved if battery materials co uld be efficiently reco vered. The
develo pment of cheap recycling metho ds is of primary impo rtance
T able 4
P reliminary S upply C onstraint of B attery M aterials
385
Battery
type
Pb-A
Ni-Zn
LiAl-FeS
Zn-Cl
Material
Lead
Antimo ny
Nickel
Zinc
Co balt
Lithium
Aluminum
Zinc
Titanium
Chlo rine
Battery
requirements
(kgkW-
1
)
22
1.6
3.29
1.28
0.055
0.25
1.0
0.74
0.39
0.80
Yearly
use level
(to ns x 10~
3
)
1400
40. 3
211
1500
8.5
3.4
6175
1500
585
7640
Battery
capacity
at 10% o f
use level
(kWh x 10~
7
)
0.64
0.025
0.64
11.7
1.54
0.11
61. 7
13.5
15
95. 5
Number o f
batteries
per year
(io-
5
)
3
3
40
700
(e.g., the present co st of recycling lead co nsiderably co ntributes to
the cost of co mmercial lead-acid batteries). The pro jected battery
co sts usually assume such metho ds to have been develo ped.
() Cost per Mile
The mo st impo rtant facto r affecting this cost is the battery
cycle life; o perating co sts determined by the energy efficiency of
the battery and range lo sses due to self-discharge will beco me
pro gressively impo rtant with the future increase of energy co st.
Maintenance co sts vary from relatively insignificant in batteries
requiring o nly water additio n (simple near-term systems) to so me-
what higher values in mo re co mplex batteries.
(a) Cycle life
Cycle life of sufficient duratio n, co mbined with acceptable
specific energy, is the most elusive of the desirable battery attributes.
Facto rs respo nsible for cycle life and reliability of a single cell vary
in different systems; they are co nnected with the mechanical, struc-
tural, and/o r chemical changes accumulating in electro des o r o ther
cell co mpo nents upo n cycling. These changes can often be
attributed to electro de reactio n mechanisms involving phase
changes: redepo sitio n of the so lid phase from a disso lved discharge
pro duct and/o r vo lumetric expansio n/co ntractio n cycles between
charged and discharged so lid phases. Surface passivatio n of the
active material o r deco mpo sitio n of the (o rganic) electro lyte may
also may beco me beco me a life-limiting facto r. Cells with inert
electro des and gaseo us o r liquid reactants (e.g., zinc-halo gen) are
less subject to limitatio ns co nnected with reactant deterio ratio n.
Their cycle life may, ho wever, be sho rtened by electro chemical
pro cesses (e.g., co rro sio n o r o xidatio n) which deterio rate inert cell
co mpo nents o r lead to pro ducts which affect the no rmal cell
o peratio n, e.g., as with some Na-S systems.
Depending on the system, cells may be sensitive to damage by
o vercharge, frequent undercharge, o verdischarge, extremes of tem-
perature, thermal cycling, and/o r mechanical effects of driving
co nditio ns, such as change of po sitio n, vibratio n, and/o r sho ck.
Among near-term and advanced systems, the lo ngest cycle life
is expected for Ni-Fe systems (sintered iro n electro des have been
repo rted to be capable of ~3000 deep discharge cycles); a very
sho rt lifetime (at most ~300 cycles achieved befo re 20% loss of
rated capacity) is characteristic of simple alkaline Ni-Zn cells.
Other near-term and advanced systems have demo nstrated battery,
mo dule, o r cell cycle life of 400-1000 cycles. Further impro vements
and reliable transfer of the cycle life achieved in mo dules into full
batteries depend, in general, on the feasibility and rate of technical
and engineering pro gress, rather than on scientific breakthro ughs
as is the case of the simple alkaline Ni-Zn system.
As it has been previo usly mentio ned, statistical pro jectio ns
based o n single-cell tests are no t sufficient for evaluatio n of a
battery's cycle life and reliability, since a multico mpo nent system
has additio nal pro blems co nnected with the effects exerted by each
cell on its neighbo rs. These effects are due to the no nideally unifo rm
electro chemical behavio r of battery cells. Small differences in charge
o r discharge rates of individual cells may accumulate in cycling,
leading to vario us degrees of o vercharge and o verdischarge (includ-
ing cell reversal) which may result in irreversible cell o r even battery
damage. The latter can also be caused by co rro sio n due to single-
cell(s) leakage. In general, suitable precautio ns are needed to
minimize spreading damage due to the malfunctio n of a single cell.
387
Attempts to increase the specific energy usually co mpro mise
the battery cycle life as exemplified in Fig. 5 for Pb-A batteries.
11
The cycle life is also affected by the depth of discharge. Voss and
Huster
19
suggested an empirical equatio n
lo gN = -kD/100+d
where N is the number of cycles, D is the depth of discharge, and
k and d are coefficients characterizing the given battery. It is
assumed here that the battery lo ses a certain percentage of its
capacity in each cycle. The equatio n has been fo und valid for a
number of batteries, such as Pb-A (cf. Fig. 6), Ni-Cd, Ni-Zn,
Ag-Zn,
20
and pro bably Zn-Br
2
, altho ugh the failure mechanism in
the latter case is different than in the case of po ro us plate batteries
and the cycle life of Zn-halo gen batteries is much less susceptible
to DOD.
These examples illustrate the tremendo us techno lo gical chal-
lenge invo lved in the simultaneo us o ptimizatio n of several attributes
required for a viable EV battery.
80
^ 7 0
i
6 0
LJ
Z
U
o 50
o
40
30
MULTILAYER ELECTRODE TYPE
>POROUS SHEET
k
ELECTRODE TYPE
' THIN MULTILAYER
CELL TYPE
EV4P?
EV2P
EV3P
J_
EV5P
I
50 100 200 500
CYCLE LIFE
1000 2000
Figure 5. Specific energy vs. cycle life o f lead/ acid
batteries.
11
388
600
500
400
UJ
300
200
100
i I 1 r
PASTE TYPE BATTE RY
CLAD TYPE BATTE RY
FO R TRAI NS **
Halina S . W roblowa
6000
J_ 1 I
5000
4000
3000
2000
1000
20 40 60 80
DEPTH OFDISCHARGE, %
Figure 6. Cycle life of lead/acid batteries as a function of
DOD.
1
(b) Energy efficiency
Energy efficiency of batteries is mainly co nnected with the
electric input to o utput ratio , because the initial energy input
required in manufacturing is a relatively small fractio n of the to tal
energy co nsumed during a battery's life.
21
The main co mpo nent of vo ltaic inefficiency is usually the o hmic
lo ss, co mpo unded by mass-transpo rt-related o vervo ltage. The
extent of co ulo mbic lo sses depends on the system and may be due
to parasitic electro de and/o r chemical reactio ns, self-discharge,
and/o r shunt currents (in flo wing systems wth a common elec-
tro lyte). The efficiency, as measured at battery terminals differs
from the effective value if a part of the battery's energy is used to
o perate auxiliaries (e.g., pumps) or if thermal losses are involved
(high-temperature batteries).
Except for zinc-halo gen co mplex and metal-air systems, trac-
tio n battery pro to types have been shown to o perate at 60-75%
efficiency (cf. Table 6). Higher values, usually quo ted for high-
temperature batteries (Na-S, LiAl-FeS) do no t take into acco unt
thermal lo sses, which, amo ng o ther facto rs, depend on the type of
insulatio n, assumed EV driving cycle, and mileage per year.
3. S afety and E nvironmental Impact
(i) Use of Batteries in EVs
Hazards co nnected with the failure (statio nary o r o n impact)
of the Pb-A and Ni-Zn batteries are co mparatively small and safety
precautio ns may be limited to explo sio n-arrest devices. In Ni-Fe
cells, catalytic reacto rs are installed to prevent hydro gen fires.
To xic substances (stilbine and arsine from Pb-A batteries),
which may be released during charging as well as, surprisingly,
during discharge, seem to require no mo re than ventilatio n of the
garage and of the battery co mpartment.
22
A po ssible destructio n upo n impact of zinc-halo gen batteries
might lead to the release of chlo rine gas o r bro mine liquid and
vapo r. A study
23
of the effects of spilling a full lo ad of chlo rine
hydrate o n ho t co ncrete co ncluded that the pro bability of lethal
accidents appears to be no mo re serio us than that caused by gaso line
fires in ICE-po wered cars. The bro mine vapo r pressure abo ve the
o rganic co mplex is lo wer than that of chlo rine abo ve chlo rine
hydrate; its lethal do se, ho wever, is smaller and the spill cleanup
and dispersio n pro blems may be mo re severe.
Among high-temperature batteries, the lithium-iro n sulfide
systems are reaso nably safe, altho ugh there are some hazards co n-
nected with the 450-500C o perating temperature. The so dium-
sulfur-system impact failure hazards are primarily co nnected with
the po ssibility of SO
2
emissio ns, so dium o xide dust, and fires
resulting from so dium expo sure to mo isture.
(ii) Environmental and Health Considerations
Urban po llutio n has been sho wn by Japanese,
24
Australian,
and U.S. researchers to be primarily due to car exhaust emissio ns.
The U.S. Enviro nment Pro tectio n Agency (EPA) repo rts transpo rta-
tio n in the USA to be respo nsible for -42% of to tal emissio ns, the
car being the largest single po lluter. Co rrespo ndingly, cars in the
USA must co nfo rm to the increasingly restrictive federal exhaust
emissio n standards. Transitio n to EVs supplied by oil-fired po wer
statio ns wo uld co nsiderably lower the level of hydro carbo ns and
nitro gen o xides (even in co mpariso n to the present EPA-allo wed
levels) and almo st eliminate carbo n mo no xide emissio ns
2
as shown
in Table 5. Mo re realistically, ho wever, this transitio n may be
expected to o ccur when co al will be the primary energy so urce.
With the exceptio n of CO, the emissio n levels from coal-fired po wer
statio ns
25
(calculated in g per EV mile) are no t superio r to tho se
allo wed by the EPA (cf. Table 5). The questio n arises whether the
po llutio n pro blem is then no t simply transferred from the car po wer
plants to the central po wer facilities. Central, large-scale co al com-
bustio n seems to alleviate the pro blem since the po llutants are well
dispersed abo ve gro und level being released from tall stacks
(~200m) lo cated away from urban areas. Also , the large-scale
central co mbustio n pro cess appears to be better suited eco no mically
for the installment of so phisticated po llutant remo val, particularly
of SO
2
than the distributed small IC engines of mo bile vehicles
po wered by co al-derived fuels.
2
'
4
No t only air but no ise po llutio n
wo uld also be decreased by use of EVs in urban enviro nments.
Enviro nmental and health hazards co nnected with mining and
milling of raw materials, battery manufacture and recycling have
been studied for near-term (lead/acid, nickel-iro n, nickel-zinc)
26
and zinc-halo gen
27
batteries. Significant increases in pro cessing
lead co uld result in an increased pro bability for lo cal (~50-km
radius) develo pment of the central-nervo us-system respo nse as well
as of renal pro teinuria due to increased cadmium emissio ns.
Increased levels of mining highly dilute o res might eventually bring
T able 5
P ollutant L evels
Po llutant
Hydro carbo ns
CO
EPA standard
(gmile"
1
)
0. 41
3.4
1.0
Emissio ns fro m po wer
statio n (g per EV mile)
Oil fired
2
Co al fired
25
0. 03 0.40
0.48 1.48
Negligible
abo ut some pejo rative eco system effects, which are o therwise co n-
sidered insignificant.
I I I . C H A R A C T E R I S T I C S O F I N DI VI DUA L S Y S T E M S
1. T he L ead/A cid B attery
The develo pment of the lead/acid battery has been steadily pro -
gressing since 1860 when Plante
28
co nstructed the first practical
device based on the co ncept of Siemens and Sisteden (1850). The
extensio n of the present tractio n-battery applicatio ns to passenger
vehicles requires primarily a substantial increase of specific energy
and peak po wer witho ut co mpro mising cycle-life-related battery
characteristics. At present, co mmercially available tractio n batteries
for fo rklift-type applicatio ns can pro vide some 2000 cycles and
20-22 Wh kg"
1
at the C/6 rate; the higher specific energy of golf-
cart batteries (-27 Wh kg"
1
at the C/3 rate) has been achieved at
the expense of battery life (400 cycles). Modified batteries for
delivery vans and similar uses which do no t require specific peak-
po wer levels expected of passenger cars have attained up to
30 Whkg"
1
and 800-1000 cycles.
29
'
30
The electro chemistry of the Pb-A cell can be represented by
PbO
2
+ H
2
SO
4
+ 2H
+
+ 2e - z PbSO
4
+ 2H
2
O
Pb + H
2
SO
4
^ PbSO
4
+ 2H
+
+ 2e -
PbO
2
+ Pb + 2H
2
SO
4
; 2PbSO
4
+ 2H
2
O
Altho ugh water deco mpo sitio n and elemental-lead co rro sio n
reactio ns are stro ngly inhibited by the low hydro gen exchange
current o n lead, o vercharge witho ut pro per co ntro ls may result in
severe damage due to the excessive gassing (see belo w).
The theo retical specific energy of the Pb-A battery varies
so mewhat with acid co ncentratio n and amo unts to 77 Wh kg"
1
for tractio n batteries which utilize mo re co ncentrated so lutio ns
(d
25
o
C
= 1.28 gem"
3
). In the limits (an ideal system o perating
witho ut o vervo ltages at 100% reactant utilizatio n, and co ntaining
no inactive materials except for the necessary dilutio n water and
~30% excess acid) the specific energy wo uld be almo st halved to
-~96 Whkg"
1
. The specific energy achieved in ISOA mo dules is
35-40 Wh kg"
1
at the C/3 rate.
30
"
32
Efforts which have resulted in
this impro vement and aim at achievement in advanced systems of
50 Whkg"
1
witho ut co mpro mising the specific po wer and cycle
life
33
have been centered aro und the fo llo wing:
1. A decrease of weight of inactive materials used for casing,
grids, co nnecto rs, terminals, and separato rs, e.g., by use of carbo n
fibers, plastics o r plastic-lead-allo y materials, lead-co ated
aluminum po sitive grids, and/o r aluminum terminals and con-
necto rs. Attempts to build batteries with bipo lar electro des have
resulted, until no w, in highly impro ved po wer (but no t energy
sto rage) characteristics at the penalty of a drastically sho rtened
cycle life due to severe sealing pro blems.
34
The co ncept is still being
pursued, amo ng o thers, in the form of a lead-bo ro n tetrafluo ride
system,
35
and a new "quasi-bipo lar" design, involving a co ntinuo us
plastic-co mpo site co nductive sheet (envelo ping co nnective cells)
which can be thermally sealed.
36
2. Increased utilizatio n of so lid reactants. Even at rates lower
than tho se required in EV o peratio n, <40% of the so lid reactant
mass is utilized. The po o r utilizatio n of PbO
2
has been blamed on
the vo lume change of the reactant between charge and discharge,
changes in its micro structure, appearance of an inactive PbO
2
form,
and/ o r blo cking of the po res by the discharge pro duct. With
increasing depth of discharge, the growth of PbSO
4
layers impedes
the mass transfer of HSO4 io ns. Simultaneo usly, the latter beco me
depleted, and water is generated at the interface affecting the
reactio n kinetics and o hmic resistance. Impro vements in reactant
utilizatio n are attempted, amo ng o thers, by o ptimizing the PbO
2
micro structure,
37
electro lyte agitatio n, o r circulatio n, and/o r by
decreasing the electro de thickness
38
witho ut affecting its mechanical
strength. (The po sitive electro de must co mbine the ability to with-
stand stresses intro duced by vo lumetric changes of the reacting
so lid phases during cycling with sufficient po ro sity to maximize the
interfacial co ntact with sulfuric acid.)
The EV range is o bvio usly affected by the level of self-
discharge. The latter is mainly due to the reductio n of PbO
2
by
lead of the grid and to the fo rmatio n of ano dic o xidatio n pro ducts
(e.g., of Sb) which diffuse to the negative plate. Their depo sitio n
decreases the hydro gen o verpo tential and results in co rro sio n of
the Pb spo nge at OCV and o n charge. This pro cess may decrease
the rated capacity by some 20-30% per mo nth.
The specific po wer of the Pb-A battery stro ngly depends on
the depth of discharge
39
owing to the previo usly mentio ned mass
transfer, kinetic, and o hmic effects. As o ppo sed to the inherently
limited range, the acceleratio n (po wer) capability of the ISOA
pro to types, is close to values required for a small passenger car
even at 80% DOD. Apart from the weight decrease, further impro ve-
ments aim at a decrease of internal resistance by use of better
separato r materials
40
and better current co llectio n at bo th flat
41
and
tubular
42
electro des. Analysis of current distributio n and co mputer-
assisted mo deling techniques have resulted in new grid structures
and designs which have already co nsiderably reduced the battery
weight and internal resistance, and have po tential for further
impro vements. Up to no w, the highest specific peak-po wer values
(440 and 220 W kg"
134
) have been repo rted for the previo usly
mentio ned sho rt-lived bipo lar batteries designed for low specific
energies. Co mbinatio n of high specific po wer with high
(SOWhkg"
1
) specific energy might co nceivably be achieved in
the future for bipo lar systems. At present, these characteristics are
co mputer pro jected for the Jet Pro pulsio n Labo rato ry's
"quasi-bipo lar" cells at a very early stage of labo rato ry
develo pment.
36
The battery cycle life is generally limited by the behavio r of
the po sitive electro des. The latter have a tubular o r flat design. The
mo re expensive tubular po sitives seem to pro vide lo nger life but
lo wer specific energy than flat electro des. Ho wever, the superio rity
or either versio n for EV applicatio ns is at present difficult to assess.
43
The life limitatio n is related to shedding of PbO
2
and its inactiva-
tio n.
44
"
48
Both pheno mena are ascribed to the changes of vo lume,
structure, and mo rpho lo gy of the po sitive electro de material which
accumulate during cycling.
Altho ugh several hypo theses have been pro po sed, the mechan-
isms of electro de degradatio n invo lved in shedding and inactivatio n
pro cesses are still no t clear. The metho d of material preparatio n
plays a substantial ro le here. Fo r example, po sitive material pre-
pared by o xidatio n of needle like crystals of tetrabasic lead sulfate
(4PbO PbSOJ maintains the latter's mo rpho lo gy and the elec-
tro de's superio r perfo rmance during cycling of statio nary cells.
49
394 H alina S . W roblona
The material has no t been used in tractio n batteries, presumably
owing to its manufacturing co st. The o riginal structure of the active
material (and retardatio n of the appearance of the deleterio us
co rallo id structure
44
) is also repo rted to be retained lo nger in gelled
electro lyte
47
used in sealed, maintenance-free batteries. Differences
in the electro chemical behavio r of a- and /3-PbO
2
have been often
blamed as a po ssible cause of inactivatio n, but see References 37
and 48. Stress and particle subdivisio n due to the disso lutio n-
precipitatio n mechanism of cyclic PbO
2
-PbSO
4
reactio ns and
acco mpanying vo lumetric changes are tho ught to cause electro de
disintegratio n, at least in antimo nial cells.
38
Severe gassing during o vercharge co nsiderably accelerates
shedding.
The "return to fundamentals" in the recently extended struc-
tural studies may help in better understanding of the po sitive
electro de pro cesses and in develo ping necessary manufacturing and
o peratio nal impro vements.
Ano ther major failure mo de is due to co rro sio n of the po sitive
grid. The fo rmatio n of co rro sio n layers at the grid-paste interface
depends o n the allo y used and determines the extent of the electro de
damage. Antimo ny, used in the lead allo y to impro ve mechanical
strength and castability,
29
is now often partly o r co mpletely
replaced
50
by o ther allo ying metal additives, primarily Ca o r Ca
and Sn. The co rro dibility and self-discharge rate is thus decreased,
and the po ssibility of to xic stilbine emissio ns during cycling is
avo ided.
The desired cycle life of Pb-A batteries depends o n their end
use. In statio nary applicatio ns, under co nditio ns of low dis-
charge/charge rates and shallo w depths of discharge, up to 4000
cycles have been achieved. The go al assumed to be sufficient for
eco no mically viable EV applicatio ns is 1000 cycles at a specific
energy of ~40Whkg~\ This is difficult to attain since the cycle
life is adversely affected by several facto rs, such as:
1. High depth of discharge (cf. Fig. 6). The effect has been
ascribed, amo ng o thers, to the develo pment of a co rallo id
structure.
44
2. Increase of specific energy (cf. Fig. 5) achieved, e.g., by
use of thinner plates o r increased po ro sity of reactants which leads,
in turn, to enhanced grid co rro sio n and faster shedding of PbO
2
.
3. Gassing due to o vercharge which sho uld be limited to the
necessary minimum (10% of rated capacity
10
'
38
Overcharge,
o therwise beneficial in preventing, by gassing, stratificatio n of the
electro lyte (water generated during discharge rises to the surface,
while sulfuric acid pro duced during charge co ncentrates at the
bo tto m) accelerates grid co rro sio n and shedding. Electro lyte agita-
tio n and/o r circulatio n has been attempted
42
'
51
as a means of
preventing stratificatio n and acid depletio n. Co nsequently, co ndi-
tio ns are impro ved for high discharge rates, deep discharge, and
reactant utilizatio n. Varta batteries with flo w-thro ugh po ro us elec-
tro des ("elo flux principle") are repo rted to impro ve reactant utiliz-
atio n in the middle range of current densities.
7
Effects o n cycle life,
ho wever, are as yet unclear. A substantial impro vement in the
reductio n of the o vercharge from 20 to 40% to some 5% has been
repo rted by the Glo be Battery Divisio n of Jo hnso n Co ntro ls due
AIR PULSE IN
ACID LEVEL K
ACID LEVEL 2-
nfi
-ACID OUT
-ACID IN
Figure 7. Pulse pump structure: Globe Battery
Division, flat Pb-A cell. (Co urtesy of Glo be Battery
Division, Jo hnso n Co ntro ls, Mr. D. Thuerk, 1984.)
to inco rpo ratio n of a light circulatio n system, it co nsists of po lypro -
pylene insert pumps in each cell
38
'
51
(cf. Fig. 7). Apart from the
extensio n of the cycle life, electro lyte circulatio n is repo rted to have
impro ved the energy efficiency (>80%), specific energy, and po wer,
to have facilitated the thermal management
52
and minimized the
water lo ss. Grid co rro sio n, o ne of the major failure mo des of the
po sitive electro de, has been inhibited, since the decrease of over-
charge allo ws the establishment of charging o vervo ltage based on
the grid allo y co mpo sitio n.
4. Operating temperature, which seems to be at o ptimum at
30-44C.
10
'
53
The severe loss of cycle life and capacity of the Pb-A
battery, particularly at low temperature may require, depending on
the driving pro file,
54
some degree of thermal management in terms
of forced co nvectio n (air co o ling), as well as a light insulatio n to
inhibit heat lo ss during pro lo nged shuto uts.
Owing to the scarcity of data co rrelating the battery perfo rm-
ance with the cycle life under co nditio ns of the EV's driving profiles
(which invo lve, amo ng o thers, high rate pulses during acceleratio n
and regenerative braking, cho pping vo ltage into rectangular high-
frequency pulses by so lid-state switches in vehicles with co ntinuo us
speed co ntro l, and frequent sto ps in urban traffic), the effects of
o ptimizing bo th specific energy and cycle life under EV driving
co nditio ns are presently difficult to assess.
Safety precautio ns may involve intro ductio n of simple
explo sio n-arrest devices integrated with the watering system.
In spite of its inherently low sto rage capability, the lead-acid
battery seems to be a realistic EV-po wer-plant candidate owing
primarily to the manufacturing and recycling experience, relatively
low co st, lo ng cycle life, and reliability. Impro vements in the tech-
nology due to the EV effort have already been inco rpo rated in
co mmercial tractio n batteries and are envisaged for intro ductio n
in SLI (auto mo tive starting) batteries.
55
2. T he N ickel-I ron B attery
The Ni-Fe system develo ped by Ediso n
56
in 1901 was the pre-
do minant co mmercial seco ndary battery till the early 1920s. Past
applicatio ns have been to railcar lighting, mine lamps, mine vehi-
cles, lift trucks, etc.
The electro chemical reactio ns (limited in the battery to a two -
electro n redo x pro cess o n iro n) can be represented by
2 NiOOH
(s)
+ 2H
2
O + 2e ^ 2Ni(OH)
2(s)
+ 2OH"
Fe + 2OH - ^ Fe(OH)
2
+ 2e
2 NiOOH + 2H
2
O + Fe ^ 2Ni(OH)
2
+ Fe(OH)
2
The relatively high exchange current of hydro gen o n iro n
(lo wered so mewhat by amalgamatio n already by Ediso n) results in
co nsiderable gassing during charge and in co rro sio n of iro n which
sho rtens the battery shelf life by self-discharge pro cesses such as
Fe + H
2
O ^ FE(OH)
2
+ H
2
3NiOOH ^ Ni
3
O
4
+ 1.5H
2
O + 0.25O
2
The capacity loss due to self-discharge is co nsiderable. It can
amo unt, in a fully charged battery, to ~2% during the first 20 min
of o pen-circuit standtime and exceeds 5%, after 4h.
10
As o ppo sed to the po sitive electro de, the redo x pro cess at iro n
do es no t pro ceed in the so lid phase but via a disso lutio n-precipita-
tio n mechanism
57
simplified belo w to
Fe + 3OH~ ^ HFeOJ + H
2
O + 2e
HFeO
2
+ H
2
O ^ Fe(OH)
2
+ OH"
Fe + 2OH~ ^ Fe(OH)
2
+ 2e
In spite of their low so lubility (~5 x 10~
5
M litre), HFeO
2
io ns
diffuse to the po sitive electro de and are o xidized to so lid FeOOH
20
causing further disso lutio n of iro n and its co ntino us transfer to the
po sitive electro de. The pro cess is irreversible, the po tential of the
nickel electro de being to o po sitive, even during discharge, for the
reductio n of trivalent iro n. Further decrease of capacity is caused
by the lo wering of oxygen o verpo tential o n the nickel o xide in the
presence of FeOOH. The self-discharge and iro n transfer pro cesses
are so mewhat inhibited by additives
58
to the electro de (sulfur) o r
electro lyte (e.g., lithium and sulfide io ns, o r hydrazine sulfate).
The theo retical specific energy of the battery is 267 Wh kg"
1
;
the effective values previo usly achieved in co mmercial applicatio ns
did no t exceed some 25Whkg~\ In spite of the limited energy
sto rage and po wer capability, the battery is under develo pment in
the USA,
59
'
60
Sweden,
61
Germany,
62
Japan,
63
and the USSR.
62
The
impro vements aim primarily at better utilizatio n of active materials
and weight decrease of inactive battery co mpo nents. The po sitive
electro de is life limiting owing primarily to vo lume difference
between charged and discharged phases (~20%).
64
Therefo re, a
sufficient mechanical stability of inactive suppo rts must be
maintained. Several new designs and materials have been utilized
in battery pro to types including, among o thers, nickel o r nickel-
co ated carbo naceo us fibers and clo ths of high po ro sity; nickel
hydro xide-graphite mixtures pressed into nickel wire screens;
sintered structures; and specially prepared reactant po wders (for
bo th electro des).
The management of water, heat, and evolved gases requires
battery designs which allow for easy replacement of water evapo r-
ated o r deco mpo sed during charge and rest perio ds, sufficient heat
exchange, and preventio n of explo sio n due to accumulating hydro -
gen and oxygen gases. Designs involving a single watering po int
and flame arresto r o r an auxiliary electro lyte circulating system are
under develo pment at Eagle-Picher Industries Inc.
65
and Westing-
ho use Electric Co rpo ratio n,
66
respectively. In the latter design,
co o led electro lyte is flo wed into the battery from a reservo ir (cf.
Fig. 8) which may be placed off-board o r o n-bo ard at some penalty
of decreased specific energy and po wer.
GAS
BATTE RY
SE PARATION GAS
CHAMBE R
BUBBLE R
PRESSURE
GAUGE
| _
FLOW METER CONTROL
Figure 8. Schematic o f the Westingho use nickel-iro n circulating battery.
66
The Ni-Fe battery rapidly lo ses its capacity and peaking-po wer
capability with decreasing temperature. Impro vements in this area
have been significant, particularly in batteries using sintered iro n
electro des
67
develo ped by the Swedish Natio nal Develo pment Com-
pany and Eagle-Picher Industries Inc.
68
They are repo rted to per-
form satisfacto rily do wn to some -20C.
61
The impro vements, aimed at a >60-Whkg~
1
system, have to
date resulted in EV battery pro to types with specific energies close
to SOWhkg"
1
at C/3. Their dynamo meter tested range is, at
best, some 20% higher than that of the Pb-A EV pro to types.
10
The specific peak po wer of the battery stro ngly depends on
the depth of discharge; nevertheless, acceptable acceleratio n seems
to be achievable even at 80% DOD (cf. Fig. 3).
The system is expensive owing to the high price of nickel and
low o perating vo ltage (1-1. 2 V) which necessitates a larger number
of cells in this battery than in mo st o ther systems. The high initial
cost can, to some extent, be offset by the pro jected lo ng cycle life.
Altho ugh the extensio n of the EV range over the Pb-A is marginal,
the pro ven ruggedness, expected reliability, and lo ng life of the
Ni-Fe system (~900 cycles have been achieved for a van battery
cycled with a simulated driving profile witho ut capacity lo ss
10
) has
made it attractive to EV battery develo pers.
3. Zinc B atteries
() The Nickel-Zinc Battery
The co ncept of a rechargeable Ni-Zn battery was first patented
by de Michalo wski in 1899 and the first railro ad battery was co n-
structed in the early 1920s by J. J. Drumm.
69
Because of its sho rt
cycle life, limited by dendritic gro wth and shape change of the zinc
electro de, little work was do ne on the system until the last few
decades when it was realized that the energy sto rage and po wer
capabilities, co upled with ambient-temperature o peratio n, make
the system most desirable for mo bile applicatio ns. The theo retical
specific energy of the battery is ~320Whkg~
1
. Extensive R&D
effort carried o ut in several co untries
4
'
70
resulted in a number of
EV battery pro to types with specific energies reaching > 100 Wh kg"
1
and specific peak po wer exceeding HOW kg"
1
. The cycle life,
ho wever, of these batteries was pro hibitively sho rt. Attempts to
impro ve the cycle life resulted in a co nsiderable decrease of specific
energy and po wer witho ut sufficient life extensio n
71
to co mpensate
for the high initial co st, due primarily to the high cost of nickel.
The lo ngest life (300 cycles) repo rted by General Mo to rs
72
appears
to be insufficient to make the system eco no mically viable.
The electro de and cell reactio ns can be represented by
2NiOOH
(s)
+ 2H
2
O + 2e z 2Ni(OH)
2(s)
+ 2OH~
Zn + 2OH~ ; ZnO
(s)
+ H
2
O + 2e
ZnO
(s)
+ H
2
O + 2K0H ^ K
2
Zn(OH)
4
2Ni00H + Zn + 2H
2
O + 2KOH ^ 2Ni(OH)
2
+ K
2
Zn(OH)
4
The key technical pro blem of the battery causing its loss of
capacity with cycling is the shape change and densificatio n of the
zinc electro de.
73
(Dendritic gro wth of zinc during charge, which
was the o riginal failure mo de of the battery by sho rt circuiting, has
been largely overcome in alkaline so lutio ns by use of suitable
separato rs and pro grammed charging mo des, and by limiting the
cell capacity by the po sitive electro de.) Both pheno mena are ulti-
mately co nnected with the high so lubility of zinc o xide (cf. the
ano dic reactio n) which results in mo rpho lo gical changes (densifica-
tio n) and/o r redistributio n during charge of the active material
to ward the electro de center (shape change). These effects accumu-
late with cycling, leading to the loss of active surface area and
eventually to bulging of the electro de which may even result in a
mechanical rupture of the cell. The mechanism of bo th pheno mena,
which are no t necessarily co nnected,
74
is no t clear. Neither of the
suggested hypo theses can satisfacto rily acco unt for the o bserved
cycling behavio r of the zinc electro de. Mo dels which have been
pro po sed to explain the center-o riented accumulatio n of the metal
invo lve:
1. Differences in the kinetics and seco ndary current distribu-
tio n between charge and discharge half-cycles, resulting
in lateral co ncentratio n gradients and material transpo rt
due to the resulting co ncentratio n cells.
75
2. Osmo tic membrane pumping effect, driving the electro lyte
away from the electro de center during charge, and to ward
B atteries fo r Vehicular Pro pulsio n 401
it during discharge, when the electro lyte is mo re co ncen-
trated.
76
This mo del seems to require the presence of an
electro lyte reservo ir. Experimental co nfirmatio n of the
mo del is so mewhat co ntro versial.
77
3. Fragmentatio n of zinc
78
'
79
due to ano malo us current distri-
butio n o r a no nunifo rm cro ss sectio n of dendritic stems
and/o r their fracturing during current reversal in the
catho dic half-cycle. Electro pho retic mo tio n of small frag-
ments wo uld then acco unt for the shape change.
Recent o bservatio n of the o ppo site cycling effectdenudation
at the electro de center and zinc accumulatio n at the electro de
edges
80
is an additio nal facto r to be taken into acco unt in future
attempts at a better understanding of the mechanism of zinc shape
change. Witho ut this understanding further semi empirical attempts
to extend the cycle life of the Ni-Zn battery witho ut co mpro mising
its high-perfo rmance capability, seem to have little chance of
success.
A number of measures have been tried to prevent the shape
change, including the use of binders,
81
the extensio n of negative
plate edges beyo nd the edges of the po sitive electro de, the use of
specially shaped electro des and/o r additives
82
to the Zn electro de
and electro lyte, and the use of vibrating,
83
mechanically wiped, o r
slurry
84
negative electro des. An interesting mo dificatio n of the Zn
slurry electro de of Co mpagnie Generate d'Electricite
85
is under
develo pment at SEREGIE, France.
17
'
86
A circulating system of small
Zn-co ated plastic spheres brings them intermittently in co ntact with
a ho rizo ntal current co llecto r. The low co ncentratio n o verpo tential
prevents dendritic gro wth. Abo ut 80% of the zinc is depo sited on
the spheres. Plating erro rs o n the current co llecto r, at which the
balance of zinc is depo sited on charge, canno t accumulate since
they are co rrected upo n discharge by co mplete disso lutio n of the
metal. High reactant utilizatio n of the system is in co ntrast with
that in co nventio nal Ni-Zn cells which require that negative elec-
tro des co ntain a three- to fo ur-times excess of Zn over the rated
capacity. A mo dule co ntaining 28 bipo lar cells has been repo rted
to deliver 70Whkg
!
(95 Wh liter"
1
). The peak-po wer capability
of 120 W kg"
1
,
17
as well as high lo ngevity have been, as yet, repo rted
only for single cells and therefo re the merits of this mo dificatio n
canno t be evaluated at the present stage of explo rato ry develo p-
ment. The low cost ($70 per kilo watt-ho urs) pro jected for a mass-
pro duced battery must be treated with cautio n, in spite of the
special, light foam Ni electro de used.
87
In all Ni-Zn batteries, vario us techniques aiming at the reduc-
tio n of the inactive Ni co ntent (e.g., 60% in sintered electro des)
have been pro po sed. The limited reserves of the metal and the
sensitivity of the battery's initial cost to nickel price wo uld require
an extremely efficient (85%) metal reco very pro gram.
The develo pment of an eco no mically viable co nventio nal Ni-
Zn battery hinges on a scientific and techno lo gical breakthro ugh
which, co ntrary to expectatio ns, has no t yet materialized, causing
a drastic dro p in the R&D effort in this area.
(II) Zinc-Halogen Batteries
The attractive features of the zinc electro de (relatively low cost
and light weight of the metal with highly negative reversible po ten-
tial and relatively high hydro gen o verpo tential) stimulated attempts
to impro ve its cycle life by replacement of the alkaline electro lyte
by a flo wing acid medium. Two systems under develo pment for
bo th statio nary and EV applicatio ns involve chlo rine hydrate and
an o rganic bro mine co mplex as po sitive electro de reatants in acidic
ZnCl
2
and ZnBr
2
electro lytes, respectively. Owing to the co rro sive
pro perties of these media, metals are almo st co mpletely excluded
as battery co mpo nents. Advantages of bo th systems involve their
po tential lo ngevity; "fo rgiving" character, e.g., in their relative
insensitivity to o verdischarge; retentio n of capacity with cycling;
little dependence of perfo rmance on the depth of discharge; and
po tentially low co st. Disadvantages, common to all flo w batteries,
include co mplexity and high weight and vo lume, which affect
specific energy and po wer, as well as perfo rmance losses due to
the o peratio n of auxiliary subsystems.
(a) The zinc-chlorine battery
Zinc and chlo rine were first suggested as battery materials
some 150 years ago .
88
Several efforts were made to build the
battery;
89
the first realistic design based o n the co ncept of using
so lid chlo rine hydrate instead of gaseo us o r liquid chlo rine had
been patented in the USA in 1968. Since then the battery has been
under develo pment primarily at EDA (Gulf + Western Co mpany)
in USA
90
for mo bile as well as statio nary applicatio ns, and at the
Furukawa Electric Co mpany in Japan.
The reversible pro cesses taking place during the charge ^ dis-
charge cycle are
2e
( H
2
O)
n ( 8
Zn
2+
+ 2C1" + nH
2
O ^ Zn + Cl
2
(H
2
O)
n
The electro chemical reactio ns pro ceed at catalyst-free graphite
co mb-like electro des arranged so that the zinc side teeth interleave
with tho se o n the chlo rine side of the next co mb
90
(cf. Fig. 9). The
low (2 g liter"
1
) so lubility of chlo rine in the acidified ZnCl
2
elec-
tro lyte allo ws separato r-free o peratio n, but see Reference 91. The
electro lyte is circulated between the sump (cf. Fig. 10) and the
battery stack. During charge, zinc is depo sited on the negative
combs while gaseo us chlo rine, which evolves at the high-surface-
area po sitive electro des, is transfered to the sto re tank where it
co mbines with chilled water to form a yellow so lidchlo rine
hydrate, Cl
2
(H
2
O)
n
(n = 6 o r 8).
92
The latter pro cess o ccurs belo w
9.6C and requires refrigeratio n. During discharge, the pro cesses
are reversed: warm electro lyte is drawn from the sump into the
sto re tank to deco mpo se the hydrate. Evolving chlo rine disso lves
in the electro lyte and, upo n transfer to the battery stack, is reduced
passing thro ugh the po ro us flow-through po sitives. Zinc can be
fully disso lved during discharge, thus plating erro rs accumulated
within intermediate-depth discharges can be perio dically co rrected.
As o ppo sed to the straightfo rward electro chemistry, the
engineering of the battery po ses serio us pro blems owing to the
co mplexity of the system and its o peratio nal demands relying on
internal feedbacks. Thus, e.g., the discharge rate is co ntro lled by
mo nito ring the pressure in the sto re tank and the rate of injecting
the warm electro lyte. Abo ut 80 cycles are claimed to have been
o btained (witho ut human interventio n) in an EDA Zn-Cl
2
battery-
, UNIT CELL
COMB
ASSEMBLY
POROUS
CHLORINE
ELECTRODE
ZINC
ELECTRODE
ZINC
ELECTRODES
Figure 9. Comb structure of EDA zinc-chlo ride electro des. (Courtesy of EDA, Gulf + Western Co mpany, Dr. Peter Carr.)
r
B atteries for Vehicular Pro pulsio n 405
STORE
Figure 10. Schematic of the EDA zinc-chlo ride battery during charge (upper
diagram) and discharge (lower diagram). (Co urtesy of EDA, Gulf + Western Com-
pany, Dr. Peter Carr.)
po wered van,
93
while o ver 1600 cycles
94
have been o btained under
labo rato ry co nditio ns with human assistance.
The theo retical specific energy of the battery is 460 Wh kg"
1
.
Several battery pro to types have been tested in specially modified
vans and vehicles.
95
Fo r example, effective values of specific energy
and peak po wer are repo rted as 64 Wh kg"
1
and 59 Wh kg"
1
, respec-
tively, when tested in a passenger car po wered by a 636-kg battery
(refrigerating system off-board) and driven at a co nstant speed.
93
The energy efficiency of the EV battery is <50%. The major
cause of co ulo mbic inefficiency (10-30%) is the chemical reactio n
of zinc with disso lved chlo rine. Thanks to kinetic inhibitio ns, only
abo ut 1% inefficiency (o ver the co mplete cycle) derives from the
evo lutio n of hydro gen and carbo n o xides. The latter derive from
the graphite po sitives which o xidize at a rate co rrespo nding to some
10% weight lo ss in 1000 10-h cycles. Both gases affect the capability
of hydrate fo rmatio n and decrease the so lubility of chlo rine in the
electro lyte. Since the accumulatio n of hydro gen exceeding 5% may
create explo sive co nditio ns, a pho to chemical reacto r
96
is used to
reco mbine hydro gen with chlo rine. Hydro chlo ric acid returns to
the sump maintaining pH of the electro lyte at a co nstant (0.2)
level. Inert gases (CO
2
with traces of CO and O
2
) are perio dically
purged o r co ntinuo usly separated from chlo rine in a small cell and
vented from the system.
97
Ano ther so urce of inefficiency are the shunt currents arising
in all series-co nnected systems with a co mmo n electro lyte. In the
EDA system, these parasitic currents are minimized to some (mo del
co mputed) 5% po wer lo ss by maximizing the hydraulic resistance.
The relative abundance of reactants and low cost of the battery
materials, co mbined with a po tential for lo ng cycle life, make the
pro jected co st of the zinc-chlo ride battery low in co mpariso n with
that of mo st o ther systems. The co mplexity of the system and its
reliance o n auto mated co ntro ls may cause reliability pro blems,
particularly under co nditio ns of vibratio ns, sho cks, etc. The fleet
o peratio n of larger vehicles, with easily available human interven-
tio n during recharge, seems mo re realistic than the use of individual
units, but see Reference 98.
(b) The zinc-bromine battery
The first U.S. patents for a seco ndary zinc-bro mine battery
were awarded in 1880s to C. S. Bradley.
99
The o bvio us disadvantages
of o perating a battery co ntaining elemental bro mineco rro sio n,
high to xicity, high self-discharge ratedid no t co mpletely prevent
its develo pment, which is still underway, e.g., at GEL Inc.
100
The
major effort, ho wever, was directed to ward alternative versio ns of
the system, bo th for mo bile and statio nary uses. EV applicatio ns
have been pursued mainly at Exxon Research and Engineering
Co
101
in the form of a flo w battery with two separately circulated
electro lytes.
The charge ^ discharge cycle invo les the following highly
reversible pro cesses:
B atteries for Vehicular Pro pulsio n
407
Zn
2+
+ 2e^Zn
2Br ^Br
2
+ 2e
B r
2
+ co mplexer^Br
2
complex
ZnBr
2
+ co mplexer^Zn + Br
2
co mplex
The co mplexing agents used at Exxo n are quaternary pyrro lidinium
and mo rpho linium co mpo unds.
101102
The bro mine co mplex formed
upo n charge is a heavy inso luble oil which accumulates at the
bo tto m of the catho lyte reservo ir (cf. Fig. 11) Co mplexing reduces
the vapo r pressure of bro mine by o ne to two o rders of magnitude,
and the self-discharge rate, as well as co rro sive bro mine attack, are
co nsiderably diminished.
The battery stack co nsists of cells formed by bipo lar planar
electro des made of co nducting (~1 ft"
1
cm"
1
) carbo n-plastic com-
po site with a high-surface-area carbo n layer on the bro mine side.
(The Exxo n system is unique, in that it is the o nly EV bipolar battery
ZINC-BROMINE
CIRCUL ATING BATTERY
ANODE L OOP
CATHODE L OOP
SEPARATOR
CARBON PL ASTIC
EL ECTRODES
Br
2
ACTIVE
EL ECTRODE
PUMP
Zn DEPOSIT
PUMP
Bra COMPL EX
STORAGE
Figure 11. Schematic of the Exxon zinc-bro mine complex cell. (Courtesy of Exxon
Research and Engineering Co mpany, Dr. R. Bellows.)
develo ped to the pro to type stage.) The electro des are framed with
a filled no nco nductive plastic with mo lded flo w channels which
separately distribute ano lyte and catho lyte pumped from their reser-
vo irs into the respective co mpartments of each cell. A micro po ro us
membrane prevents direct mixing of the electro lytes. Higher so lubil-
ity of the po sitive reactant (as co mpared to Cl
2
) allows the use of
flo w-by rather than the flo w-thro ugh electro des emplo yed in the
Zn-Cl
2
system.
The co mplexing agent decreases, pro bably by adso rptio n, the
exchange current of hydro gen evo lutio n o n zinc. Mixtures of
bro mine vapo r and small amo unts of hydro gen evolved under
charge are generally no t explo sive and no t flammable within the
o perating limits.
The theo retical specific energy of the system exceeds
400 Wh kg"
1
. The effective values of specific energy and peak po wer,
pro jected as 65 Wh kg"
1
and >115 Wkg"
1
, respectively, have no t
yet been reached in the 10- to 20-kWh pro to types built to date.
103
As o ppo sed to o ther systems the energy efficiency of the Zn-Br
2
battery increases with decreasing charging time owing to decreased
self-discharge lo sses. It is repo rted as ~65%. This value includes
lo sses due to o peratio n of auxiliaries (pumping; shunt-current
pro tectio n) but do es no t take into acco unt the extent of self-
discharge under EV o perating co nditio ns, when at each shutdo wn
the bro mine remaining at the electro de deso rbs and diffuses thro ugh
the separato r to the zinc electro de. These lo sses may co nsiderably
affect the car range under sto p/go co nditio ns.
Shunt currents are minimized in an inno vative way by use of
a pro tective current applied from the battery to the common elec-
tro lyte flo wing thro ugh the manifo ld channels.
104
The energy loss
co nnected with this type of pro tectio n is repo rted as <5%.
The demo nstrated cycle life of eight-cell mo dules has reached
400-640 cycles. The mo st serio us failure mo de seems to be the
electro de warpage. The po tential longevity of the system (stability
of the electro lyte has been demo nstrated in over 1200 cycles) can
only be realized after metho ds of warpage co ntro l have been
develo ped.
The initial cost pro jected for the battery is lower than for o ther
systems with the po ssible exceptio n of the SEREGIE Ni-Zn bat-
tery.
17
'
86
The reactants and inert battery materials are relatively
abundant and inexpensive. The manufacturing metho ds, already
highly develo ped, seem to be easy and suitable for mass pro ductio n.
Apart from the electro de warpage and shutdo wn lo sses dis-
cussed abo ve, certain o ther technical pro blems remain to be so lved.
They include internal leakage, o ptimizatio n of perfo rmance in the
lo w-temperature range, po ssible startup delays, weight decrease,
and packaging capability. It is po ssible that the bulkiness and weight
of this system may limit its po tential EV applicatio ns to vehicles
larger than co mpact.
4. H igh-T emperature B atteries
(i) The Lithium-Sulfur-Based Systems
The o riginal co ncept of co upling mo lten lithium with highly
electro negative S, Se, o r Te melts, to o btain high-vo ltage cells with
extremely high theo retical specific energies (2566 Wh kg"
1
for Li-S),
resulted in an intensive research and develo pment effort on Li-S-
based systems, carried o ut primarily in the USA (Argo nne Natio nal
Labo rato ry, Go uld Inc. , Eagle-Picher, General Mo to rs), England
(Admiralty Marine Techno lo gy), and West Germany (Varta).
Difficulties enco untered in o perating
t4
all-liquid" cells (in which Li
and S melts were co ntained in po ro us stainless steel and graphite
felt electro des, respectively, separated by a paste electro lyte of Li
halo genides
105
) led eventually to the replacement of mo lten negative
electro des by so lid lithium-aluminum
106
o r lithium-silico n
107
allo ys, and of mo lten sulfurby so lid metal sulfides.
108
The mo st
advanced systems invo lve Li-Al allo y co upled with FeS and
immersed in a eutectic mixture of mo lten halides of lithium and
(usually) of o ther alkali metals. The replacement of elemental Li
and S resulted in a loss of OCV by some 40% and of the theo retical
specific energy by 84%. The o perating temperature of the battery
is 450-500C.
The o verall electro de and cell reactio ns can be represented by
2(LiAl ^ Li
+
+ Al + e) (+0.3V vs. Li/Li
+
)
FeS + 2e ^ S
2
~ + Fe , (+1.64 vs. Li/Li
+
)
2LiAl + FeS ^ Fe + 2A1 + Li
2
S
410 H alina S . W rob Iowa
At 450C the negative electro de is o perated between 10 and 48
at. % Li. Within this co mpo sitio n range two so lid phases coexist
in the melt
109
; the o pen-circuit po tential and the o perating vo ltage
plateau are co nstant. In this two -phase regio n the lithium transpo rt
rate is high, presumably owing to a high vacancy co ncentratio n.
The lithium-silico n electro des are under develo pment mainly
at Rockwell Internatio nal and General Mo to rs. Their disadvantage,
as co mpared to the aluminum allo y, lies in several vo ltage steps
over which discharge takes place, owing to a series of co mpo unds
which are so lid at Li co ncentratio ns up to 81%
n o
(the o perating
co mpo sitio n range is 50-80 at. % Li). Ho wever, the average cell
vo ltage, gravimetric and vo lumetric theo retical specific energies are
higher than for the LiAl system.
The capacity and vo ltage of the cell can be increased by using
FeS
2
as the po sitive electro de. Partial discharge pro ceeds then at
~0.3-V-higher upper plateau co rrespo nding to the first (o verall)
reductio n step:
FeS
2
+ 2e ^ FeS + S
2
~
Both po sitive electro de reactants undergo co nsiderable
vo lumetric changes during cycling, which are mo re pro no unced in
the case of FeS
2
.
The mechanism of the po sitive electro de reactio ns is very
co mplex and even for the lower plateau o peratio n involves
numero us electro chemical and chemical steps.
111
One of the inter-
mediates, the so called " / " phase, seems to inhibit the reductio n
kinetics and limit the cell perfo rmance. Measures which eliminate
this intermediate bring abo ut some undesirable effects, such as
higher co rro sio n rates, narro wing of o perating temperature range,
increased co st, andin the case of the use of Cu
2
S as an additive
po ssibility of sho rt-circuiting due to precipitatio n of Cu in the
separato r.
Use of FeS
2
severely co mplicates the electro chemical sequence
of intermediate steps.
112
In additio n, co rro sio n pro blems beco me
even mo re serio us owing to the higher vapo r presssure of sulfur
over FeS
2
. Nevertheless, the higher specific energy and vo ltage
co ntinue to stimulate further R&D effort, particularly on the LiSi-
FeS
2
and CaSi-FeS
2
systems.
The co mpo sitio n of the electro lyte is of primary impo rtance
owing to the required high io nic co nductivity, co mpatibility with
active and inert cell co mpo nents, wetting characteristics, effects o n
the co urse of electro de reactio ns, and the cell's co st. The o ptimized
electro lyte mixtures co nsist of alkali-metal halides. An all Li
+
io n
electro lyte wo uld be preferred from the po int of view of kinetic
and transpo rt co nsideratio ns; ho wever, the decreased specific
energy and high cost are then pro hibitive.
Cell o peratio n requires the presence of separato rs which are
well wetted by the electro lyte and pro vide go o d electro nic insula-
tio n, high rates of lithium io n transpo rt, and retentio n of active
electro de material. Among materials used, the rather expensive
bo ro n nitride felt
113
seems to be superio r in terms of perfo rmance
and cycle life than the much cheaper ceramic po wders.
114
The electric-to -electric energy efficiency of the battery is very
high. Thermal losses must be minimized by use of high-efficiency,
preferably vacuum
14
, insulatio n.
The safety co nsideratio ns involve primarily the co nsequences
of the high temperature of the system. No significant reactio ns of
the battery co mpo nents with air have been o bserved under co ndi-
tio ns of rupture of cells at the o perating temperature. A massive
sho rt circuit in a 20-kWh mo dule
115
which resulted in generatio n
of ~20 kWh of heat did no t present any hazard, except for a 100C
increase of the temperature of the vessel.
The limited supply of lithium raises some co ncern.
18
The
to tal glo bal reso urces are estimated at ~7. 2 x 10
6
metric
to nsan equivalent of ~3. 6 x 10
8
30-kWh batteries. Ho wever,
the metal is expected to be readily reco verable. An alternative
system, using calcium allo ys in the negative electro de, is being
explo red.
The LiAl-FeS system has been develo ped to an EV-battery-
pro to type stage.
116
Several inherent cell and engineering pro blems
still remain to be reso lved. These include, primarily, increased
utilizatio n of active materials, preventio n of deterio rating effects of
vo lumetric changes of the po sitive electro de, and develo pment of
inexpensive no nco rro ding materials and of impro ved designs for
efficient current co llecto rs. Ohmic lo sses in the present design of
the battery have lo wered the po tentially high-po wer capability to
levels unacceptable in mo bile applicatio ns.
412
H alina S . W roblowa
(ii) The Sodium-Sulfur-Based Systems
The disco very of a so lid co nducto r of so dium io ns by Kummer
and Weber
117
made po ssible the co nstructio n of so dium-sulfur cells
which utilize mo lten o r disso lved reactants separated by the ceramic
electro lyte /3-(cf. Fig. 12), o r, usually, /3"-alumina. The latter
ceramic has a three Al-O spinel blo ck structure, a mo lar ratio of
Al
2
O
3
-Na
2
O = ~5, and co ntains 1-4% of MgO o r Li
2
O. The resis-
tivity of the po lycrystalline material at 35OC is abo ut 5 Ci cm, ~4
times lo wer than that of /3- alumina. Other recently repo rted so lid
Na
+
io n co nducto rs co ntaining pho spho rus o xides
118
do no t seem
to be stable in co ntact with so dium at elevated temperatures.
119
Figure 12. Structure of /?-alumina.
Only Na-j3"-alumina-S systems o perating at 320-350C have
reached the pro to type stage envisaged for bo th statio nary and
tractio n purpo ses. The develo pment is underway at Fo rd Aero space
and Co mmunicatio n Co
120
in the USA, the Chlo ride Gro up in
England,
121
Brown, Bo veri, & Cie
122123
in Germany, Yuasa Battery
Co mpany in Japan,
122124
and Co mpagnie Generate d'Electricite in
France.
122
A high-temperature Na-S cell co nsists of a tubular so lid elec-
tro lyte rilled, in the fully charged state, with mo lten Na (so dium
co re) o r sulfur (sulfur co re cell),
125
the o ther reactant being co n-
tained between the o uter wall of the ceramic and the inner wall of
a cylindrical co ntainer (see Fig. 13). The sulfur electro de co mpart-
ment is filled with a graphitic felt which serves as the inert elec-
tro de.
125
During discharge, so dium io ns pro duced at the negative
electro de are transpo rted thro ugh the so lid electro lyte to the sulfur
electro de co mpartment in which sulfur is reduced to po lysulfide
io ns. Within the co mpo sitio n range S to ~Na
2
S
5
, the melt co nsists
SULFUR FIL L ED
POROUS GRAPHITE
SUL FUR
SODIUM
METAL CONTAINER
CONDUCTIVE CERAMIC
SEAL S
POLYSULFIDE
Figure 13 S chematic of Ford sodium-sulfur cell.
of two immiscible phases
126
and the OCV remains co nstant (2.07 V
at 350C). Further reductio n pro ceeds in a single polysulfide phase
down to the co mpo sitio n ~Na
2
S
3
. Lower polysulfides form so lid
phases which may blo ck the interface and inhibit the discharge
kinetics. Therefo re the theo retical 100% capacity is defined on the
basis of co nversio n of S to Na
2
S
3
.
In the single-phase regio n, the OCV decreases with decreasing
value of x in Na
2
S
x
. The OCV-co mpo sitio n plo t is much to o steep
to reflect the Nernstian behavio r of the simple
reactio n. The o bserved OCV values may reflect mixed po tential
behavio r of redo x reactio ns of several po lysulfides, co nsecutive (o r
single) redo x equilibria.
127
The o verall cell reactio n can be formally
represented by
2Na + xS ^ Na
2
S
x
where x > 3 under o perating co nditio ns.
The kinetics of the polysulfide reactio ns are also little kno wn
(a recent review is available
128
) and difficult to study. At the o perat-
ing temperature the exchange currents are so high that they have
no t been reliably determined. The absence of a suppo rting elec-
tro lyte further co mplicates the interpretatio n of transient vo ltam-
metry.
The vo ltaic lo sses of the discharging cell are primarily co n-
nected with the resistance of the ceramic. During charge additio nal
losses appear which are determined by the rate of removal of the
insulating film of sulfur being evolved at the electro de, and thus
by its preferential wettability by co nducting polysulfides o r sulfur.
There are no co ulo mbic losses due to parasitic reactio ns (unless
the po sitive reactant is co nsumed in a reactio n with the co ntainer
material) and self-discharge is absent. The high-energy efficiency
(~90% electric-to -electric) is diminished by thermal lo sses which
are determined by engineering design (insulatio n) and driving
characteristics of the EV.
The theo retical specific energy of the system is ~635 Wh kg"
1
.
The effective values of specific energy and peak po wer stro ngly
depend o n the cell geo metry. The desired values of > 120 Wh kg"
1
at sufficient po wer capability have no t yet been achieved in multicell
batteries. The cell geo metry also affects the energy density and
packaging capability of the battery which is of primary impo rtance
since the range of a Na-S-po wered EV may be vo lumetrically
limited.
A number of pro blems co nnected with battery co nstructio n
and o peratio n, such as rechargeability into the two -phase regio n
which requires impro vement of sulfur transpo rt away from the so lid
electro lyte and carbo n surface,
129
and develo pment of sealing tech-
niques and of ceramic mass pro ductio n, have been to a great extent
o verco me. The remaining difficulties are primarily co nnected with
the reliability and cycle life of the battery.
One of the issues is the durability of the ceramic electro lyte
under o perating co nditio ns.
130
It depends o n facto rs which are no t
fully understo o d. The damage o ccurring at excessive current
densities may be interpreted in terms of crack pro pagatio n: abo ve
a critical charging current density, liquid so dium enters the micro -
cracks at a rate faster than it can escape. This tends to cause a
buildup of pressure and crack pro pagatio n and failure of the
ceramic.
131
This hypo thesis has some co nfirmatio n in the fact that
current densities exceeding 15 A cm"
2
are harmless when elemental
so dium forms in a gaseo us state at the ceramic interface, as in the
case of the so dium heat engine.
132
Impro vements in ceramic durabil-
ity have been attempted by impro ving the fracture to ughness and
decreasing the tensile forces at the crack tips.
133
The life-limiting increase of resistance and decrease of capacity
of cycled cells is usually attributed to the deterio rating effects of
co rro sio n of the po sitive current co llecto rthe cell co ntainer in
the case of so dium co re cells o r a ro d in the case of sulfur co re
cells. Apart from co nsuming the active material, co rro sio n may lead
to the depo sitio n of po o rly co nductive layers at the current co llecto r
surface, thus interrupting the co ntact of the inert electro de fibers
with the current co llecto r. Co rro sio n pro ducts may also depo sit
and blo ck bo th the so lid electro lyte and the electro de surface. The
thermo dynamic instability of metals in po lysulfide melts severely
limits the cho ice of materials interfacing the sulfur electro de.
134
A
fully satisfacto ry so lutio n has no t yet been repo rted.
Ano ther issue which requires a mo re satisfacto ry so lutio n is
the capability for thermal cycling of the battery. At present, freeze-
thaw cycles canno t yet be repeated with the desired reliability.
The safety of single cells and mo dules has been extensively
tested. Cells were mechanically crushed, expo sed to electrically
induced failures, and dro pped from heights with expo sure to o pen
flame. Induced failures have been shown no t to spread to surro und-
ing cells no r to lead to a thermal runaway. No data yet exist
co ncerning the level of SO
2
emissio ns and the pro bability of fire
and/o r explo sio n during a vehicle crash leading to a to tal destruc-
tio n of the battery. The po ssibility of excessive heat generatio n and
explo sio n by direct chemical reactio n of so dium with sulfur is
minimized by the cell structure, which allo ws only a very small
amo unt of so dium to co ntact the sulfur melt in case of the accidental
cracking of the so lid electro lyte (cf. Fig. 14).
The system is unique among seco ndary batteries in that it uses
extremely cheap and abundant reactants. The achievable range of
a Na-S-po wered passenger car may exceed 150 miles. It is po ssible,
ho wever, that the bulkiness of the battery may limit its applicatio ns
to larger vehicles.
Ano ther, explo rato ry versio n of the Na-S system (aimed at
present at statio nary applicatio ns) is under develo pment at Dow
Chemical Co mpany. It o perates at ~300C and utilizes ho llo w
so dium bo rate glass fibers as electro lyte
135
in the form of tho usands
of thin ho llo w fibers sealed at o ne end and o pen at the o ther to a
common reservo ir of mo lten so dium. The fibers are wrapped in
Mo -co ated aluminum foil which serves as a po sitive electro de for
the po lysulfide melt, which fills the space between the fiber wall
and the Al.
The lifetime of 6-Ah (Ampere ho urs) cells is repo rted as
250-300 cycles. The predo minant failure mo de is extensive breakage
of the fibers at their junctio ns with the tube sheet. The fragility of
glass capillaries makes mo bile applicatio ns of the system do ubtful
in spite of its very high specific energy and po wer.
Replacement of the sulfur melt by a so lutio n of sulfur and/o r
its co mpo unds offers some advantages in that the o perating tem-
perature can be lo wered, the faradaic utilizatio n of the reactant
increased (i. e. , the redo x reactio ns of sulfur may invo lve reductio n
to lower po lysulfide, so lid at 35OC, as well as o xidatio n to po sitive
valences of sulfur), the o pen-circuit vo ltage made higher, and the
two -phase o peratio n avo ided. In explo rato ry systems which follow
this ro ute, use is made of sulfur disso lved in mo lten chlo ro alumi-
nates o r in o rganic so lvents separated by /3 "-alumina membranes
from the mo lten so dium. In the first case,
136
the po sitive electro de
reactio ns invo lve po sitive, primarily S
4+
io ns. At 220C small labo ra-
to ry cells have sustained some 400 cycles when discharged at
35 mA cm"
2
. The discharge and charge plateaus were steady at >3. 5
and <4. 5 V, respectively. In the seco nd
137
case, vario us so lvents
were investigated with respect to their co mpatibility with the
ceramic electro lyte and effects o n the cell perfo rmance. In general,
the po wer capabilities of these cells may be to o low for mo bile
applicatio ns.
5. R echargeable L ithium B atteries
The high-energy density and very high cell vo ltage of o rganic
electro lyte cells, in which lithium is co upled with a suitable insertio n
(intercalatio n) po sitive electro de
138
has stimulated a substantial
R&D effort (in the USA mainly at Exxo n Research and Engineering
Co . , and EIC) aimed at the pro ductio n of an EV battery.
139
Among
a number of lamellar transitio n-metal dichalco genides,
140
titanium
disulfide has been the most co mmo nly studied material of the
po sitive electro de.
138
"
141
The cell reactio n
xLi + TiS
2
^ Li
x
TiS
2
during Li insertio n is asso ciated with o nly a slight expansio n per-
pendicular to the basal planes of the po sitive electro de matrix. This
lack of structural change (which often limits the life of electro des
remaining in so lid state during cycling) makes the intercalatio n
co mpo unds ho peful candidates for pro lo nged cycling, altho ugh
some undesirable changes, which depend o n the material/elec-
tro lyte co mbinatio n, accumulate in time.
142
The po tential EV advantages of these systems are very attrac-
tive. Nevertheless, several drawbacks have, as yet, prevented the
emergence of lithium-dichalco genide (EV) batteries: rechargeabil-
ity of lithium negatives seems to be limited to some 150 cycles in
kno wn no naqueo us electro lytes
143
owing to the shape change, den-
dritic gro wth, and/o r fo rmatio n of passivating surface layers;
lithium co st was given as a reaso n for terminatio n of the Exxo n
effort; the high vo ltages make difficult finding suitable o rganic
so lvent-salt co mbinatio ns which wo uld no t deco mpo se at either
(o r bo th) electro des; the low co nductivity of no naqueo us elec-
tro lytes makes it difficult to ensure sufficient po wer capabilities.
The mo st co mmo nly used electro lytic so lutio ns co ntain LiPF
6
,
LiAsF
6
, LiC10
4
, or LiCF
3
SO
3
disso lved in pro pylene carbo nate,
THF, methyl- o r ethyl-substituted THF, sulfo lanes, and a few o ther
so lvents.
Some of the pro blems co nnected with the presence of liquid
electro lyte can be avo ided in all-so lid-state batteries. Previo us
attempts to pro duce such systems for EV applicatio ns have been
unsuccessful.
4
With the advent of electro nically and io nically co n-
ducting po lymers, new efforts are underway: a Canadian/French
"ACEP" pro ject,
144
and the Harwell Labo rato ry/Danish Odense
Technical University
145
co llabo ratio n. The cells co nsist of TiS
2
or
V
6
O
13
po sitive separated from Li negative electro des by a so lid film
of po lyethylene o xide co mplexed with LiClO
4
o r LiCF
3
SO
3
elec-
tro lyte. Bipo lar design is envisaged for Harwell EV applicatio ns.
145
The o perating cell temperature is described as 80 to <200C depend-
ing on the system. The merits of these pro jects canno t yet be
evaluated owing to the very early stage of develo pment.
6. C onducting P olymer S ystems
It has been first demo nstrated in 1977 by MacDiarmid et al
146
that
films of po lyacetylene can be chemically do ped to semico nducting
and metallic states. Sho rtly thereafter the po ssibility of
electro chemical do ping, resulting in highly co nducting materials,
had been sho wn no t only for po lyacetylene but also for a number
of o ther po lyenes, po lyphenylenes and po lychalco genides.
147
The mo st generally accepted theo ry of co nductive pro perties
of po lyacetylene is based on the existence of so lito ns.
148
These are
tho ught to appear in the po lymer chain at po ints of imperfectio n,
where chains of cis- and trans-po lyacetylene meet. The resulting
rearrangement of valence bo nds leaves an extra electro n which
beco mes delo calized over abo ut 15 CH units. A co herent descriptio n
of the nature of charge carriers in po lymers is under develo pment.
149
The enhancement of co nductivity by do ping (ranging from 10~
9
o r
10~
3
S cm"
1
for po lyacetylene and po ly(m-phenylene), respectively
to some 10
3
S cm"
1
) is usually interpreted in terms of the charge
transfer between the po lymer backbo ne and the do pant resulting
in the fo rmatio n of a po lymeric io n and a co unterio n derived from
the do pant. The structure, electro nic pro perties, and pro po sed
mechanisms of po lyacetylene co nductio n have been recently
reviewed.
150
Electro chemical do ping is reversible and thus po lymers which
can be successfully cycled between two do pant levels can serve as
rechargeable electro des. Only po lyacetylene, po ly(/?-phenylene)
and po ly(p-phenylene sulfide) are bo th o xidizable and reducible.
Other co nducting po lymers can only be either p- o r n-do ped.
The first rechargeable cells described in 1981
151
were based o n
a do ped po lyacetylene film serving as a po sitive electro de co upled
with the negative lithium electro de in a no naqueo us electro lyte.
Later versio ns included cells co nstructed of p- and n-do ped po ly-
acetylene films. Since then, several o ther systems have also been
studied for po tential battery applicatio ns. They include do ped
derivatives of po lyquino line
152
and po ly(p-phenylene).
153
'
154
The
OCV values of the respective cells are very high, up to ~5 V. They
depend o n the system and do ping levels. The advantages of high
vo ltage are, at least presently, co untered by the instability of salts
and o rganic so lvents used as electro lytes. It appears that, in general,
salts deco mpo se at the electro des faster than the co mmo nly used
o rganic so lvents.
155
Po tential advantages of lightweight co nducting po lymer bat-
teries for mo bile applicatio ns are o bvio us. It is po ssible that only
systems based on two po lymer electro des might be envisaged. Use
of lithium in o rganic electro lytes seems to preclude cycle life exceed-
ing some 150 cycles.
143
Pro jectio ns based on sho rt-term perfo rmance
of small single cells claim extremely high-po wer capabilities com-
bined with high specific energies.
156
Ho wever, the transitio n to a
practical device may no t be easy. The difficulties involve bo th
scientific and engineering pro blems. These include, amo ng o thers:
1. Lack of known no naqueo us electro lytes with sufficiently
wide stability windo ws. Witho ut them the necessary cycle
and shelf life canno t be o btained.
2. In most cases, difficulties in achieving do ping levels which
wo uld ensure sufficiently high specific energy.
157
3. Co ncerns abo ut stability of electro des under co nditio ns of
pro lo nged cycling.
4. Instability of mo st do ped materials upo n expo sure to air
and/o r mo isture which may cause pro blems in eco no mi-
cally viable manufacturing of scaled-up electro des.
Recently, a form of p-do ped acetylene has been repo rted
158
to
be co mpatible with aqueo us electro lytes and to be reversibly o xidiz-
able by oxygen (and o ther o xidizing agents). The stability of the
material over perio ds exceeding a few days is no t yet kno wn.
Ano ther materialpo lyaniline in its quino id-benzeno id-
diimine formhas recently been repo rted to be co mpatible with
aqueo us electro lytes bo th in the o xidized and reduced states.
159
As
o ppo sed to the co nventio nal metho d o f/?-do ping o rganic po lymers
by o xidative remo val of electro ns from the po lymer TT-system,
po lyaniline can be pro to n do ped in an aqueo us pro tic acid (HC1
o r HBF
4
) to a metallic (S ~ 5 ft"
1
cm"
1
) iminium salt. Cells co n-
structed with Zn and PbO
2
co unterelectro des, have been repro duc-
ibly cycled (~ 1000 cycles) with good utilizatio n albeit at low
currents and vo ltages. The autho rs do no t invo ke vehicular
applicatio ns.
Co nductive po lymers have a wide spectrum of po tential appli-
catio ns, and a large po tential for impro vements. Their use in bat-
teries has drawn the widest attentio n.
7. M etal-A ir B atteries
Both primary and seco ndary metal-air batteries have been co n-
sidered for mo bile applicatio ns. The metal negatives involve mainly
zinc and iro n, in rechargeable, and aluminum, in primary systems.
All metal-air batteries share the well-kno wn pro blems co n-
nected with the perfo rmance of the air catho de. Additio nal difficul-
ties are faced in seco ndary systems, which require a bifunc-
tio nal
160
'
161
oxygen electro de catalyzed to functio n also as an ano de.
(An interesting co ncept aimed at avo iding this co mplicatio n has
been recently pro po sed for zinc-air-po wered fleet o peratio n of
electric vehicles. Recharge at the large central facility wo uld be
effected at the ano de by o xidatio n of hydro gen lo cally generated
from natural gas or co al
162
.)
Discussio n of the oxygen electro de perfo rmance is beyo nd the
sco pe of this chapter (recent reviews are available
163
). The main
disadvantages intro duced by state-o f-art air electro des in EV
batteries are low electric-to -electric energy efficiency (generally
<40%); low specific peak po wer which may necessitate hybridiz-
atio n with ano ther battery o r flywheel; unkno wn cycle life, par-
ticularly under co nditio ns of varying lo ad; and co mplexity due to
the presence of, at least, two subsystemsfor air circulatio n and
scrubbing of CO
2
or mo re.
The merits and disadvantages intro duced by iro n o r zinc nega-
tives have been previo usly discussed (Sectio ns III. 2 and III. 3).
The iro n-air battery has been under develo pment in Sweden
(SNDC, SAB NIFE, KTH
164
), the USA (Westingho use Electric
Co ,
160165
France (SAFT), West Germany (Siemens A. G.
166
), and
Japan (Matsushita
63
). The main advantages of this lo w-vo ltage,
lo w-po wer, high self-discharge rate system are the abundant and
cheap reactants and lo ng lifetime, ruggedness, and reliability of
iro n electro des. The specific energies repo rted by vario us develo pers
under no nstandardized co nditio ns have been repo rted as between
60 and SOWhkg"
1
, and o ptimistic pro jectio ns reach even
100 Wh kg"
1
co mbined, ho wever, with po wer capabilities which are
low and do no t allow even for a co ld start.
The zinc-air system, under develo pment primarily in France
(CGE,
85
Citro en
167
), Japan,
11
and England (Lucas)
168
seems to be
mo re pro mising from the po int of view of EV perfo rmance, par-
ticularly if slurry-type
85
'
86
zinc electro des are used. The zinc-air
system can also be envisaged as a primary battery of higher-energy
efficiency than the alkaline Al-air
169
"mechanically rechargeable"
system under develo pment primarily in the USA [Lawrence Liver-
mo re Natio nal Labo rato ry (LLL),
170
Lo ckheed Missiles and Space
Co mpany,
171
and Eltech Systems Inc.
172
]; its neutral electro lyte
versio n is being studied in Yugo slavia
173
and Germany.
174
The reactio ns and mo de of o peratio n (cf. Fig. 14) of the LLL
Al-air battery are as fo llo ws:
Al + NaOH + |H
2
O + \O
2
-> NaAl(OH)
4
The chemical reactio n in the crystallizer
169
pro duces hydrargillite
NaAl(OH)
4
-* NaOH + A1(OH)
3
which is crystallized under co ntro lled co nditio ns, washed, dried,
sto red, and perio dically remo ved (while water is added to the
system) and shipped to dedicated smelting plants. Electro chemi-
Air
Electrolyte
Hydrargillite W ater
Coolant
I g I Water A l ( j
5
Figure 14. S chematic of L awrence L ivermore N ational L aboratory aluminum-air system.
cally reco vered aluminum is returned to the service statio ns. Special
cells are necessary for recycling since aluminum must be allo yed
with metals (e.g., gallium, indium, thallium, pho spho rus) to inhibit
the parasitic co rro sio n reactio n
Al + NaOH + 3H
2
O - NaAl(OH)
4
which pro ceeds at co nsiderable rates bo th at OCV and under current
drain.
Apart from the pro blems of the air catho de, common to all
metal-air cells, the system requires develo pment of all co mpo nents
and pro cesses invo lved in battery o peratio n and in fast replacement
of spent ano des. The mo st serio us drawback of the system is its
energy efficiency, much lo wer than that of most o ther batteries.
This is due primarily to the energy intensive pro cess of aluminum
reco very from the discharge pro duct. The energy efficiency can be
increased o nly by co nsiderable impro vements in electro winning of
aluminum o r by develo pment of thermal recycling metho ds. In
spite of the low energy efficiency the battery is under develo pment
for vehicular applicatio n owing to its high energy density. The range
of an EV po wered by this system is claimed to be ~ 1500 km between
ano de replacement and ~400km between water additio n and
remo val of hydrargillite.
The viability of the Al-air battery vehicular applicatio n seems
to depend (apart from the successful so lutio n of electro chemical
and engineering pro blems) o n the cost of electric po wer. If, e.g.,
nuclear o r a renewable energy so urce will ensure in the future
abundance of electricity, user's co nvenience (range, fast refueling,
large car po wered by a safe system) may beco me a mo re impo rtant
facto r than energy savings pro vided by o ther po tential EV po wer
plants.
IV. C O M P A R A T I VE EV B A T T E R Y C H A R A C T E R I S T I C S
A very tentative co mpariso n of the quantitative characteristics of
EV battery candidates is given in Table 6 for near-term and
advanced systems. (Info rmatio n co ncerning many explo rato ry sys-
tems is hardly available, even for appro ximate extrapo latio ns).
Values quo ted in Table 6 must be treated with co nsiderable cautio n.
424 H alina S . W roblow
T able 6. A pproximate C haracteristics o
System
0
Specific energy
(C/3)
(Whkg"
1
)
Energy density
(C/3)
(Wh liter"
1
)
Specific peak po wei
(15 sat 80% DOD)
(Wkg-
1
)
Battery
size
(kWh) Present Pro jected Present Pro jected Present Pro jected
Pb-Acid
ISOA
b
(Advanced)
20 37-41 45
50
65-72 80
90
-75 85
95
N i-Fe" 25-30 45-48 60 78-95 120 - 8 0 '
Ni-Zn* 20-30 42-68 75-120 70-120 130
Zn-Cl
2 50 -58 64 68
Zn-Br
7
2D-30 65 80
90
LiAl-FeS"
Na/j3"-alumina/S
d
30
35
- 55
- 65
100
100
- 9 0
- 9 0
125
120 ~100
e
100
115
1
System A was tested at NBTL and/o r JPL fo r specific energy and peak po wer; B is based o n develo per
data.
b
Based o n multicell mo dule o r pro to type battery data.
425
N ear-T erm and A dvanced EV B attery C andidates
Energy
Cycle life (80% DOD)
Demo nstrated in
efficiency Mo dule o r
(%)
60-75
60-70
65-75
45-50
65-70
- 70
- 70
c
30 s at
d
Based
e
30 s at
Cell battery
- 800
-3000 - 900
100-300
-1600 with and
80 witho ut
human assistance
- 400
>200
>1500
50% DOD.
mainly o n cell data.
80% DOD.
Pro jected
fo r battery
>1000
- 2000
>1000
>1000
- 500
-1000
Co st
pro jected
by develo per
($/kWh)
60-80
- 100
- 100
- 100
- 6 0
- 120
<100
Auxiliaries
May include air
pump in each cell
May include
circulating
electro lyte
Circulating
electro lyte
refrigerato r;
Cl
2
(H
2
O)
n
sto re
Two circulating
electro lytes; two
tanks
Vacuum insulatio n
Vacuum insulatio n
Main develo pers
(so me no t active
presently in
the area)
US: Eagle-Picher,
Eltra, ESB, Glo be
Unio n, Go uld,
Westingho use.
Eur. : Lucas
Chlo ride, Varta.
Jap. : Japan
Sto rage, Shin-
Ko be, Yuasa
US: Eagle-Picher,
Westingho use.
Eur. : Daimler-
Benz, DAUG,
INCO, Swed.
Nat. 'l Dev. , NIFE
Varta. Jap. :
Matsushita.
US: Eagle-Picher,
ERC, ESB, GM,
Go uld, Westing-
ho use, Yardney.
Eur. : AGA, CGE,
DAUG. Jap. :
Furukawa, Japan
Sto rage.
US: EDA.
US: Exxo n. Austr. &
Eur. : Exxo n
licencees.
US: ANL (Al, CRC
EPI, Go uld), GM
US: Fo rd, GE. Eur. :
Brit. Rail, Bro wn-
Bo veri, CGE,
Chlo ride. Jap. :
To shiba, Yuasa.
Very few batteries have been tested for any reaso nable perio d of
time and/o r under driving co nditio ns. System characteristics are
pro jected o n the basis of perfo rmance of single cells, o r mo dules.
Data quo ted by battery develo pers lack standardizatio n. Often, the
repo rted specific-energy values refer to deliverable rather than
available energy and are quo ted at unspecified discharge rates
and/o r at depths of discharge at which sufficient acceleratio n can
no lo nger be attained. This leaves a co nsiderable margin of uncer-
tainty when quantitative descriptio ns are attempted. Numbers
quo ted in the Table as "pro jected" refer to go als expected by the
develo pers to be reachable in relatively sho rt times and do no t
reflect limits which might be achievable.
Taking into acco unt the values of specific energy
(~60Whkg"
1
) and of specific po wer (85 Wkg"
1
) required for
driving a small (1500 kg) passenger EV in urban, mixed with ICEV's
traffic,
8
it can be seen from Table 6 that amo ng simple systems only
Ni-Zn might pro vide, at sufficient acceleratio n, a range co nsidered
to be acceptable for a marketable small passenger EV. (This range,
arbitrarily set at >100 miles, is of co urse relative and depends o n
the driving habits determined by the energy situatio n at the given
time and place
6
. ) Unfo rtunately, the sho rt cycle life of Ni/Zn
precludes, at present, its co mmercializatio n. The lead-acid battery
wo uld require a co nsiderable advancement to appro ach the 80-mile
range, while the nickel-iro n system may be clo ser to the 100-mile
go al. The zinc-chlo ride battery seems to lack sufficient po wer and
can hardly be scaled do wn to the size demanded by a small
passenger car. It is no t clear, at present, whether the 100-mile range
can be exceeded in small, Zn-Br
2
-po wered EVs. Only the high-
temperature batteries might, in principle, pro vide ranges of the
o rder of 150 miles, and primary metal-air systems, mileages com-
parable with ICEVs.
Much higher ranges than tho se quo ted here, often enco untered
in EV literature,
2
'
4
'
611
usually pertain to so mewhat unrealistic co ndi-
tio ns of cars driven witho ut sto ps at a co nstant low speed.
At present, there is hardly a market for widespread EV use.
Were it to emerge in the near future, no electro chemical plants
wo uld be ready to po wer electric vehicles, except for the lead-acid
battery. The develo pment of candidate systems, capable of better
perfo rmance, requires a lo ng time and extensive scientific and
engineering effort since the pro blems still to be overcome are very
serio us. The pro duct, when perfected, will be inferio r in perfo rm-
ance to the internal co mbustio n engine but, in general, superio r to
it in terms of energy co nservatio n and enviro nmental advantages.
ACKNOWLEDGMENTS
The autho r wishes to thank Dr. N. A. Gjo stein and Mr. L. R. Fo o te
for most helpful discussio ns and co nstructive criticism.
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S tructural and T ransport P roperties of
P erfluorinated I on-E xchange M embranes
Richard S. Yeo t
Pinnacle Research Institute, Cupertino, California 95014
and Ho ward L. Yeager
Department of Chemistry, University of Calgary, Calgary, Alberta TIN 1N 4, Canada
1. H istorical B ackground of I on-E xchange M embrane C ells
Cell separato rs (o r dividers) are generally required in an
electro chemical cell in o rder to prevent bo th intermixing of ano lyte
and catho lyte, and, po ssibly, sho rting between ano de and
catho de.
1
'
2
In many cases, witho ut a separato r, the cell either do es
no t work at all o r works at a much lo wer efficiency and with a
sho rter cell life. This is particularly true for the chlo r-alkali cell
3
and the Fe-Cr redo x cell,
4
bo th of which require membrano us
separato rs.
Io n-exchange membranes are widely used in electro chemical
cells. These membranes include, in their po lymeric structure, many
io nizable gro ups. One io nic co mpo nent of these gro ups is fixed
into or retained by the po lymeric matrix (so -called fixed io n), while
the o ther io nic co mpo nent is a mo bile, replaceable ion (so -called
co unterio n) which is electro statically asso ciated with the fixed
t Present Address Kimberly-Clark Co rpo ratio n, 1400 Ho lco mb Bridge Ro ad,
Ro swell, Geo rgia 30076
437
438 Richard S . Y eo and Howard L . Y eager
co mpo nent. These membranes are permeable to o ne kind of io n
while resisting the passage of direct flo w of liquids and io ns of
o ppo site charge.
The co ncept of using an io n-exchange membrane as an "elec-
tro lyte" in electro chemical cells was first intro duced by Grubb in
1959.
5
Since then, extensive research and develo pment pro grams
have been undertaken by the General Electric Co mpany and
o thers,
6
"
9
resulting in the present so lid po lymer electro lyte (SPE)
cells in which Nafion serves as the so le electro lyte as well as
separato r. High vo ltaic efficiency can be achieved in SPE cells
because of the minimum co ntact resistance between electro de and
separato r.
2. R equirements of H igh-P erformance M embranes
The success of an electro chemical pro cess can depend critically o n
the selectio n of the pro per membrane. Yet, general criteria by which
a membrane can be selected do no t exist. The essential pro perties
of the membrane for electro chemical applicatio ns include go o d
permselectivity, high io nic co nductivity, no electro nic co nductivity,
adequate chemical and thermal stability, and sufficient mechanical
strength under o perating co nditio ns.
The membrane is a co mpro mise of pro perties: the requirement
for low internal resistance suggests that the membrane be po ro us
and thin; go o d separatio n dictates that the membrane be of low
permeability and high fixed charge co ncentratio n; and adequate
physical strength requires that it be sufficiently thick. At any rate,
membranes can generally be "tailo r-made," so that their pro perties
can be adjusted to yield o ptimal cell perfo rmance and cell life.
10
Cell efficiency very often impro ves at elevated temperatures
because of better co nductivity and impro ved kinetics. Ho wever,
hydro carbo n-type membranes are often unstable in such enviro n-
ments. This is particularly true for cells in which o xidizing agents,
such as chlo rine o r pero xide, are present. The membrane degrades
due to the cleavage of carbo n-hydro gen bo nds, particularly the
a-hydro gen ato m where the functio nal gro up is attached.
11
'
12
Per-
fluo rinated materials are better for these electro chemical applica-
tio ns because of their excellent chemical inertness and mechanical
integrity in ho t co rro sive and o xidative enviro nments.
12
P roperties of P erfluorinated I on-E xchange M embranes 439
3. Development of P erfluorinated Ionomer M embranes
The interest in perfluo rinated io n-exchange membranes has
increased extensively in recent years because of their industrial
impo rtance. A growing bo dy of research co ncerning their structure
and pro perties has develo ped.
13
"
183
Much of this work has been
summarized in a recent mo no graph.
184
While perfluo rinated anio n-
exchange membranes have no t yet been pro duced, several perfluo ri-
nated catio n-exchange types have been synthesized and fabricated
into membrane form, as listed in Table 1.
The perfluo rinated sulfo nate (Nafio n) po lymer was synthesized
and develo ped by du Po nt abo ut 17 years ago .
154185186
It was
initially intro duced as SPE in fuel cell applicatio ns in 1966. It
exhibits excellent stability over co nventio nal cro ss-linked po ly-
styrene sulfo nic acid membranes and beco mes the unique candidate
for this type of applicatio n. Subsequently, further develo pment has
been made
79181
in impro ving its chemical stability against pero xide
T able 1
P erfluorinated C ation-E xchange M embranes
Structure
XF-OCF
2
CO
2
H/SO
3
H
XF-O(CF
2
)
M
CO
2
H
XF-OCF
2
CF
2
SO
3
H
XF-OCF
2
CF
2
SO
2
NH
2
XF-OCF
2
CF
2
CO
2
H/SO
3
H
XF-O(CF
2
)
M
CO
2
H/SO
3
H
XF=-(CF
2
CF
2
)
X
-(CFCF
2
), -
i
( OCF
2
CF)
W
-
1
CF
3
Trade name
Flemio n
Nafio n 1000
series
Nafio n
Sulfo namide
Nafio n 901
Neo septa-F
Pro ducer
Asahi
Chemical
Asahi
Glass
du Po nt
du Po nt
du Po nt
To kuyama
So da
References
133
134
145, 146"
150-152
49
62
187
149
169
129
130
degradatio n. Vario us mo dificatio ns have been made to a basic
Nafio n ho mo geneo us po lymer film to pro duce materials with special
characteristics. Open weave Teflo n fabric can be laminated into the
po lymer film fo r increased strength. Also , co mpo site membranes
have been made in which layers o f two different equivalent weights
o f po lymer film are laminated to gether. Mo reo ver, surface treatment
has been emplo yed to generate membranes in which a thin layer
o f weakly acidic sulfo namide exchange sites is fo rmed.
187
Thin
amine-treated membranes
29
'
31
have fo und applicatio ns in chlo r-
alkali cells, because impro ved hydro xyl io n rejectio n is realized
when this treated surface faces the catho lyte.
62
Perfluo rinated carbo xylate membranes were intro duced abo ut
seven years ago . These membranes can be synthesized by a variety
o f metho ds o r by vario us chemical co nversio ns fro m the Nafio n
po lymer.
129133
'
150151
Co mpo site membranes which co ntain bo th
sulfo nate and carbo xylate functio nal gro ups have also been pro -
duced (see Sectio n IV. l fo r mo re details). These carbo xylate mem-
branes have been widely emplo yed in the advanced membrane
chlo r-alkali cells. This majo r chemical techno lo gy is in the pro cess
o f being revo lutio nized by the use o f these materials, a remarkable
acco mplishment fo r such a small gro up o f po lymers.
143
4. T ypes of A pplications
The perfluo rinated sulfo nic acid (Nafio n) membranes have fo und
a great variety o f electro chemical applicatio ns. These include the
SPE water electro lyzers,
79
'
80
'
131
'
144
'
181
-
183
alkaline water elec-
tro lyzers,
82
'
142
'
176
hydro chlo ric acid electro lyzers,
174
'
175
'
181
Na
2
SO
4
electro lyzers,
80
hydro gen-air fuel cells,
72181
hydro gen-halo gen fuel
cells,
174175181
zinc-bro mine cells,
158
zinc-ferricyanide redo x cells,
zinc-ferric redo x cells, Do nnan dialyzers,
32100
"
102
electro chro mic
devices,
116
chemically mo dified electro des,
26
'
27
'
58
'
89
'
90126127
'
157
io n-
selective electro des,
87
and many o thers. See References 52, 71, and
181 fo r detailed discussio ns.
Po tential applicatio ns o f perfluo rinated carbo xylate mem-
branes have been fo cused to date o n the chlo r-alkali pro cess. It
has been po inted o ut previo usly that these po lymers in acid fo rm
are no t desirable fo r electro chemical applicatio ns because o f rather
high resistance.
178
Perfluo rinated io no mer membranes show co nsiderable pro mise
with respect to their perfo rmance characteristics, low resistivity,
high permselectivity, and lo ng-term stability. Ho wever, the present
cost of these membranes is mo re than $300 per square meter. The
relatively high cost limits their applicatio n in many electro chemical
cells when co st effectiveness is a major co ncern.
5. T he S cope of this Review
This article aims at describing the micro structure and transpo rt
pro perties of these po lymeric membranes from an electro chemical
po int of view. It is intended to pro vide some directio n for the future
develo pment of high-perfo rmance membrane cells in industrial
electro lytic o r separatio n pro cesses.
Sectio n II deals with the micro structure of the perfluo rinated
io no mers. These structural pro perties and their effect on transpo rt
pro perties are currently understo o d o nly qualitatively. Altho ugh
there are diverse o pinio ns o n the detailed mo rpho lo gy of these
po lymers, it is generally agreed that micro phase separatio n and io n
clusters do exist. The presence of io n-clustering mo rpho lo gy and
the amo unt of electro lyte in these membranes can stro ngly affect
the transpo rt pro perties. The io n-clustering theo ry of Eisenberg will
be used to pro vide a basic understanding abo ut these materials.
Since mo st electro chemical applicatio ns of the materials invo lve
electro lytes, the so lvatio n pheno mena as well as the co ncentratio ns
of fixed io ns and co -io ns in the po lymers are of particular interest.
Membrane transpo rt pro perties in bo th dilute and co ncentrated
so lutio n enviro nments are presented in Sectio n III. The membrane
transpo rt pro perties under industrial electro lysis co nditio ns will be
dealt with in Sectio n IV. Fo r practical cell applicatio ns, the co nduc-
tivity and permeability of the membrane are of great impo rtance.
These pro perties can significantly affect cell perfo rmance. These
subjects are treated in Sectio n V.
I I . M I C R O S T R UC T UR E
1. S tructural S tudies of Ionomers
Perfluorinated io n-exchange membranes belo ng to a class of
materials called io no mers.
188
These perfluo rinated io no mers differ
442 R ichard S . Y eo and Howard L . Y eager
from co nventio nal io n-exchange membranes in that they are no t
cro ss-linked po lyelectro lytes but thermo plastic po lymers with pen-
dant acid gro ups (in co ncentratio ns belo w ~15 mol %) partially or
co mpletely neutralized to form salts. These perfluo rinated materials
beco me so luble when the io nic co -mo no mer exceeds 15 mol % and
wo uld be co nsidered as po lyelectro lytes.
188
Research on the structure and pro perties of so lid io n-
co ntaining po lymers has been carried o ut extensively in several
labo rato ries during the last two decades.
189201
The structure of io n
aggregates in these po lymers, and the mo dificatio ns which o ccur
on so lvatio n are generally no t kno wn quantitatively. The reaso n
for the lack of understanding of the micro structure of io n-co ntaining
po lymers lies in their co mplexity. The micro structure of io n-
co ntaining po lymers, particularly tho se aspects dealing with micro -
phase separatio n, presents a particularly challenging pro blem
because no ne of the usual to o ls of structure characterizatio n are
readily applicable. Also , results o btained by these techniques are
subject to different interpretatio ns by the vario us gro ups wo rking
in the field.
L ABIL E
CROSSL INKS
fTHERMOPLASTICrrY)
1
MODUL US
INCREASE
(CRYSTAL UNITY?)
NEW
REL AXATION
MECHANISMS
I
THERMO-
RHEOL OGICAL
COMPL EXITY
SL OWDOWN OF
MOL ECUL AR
MOTIONS
\ t
ION
AGGREGATION
\ 1
PHASE
SEPARATION
i
WATER/SOL VENT
ABSORPTION
(SELECTIVE
PLASTICIZ'N)
VISCOSITY
INCREASE
/ t
MATRIX
T
9
INCREASE
i
NEW
IONIC PHASE
T
9
\
PERMSEL ECTIVITY
DIFFUSION
CONTROL
(CHANNEL S)
Figure 1. Characteristic io no mer pro perties and their interre-
latio nships. (Ref. 18; reprinted by permission of the publisher,
The Electro chemical Society, Inc.)
It is traditio nally co nsidered that for co nventio nal io nic po ly-
mers
198
"
200
the io ns are dispersed thro ugho ut the sample in a very
low state of aggregatio n, either as io n pairs o r io n quartets. The
evidence to suppo rt this co ncept is derived from nuclear magnetic
reso nance data,
199
visco sity data,
198
and dynamic mechanical
measurements.
200
As a recent trend, it is widely accepted
that
43,44. 46,l 19.163.171.173,183.189-193.196 ^ ^ ^ ^
Q f
^
e m b e d d e d
in the surro unding o rganic medium can also exist in the po lymers,
the most direct evidence co ming from small-angle X-ray scattering.
The presence of these large io n aggregates can influence
directly, o r indirectly, vario us pro perties of these po lymers. Such
relatio nships have recently been demo nstrated by Besso and Eisen-
berg
18
and Eisenberg
202
and are shown in Fig. 1. In the light of the
impo rtance of io n clustering in determining the structural and
transpo rt pro perties of the perfluo rinated materials, some theo reti-
cal aspects of cluster fo rmatio n will be briefly described in the
following sectio n.
2. E isenberg' s T heory
In 1970, Eisenberg
201
set fo rth an initial theo ry of io no mer structure
which co ntains some co ncepts of general merit. Two basic types of
io nic aggregatio ns have been po stulated: small aggregates co ntain-
ing few io n pairs, termed multiplets, and larger aggregates, termed
clusters, which co nsist of a no nio nic backbo ne material as well as
many io n pairs. The structure of the io no mer can thus be bro adly
described as that of a micro phase-separated system in which a
matrix of low io n co ntent (due to multiplets) is interspersed with
io n-rich do mains (clusters). The bulk of the experimental evidence
has suggested that o nly multiplet fo rmatio n o ccurs at low io n
co ncentratio n whereas, beyo nd a certain io n co ncentratio n (which
depends o n the material), the multiplets may very well aggregate
to form clusters.
The fo rmatio n of io nic do mains o r clusters is regarded as being
a co nsequence of the thermo dynamic inco mpatability of the io nic
gro ups with the low dielectric co nstant o rganic matrix. The enthal-
pic advantages of phase separatio n are o bvio us but large entro pic
forces o ppo se the pro cess. Eisenberg
201
has analyzed the thermo dy-
namics of phase separatio n in io no mer systems. He has evaluated
the distances between clusters and the cluster sizes by impo sing
vario us geo metries o n the cluster. The facto rs invo lved in this
co mputatio n are: (1) wo rk do ne to stretch the po lymer chains in
cluster fo rmatio n; (2) electro static energy released when clusters
co llapse; and (3) the temperature thresho ld T
c
where the elastic
and electro static forces just balance each o ther. A brief descriptio n
of his analysis is presented as follows.
The elastic work in cluster fo rmatio n is related to the energy
changes in two different kinds of chain defo rmatio ns. The first kind
is the wo rk of stretching a po lymer chain from a distance X
o
to X,
the distance co rrespo nding to a cluster size of JV. The o ther kind
is the wo rk of co ntracting a chain from a distance of X
o
to 0.
Acco rdingly, the elastic work per chain in cluster fo rmatio n is given
by
W
ch
= (3kT/4h
2
)(X
2
-2X
2
) (1)
where h
2
= 4a
2
l
2
MJM
o
, the mean square end-to -end distance of
the po lymer chain; a
2
= chain expansio n facto r; / = length of
repeat unit; M
c
/M
0
= degree of po lymerizatio n between io nic
gro ups; X = (NM
C
/pN
A
)
1/3
, the average distance between clusters;
ô = (N
O
M
C
/pN
A
)
l/3
, the average distance between multiplets
above T
c
, p = density of po lymer, and k, T, and N
A
have their
usual meanings.
The electro static energy per io n pair released upo n cluster
co llapse is a functio n of the geometry of the cluster and the dielectric
co nstant e of the medium. It is given by
W' = -\e
2
/er (2)
where A = the fractio n of energy released, e = electro n charge, and
r = distance between centers of charge in the io n pair.
The cluster is no t infinitely stable. At some temperature T
c
the
cluster deco mpo ses, and at that temperature the elastic forces and
the electro static forces just balance each o ther. Since the elastic
force was calculated per chain and the electro static force per io n
pair, W
ch
can be set equal to W at T
c
\ thus
\e
2
/er = (3kT
c
M
0
/16a
2
1
2
M
C
)[(NM
C
/ pN
A
)
2/3
-2(N
0
MJpN
A
)
2/3
] (3)
After rearrangement, Eq. (3) yields
N = (pN
A
/M
c
)[16
2
/
2
M
c
Ae
2
/3/cr
c
M
0
r
+ 2(N
0
M
c
/pN
A
)
2/3
]
3/2
(4)
Since, T
c
can be determined experimentally and A calculated for
any particular cluster geo metry, JV and X can be calculated from
Eq. (4).
The Eisenberg theo ry indicates that at low io n co ncentratio n,
as the distance between multiplets increases, the interactio n between
multiplets is expected to decrease to the po int where the elastic
forces beco me to o large to be o verco me; belo w that co ncentratio n
clustering wo uld no t be expected. This is co nsistent with the experi-
mental findings. This theo ry has been applied well to bo th ethylene
and styrene io no mers which co ntain carbo xylate gro ups.
188
Hash-
imo to et al
43
'
44
'
54
have recently sho wn that the Eisenberg theo ry
can be used to explain the small-angle X-ray scattering (SAXS)
results o n vario us perfluo rinated io no mer membranes.
It sho uld be mentio ned that the Eisenberg theo ry is so mewhat
appro ximate and sho uld be regarded only as demo nstrating feasibil-
ity rather than predicting true cluster geo metries. The theo ry has
been co nsulted extensively in many recent mo dels pro po sed for
Nafion membranes (see Sectio n II. 4).
3. I ons in P erfluorinated Ionomers
(i) Ion-Exchange Capacity
The amo unt of io nic gro ups in these membranes is co nven-
tio nally expressed in terms of the equivalent weight (EW) of the
po lymer.
49
EW is defined as the weight of po lymer which will
neutralize o ne equivalent of base. It is inversely pro po rtio nal to
the io n-exchange capacity (IEC) acco rding to the following
relatio nship:
EW=1000/IEC (5)
where IEC is given in terms of milliequivalents per gram of po lymer.
As for the sulfo nate membrane, the range of EW of greatest interest
for electro chemical applicatio ns is 1100 to 1350, co rrespo nding to
0.741-0.909 meqg"
1
.
(11) Ion Clustering
The existence o f io n clustering in perfluo rinated sulfo nate
io no mers was first repo rted by Yeo and Eisenberg in 1975.
171
This
pheno meno n has been subsequently studied fo r perfluo rinated sul-
fo nate and carbo xylate io no mers by many o thers.
43
'
46
'
56119163183
Experimental evidence to suppo rt the co nclusio n that io n clustering
o ccurs in these materials includes thermo rheo lo gical behavio r,
173
X-ray diffractio n results,
43
'
44
'
46118139173
IR data,
41
'
55
NMR data,
22
'
74
ESR data,
153
Mo ssbauer spectro sco pic data,
14
'
56120121172
fluo res-
cence behavio r,
81
" neutro n scattering spectro sco pic data,
118119
extended X-ray abso rptio n fine structure (EXAFS) data,
108
electro n
micro sco pic data,
28
'
46
swelling behavio r,
177
acidity,
183
and transpo rt
pro perties.
46
'
63
'
159
'
163
'
183
Io n clusters are co mmo nly o bserved in the io nized fo rms o f
the perfluo rinated membranes. The size o f the clusters appears to
be larger fo r sulfo nate than fo r carbo xylate membranes.
44
The size
increases in the o rder H
+
, Na
+
, and Cs
+
and decreases with increas-
ing number o f functio nal gro ups per chain and with increasing
temperature.
43
As in the case o f ethylene io no mers, the perfluo ri-
nated carbo xylic acid membranes do no t fo rm io n clusters, at least
in the dry state.
43
The electro static interactio n may be to o weak to
fo rm io nic clusters. These o bservatio ns are expected acco rding to
the Eisenberg theo ry (see Sectio n II. 2).
Different io nic enviro nments in Nafio n have been indicated
fro m Mo ssbauer experiments.
14
'
56120121
Heitner-Wirguin et al
14
suggested the existence o f clusters and dimers. Mo st o f the io nic
gro ups are in clusters while the remaining gro ups are co nsidered
to fo rm multiplets o r small io n aggregates. The relative amo unts
o f io nic gro ups which are no t present in clusters is difficult to
evaluate because o f the limitatio n o f available research to o ls. In
additio n, the amo unt changes with the prehisto ry o f the membrane
and the enviro nment the membrane enco unters. Ro che et al
119
have
made a ro ugh estimate (with an accuracy o f 20%) o n Nafio n in
the so dium salt fo rm fro m small-angle neutro n scattering results.
They fo und that the amo unt o f io nic gro ups in the o rganic phase
is <60% and <40%, respectively, fo r N-fo rm and E-fo rm samples
[see Sectio n II. 5(i) fo r definitio ns].
(H I ) Ionic Cross-Linking
In co ntrast to co nventio nal io n-exchange resins o r membranes,
there is no cro ss-linking in these perfluo rinated membranes. In
so lvents which might disso lve the no nio nic prepo lymer, the io nic
aggregates are very stable and act as cro ss-linkage sites. Co nversely,
highly po lar so lvents, which interact with the io nic gro ups, do no t
so lvate the po lymer. The crystalline do mains o riginating from tetra-
fluo ro ethylene (TFE) backbo ne behave like cro ss-linked
po ints.
88177
Also , the clusters of the perfluo rinated io no mer mem-
branes never fall apart upo n hydratio n as indicated by SAXS
results.
43
Thus, either the io nic regio ns o r the no nio nic areas act as
cro ss-linkings which make the 1100 and higher-EW materials
inso luble, while the 970-EW material, with less TFE co ntent, is to o
weak for use in the swo llen form and is so luble.
26
'
27
'
58
'
89
'
95126127157
The high-EW membranes abso rb a range of so lvents to varying
extents
177
'
178
'
180
and exhibit two so lubility parameter values. This
behavio r is referred to by Yeo as "dual" co hesive energy densities
of the po lymer.
177
High temperatures are required to melt the crystalline do mains
in the high-EW samples and pro mo te disso lutio n. Martin et a/.
88
have recently fo und that Nafions with EWs of 1100 and 1200
disso lve in bo th 50:50 pro pano l-water and 50:50 ethano l-water,
at 250C and elevated pressure, because the crystallites of the
materials are eliminated. McCain and Co vitch
95
have also repo rted
a similar disso lutio n technique. The io nic membrane was chemically
co nverted into the no nio nic precurso r (sulfo nyl fluo ride) form prio r
to the disso lutio n pro cess. Due to the no nio nic nature of the
precurso r, it disso lves under relatively mild co nditio ns. These
disso lutio n techniques for Nafion po lymers pro vide an im-
po rtant means for preparatio n of chemically modified
electro des
26
'
58
'
89126157
and membranes of any desired geo metry.
95
4. S tructural M odels of N afion
Several structural mo dels of Nafion have been pro po sed which are
based o n vario us transpo rt and spectro sco pic pro perties of the
po lymer.
46
'
60
'
64
'
72122
A detailed picture which is co nsistent with all
the experimental o bservatio ns has no t yet emerged. Also , the pro -
po sed mo dels are either only qualitative o r have vario us adjustable
parameters and assumptio ns.
In 1977, Gierke pro po sed a pheno meno lo gical cluster netwo rk
mo del. The co ncept of io n clustering is ado pted in this mo del,
except it is assumed that bo th the io ns and the abso rbed so lvents
are all in the clusters. This is only an appro ximatio n in view of the
mo re recent spectro sco pic o bservatio ns.
41119
The clusters are
assumed to be appro ximately spherical and the cluster size, for
varying po lymer equivalent weight, has been calculated from so l-
vent abso rptio n data. Fo r so dium-fo rm Natio n of 1200 EW and a
water co ntent of 9 wt %, the cluster diameter is abo ut 3 mm.
Ho wever, based on infrared data, Falk
41
has suggested that the
hydrated io n clusters are either much smaller than Gierke estimates,
o r more likely are highly no nspherical in shape, with frequent lo cal
intrusio ns of the fluo ro carbo n phase. Extensive intrusio ns of
fluo ro carbo n material into io n-clustered regio ns is inferred from
these results.
41
The evidence for extensive interactio n of the catio ns
with the fluo ro carbo n phase has also been indicated by Lee and
Meisel.
81
Gierke also co nsidered that these clusters are interco nnected
by sho rt, narro w channels in the fluo ro carbo n backbo ne netwo rk.
The diameter of these channels is abo ut 1 mm estimated from
hydraulic permeability data. He further co nsidered that the Bragg
spacing (~5nm from SAXS data) can represent the distance
between clusters. The cluster-netwo rk mo del is a pheno meno lo gical
descriptio n. Recently, Hsu and Gierke
64
have derived a semi-
pheno meno lo gical expressio n to co rrelate the variatio n of cluster
diameter with water co ntent, equivalent weight, and catio n form
of the membrane. They have shown that the sho rt channels are
thermo dynamically stable.
Hopfinger and Mauritz
60
and Ho pfinger
61
also presented a
general fo rmalism to describe the structural o rganizatio n of Nafion
membranes under different physico chemical co nditio ns. It was
assumed that io nic clustering do es no t exist in the dry po lymer.
This assumptio n is applicable to the perfluo rinated carbo xylic acid
po lymer
43
but no t the perfluo ro sulfo nate po lymers.
46
They co nsider
the balance in energy between the elastic defo rmatio n of the matrix
and the vario us mo lecular interactio ns that exist in the po lymer.
The calculatio n depends on many mo lecular parameters, which are
estimated from a co mbinatio n of experimental bulk thermo dynamic
data and mo lecular structure calculatio ns, emplo ying bo th
mo lecular and quantum mechanics. The mo del semiquantitatively
repro duces water abso rptio n, po lymer density, and the number of
water mo lecules per exchange site in these po lymers. Fo r a co mpre-
hensive descriptio n of this wo rk, see References 60, 91, and 92.
Pineri et al. have perfo rmed a series of investi-
gatio ns
38
'
40118
"
123153155
o n the structural pro perties of Nafion po ly-
mers and have derived a three-phase mo del in which fluo ro carbo n
crystallites, io nic hydro philic clusters, and an amo rpho us hydro -
pho bic regio n of lower io nic co ntent co exist.
122
The micro crystallites
can be eliminated by heating the Nafio n-Na sample to 330C, and
then quenching it to ro o m temperature.
118
They showed that at high
water co ntent (>15wt%) the quenched Nafion membranes are
essentially two -phase systems.
119
These phases are rather well sepa-
rated and mo st of the water is in the io nic clusters. Samples of lo wer
water co ntent (8 wt %) show deviatio ns from two -phase behavio r.
119
A structural mo del, which co rrelates vario us spectro sco pic and
io nic diffusional results, has been pro po sed recently.
163
Figure 2
represents a schematic diagram of the mo del in which three regio ns
are indicated. Region A co nsists of fluo ro carbo n backbo ne material,
some of which is in a micro crystalline fo rm, as detected by Pineri
et al.
us
Io n clusters form Regio n C, in which the majority of
sulfo nate exchange sites, co unterio ns, and so rbed water exist. The
interfacial Regio n B is seen as o ne of relatively large fractio nal
vo id vo lume, co ntaining pendant side-chain material, a smaller
amo unt of water, some sulfo nate exchange sites which have no t
been inco rpo rated into clusters, and a co rrespo nding fractio n of
co unterio ns. The relative numbers of io ns in Regio ns B and C
wo uld depend on the size, charge density, and hydratio n energy of
the catio n. Io ns of low charge density o r large size, such as Cs
+
o r
Ru(bpy)
2+
, wo uld prefer Region B, while tho se of larger charge
density and hydratio n energy wo uld beco me lo calized in the mo re
aqueo us io nic clusters (within electro neutrality limitatio ns).
Hashimo to et al
43
'
44
have recently studied the effects of po ly-
mer swelling and defo rmatio n on the small-angle X-ray scattering
profiles of perfluo rinated io no mer membranes. The size of io n
clusters appears to be larger for sulfo nate than for carbo xylate
450
Richard S . Y eo and Howard L . Y eager
Figure 2. Three-region structural model for Natio n:
A, fluo ro carbo n; B, interfacial zo ne; and C, io nic
clusters. (Ref. 163; reprinted by permission of the
publisher, The Electrochemical Society, Inc.)
po lymers. The extent of micro crystallinity is less for the sulfo nate
po lymers for a given co unterio n form. Furthermo re, the results have
suggested that the micro structure of perfluo rinated io no mer mem-
branes can be described better by the co re-shell mo del than the
two -phase mo del. The co re-shell mo del was pro po sed by Mac-
Knight and co -wo rkers,
203
in which the io nic cluster (i.e., io n-rich
co re) is surro unded by the fluo ro carbo n phase (i. e. , io n-po o r shell).
The co re-shell particles are dispersed in the matrix co mpo sed of
fluo ro carbo n chains and no nclustered io ns.
5. S olvation P henomena
(i) Electrolyte Uptake
Vario us physical and transpo rt pro perties of these catio n-
exchange membranes are largely influenced by the amo unt of elec-
tro lyte abso rbed. The electro lyte uptake of these no n-cro ss-linked
membranes is stro ngly affected by the po lymer functio nal gro up,
the po lymer equivalent weight, the histo ry of pretreatment, and the
electro lytic enviro nment.
The amo unt of water a membrane will initially abso rb increases
with temperature, as is sho wn in Fig. 3 for a 1200-EW po lymer in
the sulfo nic acid form. These samples are assigned as no rmal (N)
form o r as-received form. It is interesting that a sample, which has
been expo sed to water at a higher temperature, say 100C, shows
greater water abso rptio n and will co ntinue to retain that same
amo unt of water at ro o m temperature, unless the effect is destro yed
by drying at elevated temperatures. These samples are deno ted as
expanded (E) form. On the o ther hand, the water abso rptio n can
be decreased if the sample is heated in the dry state at elevated
temperatures. These samples are deno ted as shrunken (S) form.
Again, the membrane is particularly sensitive to these treatments
if it is in the acid form. As sho wn in Tables 8 and 9 (Sectio n V),
100
TEMPERATURE, C
200
Figure 3. Water uptake for Nafion of 1200 EW as a function
of temperature. (Ref. 49; reprinted by permission of the
publisher, The Electro chemical Society, Inc.)
452 R ichard S . Y eo and H oward L . Y eager
' 0 2 4 6 8 10 12
NaOH CONCENTRATION, mole/liter
Figure 4. Water uptake for per-
fluo rinated io n-exchange mem-
branes for vario us EW as a function
of NaOH co ncentratio n: ( )
sulfonate and ( ) carbo xylate
(Ref. 133).
the water co ntent alters appreciably by pretreatment, which is a
classical effect with no n-cro ss-linked po lymers.
Figure 4 shows the dependence of water abso rptio n o n NaOH
co ncentratio n for the carbo xylate and sulfo nate membranes. The
water abso rptio n of perfluo ro carbo xylate membranes is much lo wer
than that of perfluo ro sulfo nate membranes. The water abso rptio n
decreases with increasing equivalent weight. This can be expected
because the higher the equivalent weight, the lo wer the co ncentra-
tio n of io nic gro ups per unit po lymer weight. The data in Fig. 4
can be expressed by the following empirical equatio ns,
49133
where
Eqs. (6) and (7) represent sulfo nate and carbo xylate membranes,
respectively:
where W
e
is expressed in terms of weight percent of water, based
on the dry po lymer weight, M is the mo larity of the electro lyte
(0 < M < 14), A is a co nstant (H
+
= 1, Li
+
= 0.95, Na
+
= 0.79,
K
+
= 0.57), and B is a co nstant dependent o n the histo ry of pretreat-
ment of the membrane (B = 1 for E-form samples); and
0.001855
1+0. 1065M
exp(5104/EW)
(7)
and 1100 < EW < 1400.
Figure 5 shows the electro lyte uptake of the sulfo nic acid
membrane as a functio n of electro lyte co ncentratio n for three
different acid electro lytes. The electro lyte co ntent of the membrane
decreases with increasing acid co ncentratio n. As shown in Table
2, bo th sulfo nate and carbo xylate membranes so rb large amo unts
of o ther so lvents as well, particularly alco ho ls and o ther pro tic
so lvents.
151
'
177
'
180
0 4 8
ELECTROLYTE CONCENTRATION, mole/liter
Figure 5. Electro lyte uptake for Nafion of 1200 EW as
a function of electro lyte co ncentratio n: (O) HC1, (A)
HBr, and ( ) H
3
PO
4
. (Ref. 182; reprinted by permission
of the publisher, The Electro chemical Society, Inc.)
T able 2
Degree of S welling for N ation* and Flemion M embranes
0
So lvent
Water
Fo rmamide
Glycero l
Ethylene glyco l
Methano l
Ethano l
Pro pylene glyco l
1-Pro pano l
2-Pro pano l
Amyl alco ho l
Decano l
Aceto ne
2-Ethyl hexano l
Diethyl amine
Triethyl amine
So lubility
parameter
23.4
19.2
16.5
14.6
14.5
12.7
12.6
11.9
11.5
10.9
10.0
9.9
9.5
8.0
7.4
Nafio n
acid fo rm
21
56
56
66
54
50
55
58
73
70
21
17
Nafio n
Li fo rm
12
45
44
56
48
45
47
32
75
72
47
Flemio n Flemio n
Na fo rm ester type
14
80
800 1
15
130
7
10 11
a
Fro m References 151, 177, and 179.
b
So lvent swelling fo r Nafio n (1100 EW) is given in terms o f weight percent o f dry
po lymer.
(ii) Sorption Rate of Electrolyte
Go o d wettability is essential for membranes that serve as
separato rs in electro chemical cells. While fluo ro carbo n po lymers
are generally kno wn to be quite hydro pho bic substances, these
membranes are certainly an exceptio n. They so rb water rapidly
even at ro o m temperature. The so rptio n rates of water and o ther
T able 3
A pparent Diffusion C oefficients of H C l E lectrolytes
in N afion"
Electro lyte co ncentratio n Diffusio n co efficient
(wt%) ( xl O^n^s"
1
)
0 1.66
10 1.31
20 0.64
25 0.33
a
Fro m References 182 and 183.
stro ng electro lytes in Nafion have been repo rted.
146147183
Table 3
represents the diffusion coefficients of HC1 electro lytes in Nafio n.
The diffusion of these electro lytes in Nafion is very rapid. Fo r dilute
electro lytes, it is o ne o rder of magnitude smaller than the self-
diffusion of water o r HC1. The diffusion rate decreases with increas-
ing co ncentratio n due to the dehydratio n of the membrane.
(I I I ) State of Water in Nafion
Several studies on the state of water in Nafion have been
repo rted recently.
21
'
38
'
41119122136
'
140
'
155
A part of the water is asso ci-
ated with the sulfo nic acid gro ups, part interacts with the o rganic
matrix,
41119136
while still ano ther part forms water clusters.
21119
Water present in small quantities tends to be preferentially abso rbed
into the io nic phase.
43
The io n clusters in Nafion do no t fall apart
with water saturatio n.
43
Falk o bserves evidence for two enviro n-
ments of so rbed water in Nafion from infrared spectro sco pic
studies.
41
The first enviro nment appears to be aqueo us in nature.
It is much less stro ngly hydro gen bo nded than water in aqueo us
salt so lutio ns
41
and it behaves as a liquid which is significantly
different in its physical pro perties from tho se of bulk water.
136
In
the seco nd enviro nment, the water mo lecules are no t hydro gen
bo nded and appear to be expo sed mainly to fluo ro carbo n.
In a dielectric relaxatio n study of Nafio n, Yeo and Eisenberg
173
have o bserved two dielectric peaks of different energy abso rptio n
level. Both of these peaks are highly sensitive to the presence of
water in the materials. The activatio n energies are lOSkJmo l"
1
and ~67 kJ mo l"
1
, respectively, for the peaks appearing at lo wer
and higher temperature.
22173
The amo unt of water in the o rganic
phase is <24% and <20%, respectively, for N-form and E-form
samples, based on neutro n scattering data.
119
Falk
41
also co ncludes
from infrared data that abo ut three quarters of the water is in the
io n cluster.
(it?) Concentration and Acidity of Exchange Sites
The calculatio n of the co ncentratio n of fixed io ns (o r exchange
sites) is co mplicated by the existence of the io n-cluster mo rpho lo gy
in these materials. Recently, an analysis was perfo rmed on
e\fJ
Nafion based o n io n-cluster mo rpho lo gy and spectro sco pic info r-
matio n.
183
The amo unt of io nic gro ups within the hydrated io n clusters
is equal to IEC x/ , where / is the fractio n of io nic gro ups in the
io n clusters. The vo lume of the io n cluster is given by V
w
xf
W9
where V
w
is the vo lume of electro lyte abso rbed by the membrane
and f
w
is the fractio n of electro lyte so lutio n in the io n clusters. V
w
can be calculated from the electro lyte uptake of the membrane.
The co ncentratio n of fixed io n (in terms of mol liter"
1
) is thus given
by
IEC/
V f
where W
e
and d
e
are the weight fractio n and density of the elec-
tro lyte abso rbed by the membrane, respectively. The value of /
varies between 0.4 to 1.0 whereas the value of f
w
varies in the range
of 0.76-1.0, based on neutro n scattering
119
and infrared data.
41
It
follows that the ratio of fjf
w
varies between 0.4 to 1.32. Because
of the hydro philic nature of the io nic gro ups, it is very likely that
the fractio n of water in the clusters depends o n the fractio n of io nic
gro ups in the clusters, i. e. ,///*; ~ I.
183
Figure 6 shows the co ncentratio n of fixed io ns for Nafion of
vario us EW in equilibrium with water. These co ncentratio ns are
calculated by assuming//^ = I.
183
The co ncentratio n of fixed io ns
increases with EW because the decrease of io nic gro ups with
increasing EW is less significant in co mpariso n with the decrease
of V
w
, which in turn is related to the water uptake. Ano ther impo r-
tant feature is that membrane pretreatment has a stro ng effect o n
the co ncentratio n of fixed io ns. The co ncentratio n of fixed io ns is
higher for N-form samples than for E-form samples since water
uptake increases by bo iling the sample in water. It is expected that
the co ncentratio n of fixed io ns in the S-form samples sho uld be
higher.
The perfluo rinated sulfo nic acid membrane exhibits a very
stro ng acidic behavio r in water. As shown in Figure 6, the co ncentra-
tio n of fixed io n for Nafion of 1200 EW in E-form is equivalent to
13 wt % sulfuric acid. A similar value of 10 wt % sulfuric acid was
o bserved by LaCo nti et al
19
The pK
a
value is a go o d indicatio n
of the acidity of a material. A recent study has repo rted that
149
the
_ 6
o
CO
z
2 4
Q
LU
X
o
(J
I 1 1 1 I
1000 1200 1400 1600 1800
EQUIVAL ENT WEIGHT
Figure 6. Calculated co ncentratio n of fixed ion for Nafion of vario us EW in
equilibrium with water at 25C. ( ) N-form and ( ) E-form. (Ref. 183;
reprinted by permissio n of the publisher, The Electro chemical Society, Inc.)
apparent pK
a
of the sulfo nate and carbo xylate membranes are <1
and 1.9, respectively.
Figure 7 shows the co ncentratio n of fixed io ns of Nafio n. The
co ncentratio n of fixed io ns increases drastically with electro lyte
co ncentratio n because of the io n-cluster mo rpho lo gy
183
and the
highly dehydrated state of the membrane in co ncentrated elec-
tro lytes, as well as the mass-actio n effect in co unterio n activity.
Kimo to
70
has recently sho wn that in co ncentrated alkaline so lutio ns
the "effective" co ncentratio n of fixed io ns is less than half of the
value calculated from Eq. (8). This decrease is due to the io n-pair
fo rmatio n and stro ng asso ciatio n in the io n cluster.
(v) Donnan Exclusion Effect and Superselectivity
These perfluo rinated membranes, similar to o ther io n-exchange
materials, exhibit a Do nnan exclusio n effect.
70183
Figure 8 shows
the co ncentratio n of co -io n of N-form Nafion with varying HC1
20
- 16
o
</)
z
o 12
o
LU
X
9 8
Sc
o
8 4
6 12
Figure 7. Calculated co ncentratio n o f fixed io n fo r Nafio n o f
1200 EW fo r varying HCI co ncentratio ns at 25C: ( ) N-
fo rm and ( ) E-fo rm. (Ref. 183; reprinted by permissio n o f
the publisher, The Electro chemical So ciety, Inc. )
electro lyte. The so lid curve is calculated from the Do nnan
equatio n
204
:
C
2
=C
n
(C
n
+ C
f
)(y/y)
2
(9)
where C
f
and C
n
are the co ncentratio ns of fixed io n and co -io ns,
respectively, y and y are the activity coefficients in the external
and membrane phase, respectively. The activity coefficient ratio
(y/y) is, for most cases, unity.
183
The dashed line is for the case
in which there is no Do nnan exclusio n effect for the membrane
5 12
o
CO
1 8
O
o
LL.
O
z
o
o
o
o
I I I I I J_
0 4 8 12
Figure 8. Co ncentratio n of co -io n for N-form Nafion of 1200
EW in equilibrium with vario us HC1 electrolytes at 25C:
( ) no Do nnan effect and ( ) calculated from Eq. (9).
(Ref. 183; reprinted by permissio n of the publisher, The
Electro chemical Society, Inc.)
(Cf = 0). The Do nnan exclusio n effect imparts the permselectivity
characteristics to these materials. Go o d permselectivity generally
o ccurs in dilute so lutio ns while there sho uld be no permselectivity
in highly co ncentrated so lutio ns. Ho wever, the permselectivity of
Nafion persists beyo nd the Do nnan limit and is referred to as
"superselectivity" by Reiss and Bassignana.
117
The superselectivity
pro vides enhanced current efficiency beyo nd the Do nnan limit. This
extremely valuable pro perty o riginates from the unusual io n-cluster
mo rpho lo gy of these materials.
I I I . I O N A N D W A TE R DI FFUS I O N
Studies of the diffusional pro perties of perfluo rinated io no mer
membranes pro vide the necessary basic info rmatio n which is
needed for their applicatio n in vario us co nfiguratio ns. Large io nic
diffusion coefficients in the membrane phase are desirable, no t only
to minimize o hmic lo sses in electro chemical cells, but also to
maximize transpo rt rates for pro cesses driven by co ncentratio n
gradients such as Do nnan dialysis.
32
Solvent transpo rt thro ugh the
membrane may or may no t be desirable, depending upo n the
applicatio n. A seco nd go al for the study of diffusion in perfluo ri-
nated io no mers is to develo p insight into the relatio nship between
the unusual mo rpho lo gy of these po lymers and their transpo rt
pro perties. In the latter regard, the determinatio n of self-diffusion
coefficients is of particular usefulness. In such experiments the
membrane is in equilibrium with the external so lutio n, so that no
gradients in internal chemical po tential exist. Radio active tracers
can be used to evaluate self-diffusion coefficients which depend
upo n membrane co mpo sitio n, but are no t co upled to chemical
po tential gradients o r the fluxes of o ther species. These values are
therefo re mo re straightfo rward in their interpretatio n. Results of
such measurements for perfluo rinated sulfo nate and carbo xylate
membranes are discussed in this sectio n.
1. Diffusional P roperties in Dilute S olution E nvironments
The self-diffusion coefficients of so dium and cesium io ns have been
measured for perfluo rinated sulfo nate (Nafion) and carbo xylate
membranes of similar structure.
159163
'
165
The exchange-site co n-
T able 4
E xchange-S ite C oncentration and W ater C ontent for P erfluorinated
Ionomer M embranes
0
Membrane
Sulfo nate
Carbo xylate
a
Fro m Reference
b
N-fo rm samples.
Io nic
fo rm
Na
+
Cs
+
Na
+
Cs
+
165.
Exchange-site
co ncentratio n
6
mo l liter"
1
1.20
1.35
1.30
1.37
Mo l
H
2
O/mo l
exchange site
N-fo rm E-fo rm
11.9 18.4
6.6 11.3
9.5 13.9
5.0 9.1
centratio ns and water-to -exchange-site ratio s for these io nic forms
of the po lymers are listed in Table 4. The exchange site co ncentra-
tio ns of the two po lymers are quite similar, which is useful for the
co mpariso n of their diffusional pro perties. The water co ntents
stro ngly depend on the co unterio n form and pretreatment [Sectio n
II. 5(i)]; the carbo xylate po lymer so rbs abo ut 20% less water in all
cases. The variability of water co ntent with co unterio n form is a
reflection of the dynamic character of these io n-clustered, no n-
cro ss-linked po lymers. This is in co ntrast to co nventio nal cro ss-
linked io n-exchange resins such as the cro ss-linked po lystyrene
sulfo nates, where water co ntent is largely independent of co unterio n
form for a given co unterio n charge type.
205
Self-diffusion coefficients for so dium io n, cesium io n, and water
in these po lymers are sho wn in Fig. 9, as Arrhenius plo ts from 0
to 40C.
165
Diffusion of so dium io n and water is remarkably similar
10-V
1000/T, K"
Figure 9. Membrane self-diffusion coefficients vs. the recipro cal
of abso lute temperature for perfluo ro carbo xylate (light symbols)
and perfluo ro sulfo nate (dark symbols) po lymers: (A, A) H2O,
(O, ) , Na
+
and ( , ) Cs
+
. (Ref. 165; reprinted by permissio n
of the publisher, The Electro chemical Society, Inc.)
in the two membranes. Diffusion coefficients are slightly larger for
the carbo xylate in each case, even tho ugh the membrane always
co ntains less water per exchange site. In general, these diffusion
coefficients are quite large in relatio n to the membrane water so rp-
tio n, abo ut a facto r of 10 larger than for po lystyrene sulfo nate
resins of co mparable water co ntents.
206
'
207
This is a reflection of
the micro phase separatio n of water, exchange sites, and co unterio ns
in these io no mers, which pro duces highly efficient transpo rt paths.
Average activatio n energies of diffusion in these membranes are
24.9 kJ mo l"
1
for the so dium io n and 23.3 kJ mo P
1
for water, which
are only marginally higher than their values in pure water, 19.1 and
17. 8k. Jmo r
1
, respectively. Therefo re a so lutio nlike diffusion
mechanism for so dium io n and water thro ugh a netwo rk of io n-
clustered regio ns is indicated for bo th po lymers. The self-diffusion
coefficients for cesium io n in these perfluo rinated io no mers, which
are smaller than tho se for so dium io n in all cases, are less easily
interpreted. No rmally, cesium io n has a larger diffusion coefficient
than so dium io n in aqueo us enviro nments. Fo r example, in water
the ratio of >
Na
+ to D
Cs
+ is 0.65, and in an 8% DVB po lystyrene
sulfo nate resin the ratio is 0.69.
206
Fo r these cases equal amo unts
of water are present in the diffusing medium tho ugh, which is no t
the case for these io no mers. The values listed in Table 4 indicate
that the expanded Cs
+
form of each membrane has abo ut the same
water co ntent as the no rmal Na
+
form. A co mpariso n of the so dium
io n/cesium io n diffusion coefficient ratio s for these cases yields
values of 0.71 and 5.3 for the perfluo ro carbo xylate and perfluo ro sul-
fo nate po lymers, respectively.
165
Thus the apparent ano maly in this
ratio is remo ved if we co mpare systems with equal water co ntents
for the carbo xylate, but no t for the sulfo nate po lymers.
Further ano malies are seen in the diffusional behavio r of
cesium io n for the perfluo ro sulfo nate membrane. Figure 10 rep-
resents the plo t of the lo garithm of the diffusion coefficient vs. the
function v
p
/(l-V
p
), where V
p
is the vo lume fractio n of po lymer in
the water-swo llen material
163
and 1 - V
p
is the vo lume fractio n of
water, as calculated from so rptio n measurements. This plo t co rre-
spo nds to a test of the equatio n
D=Dexp[-fcV
p
/(l - V
p
)] (10)
which has been develo ped by analo gy to Co hen and Turnbull's
P roperties of P erfluorinated I on-E xchange M embranes
463
10~
5
Figure 10. Lo garithm o f self-diffusio n co efficient vs. po lymer-fractio n functio n
fo r 1200-EW perfluo ro sulfo nate po lymer, at 25C. Na
+
and Cs
+
lines witho ut
data po ints: po lystyrene sulfo nate behavio r. (Refs. 163 and 207; reprinted by
permissio n o f the publisher, The Electro chemical So ciety, Inc. )
free-volume theo ry of diffusion.
207
"
209
This equatio n pro vides an
excellent co rrelatio n of the self-diffusion coefficients of so dium io n
and cesium io n in po lystyrene sulfo nate resins of varying water
co ntent, as sho wn in Fig. 10.
207
The D intercepts are abo ut o ne-half
of the so lutio n D values in water, presumably due to electro static
attractio ns (Wang effect) exchange sites in the po lymer phase.
Sodium io n/cesium io n hetero io nic forms of the perfluo ro sulfo nate
po lymer were used to pro duce samples of varying V
p
, in additio n
to the no rmal and expanded ho mo io nic fo rms. No co rrespo ndence
is seen between the po lymer diffusion results for this and po ly-
styrene sulfo nates. Mo st no table perhaps is the co mplete lack of
dependence of D
Cs
+ in the perfluo ro sulfo nate membrane on water
co ntent. The activatio n energy for cesium io n diffusion, abo ut
36 kJ mo l"
1
, is largely independent of water co ntent as well. Water
diffusion again is similar to so dium io n diffusion, this time in terms
of the membrane's water co ntent, with no ano maly seen for the
cesium io n form.
The unusual features of cesium io n diffusion in the per-
fluo ro sulfo nate po lymer are related to the micro structure of these
po lymers. The micro phase separatio n into io n-water and fluo ro car-
bo n regio ns is mo re co mplete for the perfluo ro carbo xylate than for
the perfluo ro sulfo nate po lymer. Fo r the carbo xylate material,
stro nger hydro gen bo nding in the aqueo us phase wo uld result due
to less fluo ro carbo n interference with extended intermo lecular
water interactio ns. A greater degree of fluo ro carbo n crystallinity
and a smaller fractio n of no nhydro gen bo nded water for the car-
bo xylate membrane wo uld also be expected co nsequences of mo re
co mplete phase separatio n. Spectro sco pic studies of the co unterio n
enviro nments in the perfluo ro sulfo nate po lymer pro vide additio nal
info rmatio n of interest. The mid- and far-infrared spectra of alkali
metal in forms of Nafion perfluo ro sulfo nate films indicate that no
io n pairing of co unterio ns to exchange sites o ccurs, even for
co mpletely dehydrated fo rms.
109
Thus io n pairing is no t a relevant
facto r in the interpretatio n of small cesium io n diffusion coeffi-
cients. A luminescence quenching study of Ru(bpy)3
+
(bpy =
2,2'-bipyridine) in Nafion has been perfo rmed.
81
The autho rs co n-
clude that this large, low charge density catio n is preferentially
situated in a fluo ro carbo n enviro nment rather than an aqueo us o ne.
This suggests that the distinctio n between io n cluster and fluo ro car-
bo n may no t be as simple as suggested in vario us structural mo dels,
and that interfacial regio ns must also be co nsidered.
The less co mplete degree of phase separatio n for the sulfo nate
po lymer may well lead to interfacial regio ns of partly aqueo us
character and relatively high void vo lume, as depicted in Fig. 2. A
preference of large, low charge density co unterio ns such as
Ru(bpy)3
+
and cesium io ns for such regio ns wo uld help to explain
the Cs
+
diffusional ano malies discussed earlier. Diffusion alo ng
interfacial bo undaries rather than thro ugh io n-clustered regio ns
wo uld result in lo wer bulk diffusion coefficients for cesium io n
co mpared to so dium io n. The lack of dependence of D
Cs
+ o n water
so rptio n can then be understo o d by first no ting that, as water
so rptio n increases in Nafio n, it enters o nly into io n-clustered
regio ns.
41
Thus to rtuo sity wo uld no t be reduced for a catio n
diffusion in peripheral regio ns of the aqueo us clusters. Altho ugh
these interpretatio ns are speculative, it is clear that bo th spectro -
sco pic and diffusional measurements indicate a mo re co mplete
micro phase separatio n into aqueo us and fluo ro carbo n regio ns for
the carbo xylate co mpared to the sulfo nate po lymer.
Self-diffusion coefficients of po lyvalent catio ns in these per-
fluo rinated io no mer membranes have no t been repo rted. It can be
inferred from the use of the sulfo nate membranes as Do nnan
dialysis devices that transpo rt of catio ns such as Cu(II), Mg(II),
and Al(III) under a co ncentratio n gradient is rapid.
32100
'
210
Also ,
co lumn chro mato graphic separatio n of the alkaline-earth io n is
readily acco mplished with a po wdered Nafion perfluo ro sulfo nate
po lymer, which is again an indicatio n of facile diffusion of these
catio ns within the po lymer phase.
160
Recently, several interesting studies of the electro chemical
pro perties of electro des co ated with thin films of Nafion have been
repo rted.
26
'
58
'
89126157
These chemically modified electro des are pre-
pared using low-EW po lymers which are alco ho l so luble,
26126
o r
using a so lutio n of a 1100-EW po lymer which has been disso lved
at high pressure and temperature.
88
Electro chemical studies for
catio ns such as the Ru(bpy)3
+/2+
co uple yielded estimates of io nic
diffusion coefficients in the po lymer films. Ho wever, results also
indicate that these films are far mo re po ro us than co nventio nal
Nafion membranes, so it is no t po ssible to co mpare values directly
with tho se discussed abo ve.
2. Diffusion P roperties in C oncentrated S olution E nvironments
Industrial applicatio ns of perfluo rinated io no mer membranes such
as the electro lysis of so dium chlo ride so lutio n to pro duce chlo rine
and so dium hydro xide often invo lve the use of highly co ncentrated
so lutio ns at elevated temperatures. The o ptimizatio n of these sys-
tems depends upo n a so und characterizatio n of membrane transpo rt
pro cesses under such co nditio ns. So dium io n is the major current-
carrying species thro ugh the membrane in a chlo r-alkali cell, and
some attentio n has been focused on its diff usio nal behavio r in these
enviro nments.
The self-diffusion coefficient of so dium io n is plo tted in Fig.
11 vs. the recipro cal of abso lute temperature for the perfluo ro sulfo -
nate and perfluo ro carbo xylate membranes which were discussed in
Section III. I.
149168
Here tho ugh, the membrane enviro nment co n-
sists of co ncentrated so dium hydro xide so lutio ns of varying co n-
centratio ns at temperatures of 70-90C. Under these co nditio ns,
1000/ T , K"
1
Figure 11. Sodium ion self-diffusion vs. the recipro cal of abso lute
temperature for perfluo ro carbo xylate (light symbols) and perfluorosul-
fonate (dark symbols) polymers in co ncentrated NaOH so lutio n
enviro nments. (Refs. 149 and 168; reprinted by permission of the
major differences between the two types of membrane are also seen,
even for so dium io n diffusion, unlike the results for dilute so lutio n
enviro nments.
In 5 M NaOH, the carbo xylate now sho ws slightly lower values
of the diffusion coefficients co mpared to the sulfo nate membrane.
This pattern is repeated for values measured with 4 M and
5 M NaCl so lutio ns as well.
149
At higher NaOH so lutio n co ncentra-
tio ns, values for the carbo xylate beco me much smaller, averaging
130
120
110
_o> 100
o
^ 90
_ ACTIVATION ENERGY OF Na
+
SELF- DI FFUSI ON, 70 - 90 C
CARBOXYLATE
<
80
*
20
10
SULFONATE

10 12 14
NaOH CONCENTRATI ON , M
Figure 12. Activation energy of Na
+
diffusion in perfluo rinated io no mer
membranes vs. NaOH so lutio n co ncentratio n, 70-90C temperature
interval. (Ref. 168; reprinted by permissio n of the publisher, The
Electrochemical Society, Inc.)
abo ut an o rder of magnitude lo wer than tho se for the sulfo nate
membrane. This is acco mpanied by a pro no unced increase in the
activatio n energy of diffusion for the carbo xylate po lymer, as shown
in Fig. 12. It wo uld appear that the mechanism of so dium io n
diffusion changes for o nly the carbo xylate po lymer over this co n-
centratio n regio n.
The results of io n and water so rptio n measurements for the
two po lymers under these so lutio n co nditio ns help to explain this
difference. Table 5
149
lists the co ncentratio ns of vario us so rbed
species and the mole ratio of water to catio n/ anio n in the po lymer
phase for NaCl and NaOH so lutio n enviro nments. This ratio
decreases bo th in the po lymers and in so lutio n with increasing
co ncentratio n. In so lutio n, the ratio varies from 10.8 to 4.0 over
the co ncentratio n range of 5-12.5 M NaOH, so that io ns in the
po lymer phase exist in a significantly less aqueo us enviro nment
co mpared to the so lutio n phase. As no ted by Mauritz and co -
wo rkers
93
for perfluo ro sulfo nate membranes, these water co ntents
are insufficient to pro vide even primary hydratio n spheres for
so dium io ns, so rbed anio ns, and exchange sites, and the likeliho o d
T able 5
E quilibrium S orption of S odium I on, A nion, and W ater in
P erfluorinated C arboxylate and S ulfonate P olymers, 80C
a
Po lymer type
Carbo xylate
S ulfonate
So lutio n
4. 0 M NaCl
5.0 M NaCl
5.0 M NaOH
9.5 hi NaOH
11.0 M NaOH
12.5 M NaOH
4. 0 M NaCl
5.0 M NaCl
9.5 M NaOH
11.0 M NaOH
12.5 M NaOH
Po lymer co ncentratio n
(mo l dm"
3
)
Na
+
2.15
2.18
2.06
3.06
2.74
3.36
1.76
1.92
2.61
2.72
2.80
cr
0.7
0.7
0.4
0.5
OH~
0.6
1.6
1.2
1.9
1.2
1.3
1.4
H
2
O
11.6
10.2
9.2
8.2
7.0
5.8
9.9
8.9
8.0
7.7
7.6
mo l H
2
O/
mo l Na
+
5.4
4.7
4. 5
2.7
2.5
1.7
5.6
4. 6
3.1
2.8
2.7
a
From R eference 149.
of io n pairs and higher io n multiples increases with decreasing
water levels. The carbo xylate po lymer generally has even less water
available for io nic hydratio n than the sulfo nate, so that the stability
of such species wo uld be expected to be even stro nger. An additio nal
facto r is the relative charge densities of the two types of exchange
sites. While the perfluo ro sulfo nate site is well kno wn to be a very
stro ng pro to n do no r, the perfluo ro carbo xylate has a pK
a
of abo ut
2.
149
Thus, it is suspected that stro ng co ntact io n pairing in the case
of the carbo xylate is respo nsible for the low so dium io n diffusion
coefficients and high diffusional activatio n energies. Fo r the sulfo-
nate, so dium io ns that functio n as exchange-site co unterio ns may
be less stro ngly bo und than for the carbo xylate case, resulting in
mo re facile so dium io n self-diffusion in the po lymer.
So lutio n pH can also affect the diffusional pro perties of per-
fluo rinated io no mer membranes. The perfluo ro sulfo nate exchange
site po ssesses very little basicity and thus these membranes can be
used even in co ncentrated acid so lutio ns. Ho wever, it has been
shown that modified fo rms, in which the exchange sites are co nver-
ted to sulfo namide gro ups, pro to nate at so lutio n pH values belo w
13.
161
This pro to natio n severely reduces the ability of so dium io n
to diffuse thro ugh the membrane. The exchange-site acidity of the
perfluo ro carbo xylate membrane is far higher than that of the per-
fluo ro sulfo namide of co urse. Thus no pro to natio n of exchange sites
o ccurs in neutral o r alkaline media. Pro to natio n do es o ccur in
mo derately acidic so lutio ns ho wever. So dium io n diffusion flux in
this membrane in a 5 M NaCl so lutio n enviro nment at 80C is
plo tted vs. so lutio n pH in Fig. 13.
149
Also plo tted is the membrane
so dium io n co ncentratio n, which begins to fall from the neutral
so lutio n value at a so lutio n pH of 2.5. This co rrelates well with the
calculated so lutio n pH of membrane pro to natio n acco rding to the
pK
a
of the exchange sites. Ho wever, the membrane so dium io n
diffusion flux dro ps by over an o rder of magnitude befo re this
exchange-site pro to natio n is seen. It wo uld appear then that small
amo unts of pro to natio n, o n the o rder of 1-5% of membrane
exchange sites, causes a pro no unced lo ss in the ability of the
membranes to transpo rt co unterio ns. Diffusion amo ng clusters is
acco mplished thro ugh interco nnecting regio ns of lower io n and
water co ntent, acco rding to the cluster-channel mo del (Sectio n
II. 4). If these regio ns were preferentially pro to nated, the o verall
CARBOXYLATE FILM, 5M NaC
f
3 4 5 6
pH (at25C)
Figure 13. Na
+
self-diffusion flux in a perfluorocarboxylate mem-
brane and membrane Na
+
co ncentratio n vs. so lutio n pH, 5 M NaCl
so lutio n enviro nment, at 80C. (Ref. 149; reprinted by permission
of the publisher, The Electrochemical Society, Inc.)
effect on sodium ion diffusion might well be what is observed
experimentally. A lthough this interpretation is only speculative, it
is evident that solution pH is an important consideration in the use
of the perfluorocarboxylate membranes.
IV. T R A N S P O R T P R O P E R T I E S UN DE R I N DUS T R I A L
E L E C T R O L Y S I S C O N DI T I O N S
T he most important commercial application of perfluorinated
ionomer membranes is currently in the chlor-alkali industry. T hese
materials are used as permselective separators in brine electrolysis
cells for the production of chlorine and sodium hydroxide. T his
appro ach to chlo r-alkali manufacture is no w eco no mically co mpeti-
tive with the two o lder techno lo gies of asbesto s diaphragm and
mercury catho de cells. Ho wever, develo ping a so und scientific basis
for understanding membrane dynamic pro perties under industrial
electro lysis co nditio ns still presents a fo rmidable challenge as this
impo rtant techno lo gy is bro ught to full co mmercializatio n.
The membrane in a chlo r-alkali electro lysis cell experiences
rather harsh o perating co nditio ns. The ano lyte so lutio n co nsists of
2-5 M NaCl so lutio n which is mildly acidic and is mixed with
evo lving chlo rine gas. The catho lyte so lutio n co ntains 6-
17 M NaOH (20-45 wt %) and hydro gen gas from the reductio n
of water. Cell temperature and current densities are typically in the
ranges of 80-90C and 0. 2-0. 5 A cm"
2
, respectively. While the per-
fluo rinated sulfo nate and carbo xylate membranes are indefinitely
stable, even under these o perating co nditio ns, they are subject to
rather severe physical fo rces during electro lysis. Thus, electro lyte
and water so rptio n, transpo rt pro perties, and even po lymer mo r-
pho lo gy might be expected to differ from tho se seen under near-
equilibrium, dilute-so lutio n co nditio ns. Also , the slo w accumula-
tio n of brine impurities within the membrane phase affects its
pro perties. Thus, perfo rmance is a functio n of many variables, so me
of which are related to cell o perating co nditio ns and o thers which
are a functio n of membrane co mpo sitio n.
1. C haracteristics of P erfluorinated C hlor-A lkali M embranes
Thro ugh the intense research efforts of a small number of co mpanies
o ver the past 10 to 15 years, several types of high-perfo rmance
perfluo rinated membranes have been develo ped for chlo r-alkali
pro ductio n.
49
-
52
'
62
'
86
'
97
'
98
'
129
'
132
'
133
'
143
'
145
'
146
'
150
'
151
'
211
As discussed in
Sectio n 1.2, the requirements of these membranes are several: go o d
physical strength, chemical inertness, high rejectio n of hydro xide
transpo rt, and lo w electrical resistance. The degree to which a given
material satisfies these requirements generally depends o n cell pa-
rameters such as brine and caustic co ncentratio ns, temperature,
and current density, and no single type has superio r perfo rmance
o ver all co nditio ns.
Three types of perfluo rinated chlo r-alkali membranes are
no tewo rthy. The first of these, the ho mo geneo us carbo xylate films,
472 Richard S . Y eo and H oward L . Y eager
show high current efficiencies, even at the highest co ncentratio ns
of caustic. Bilayer or multilayer membranes co mprise a seco nd
type. Here each layer has either sulfo nate o r carbo xylate functio nal-
ity, with perhaps different equivalent weights of po lymer in each
layer. Fo r this type, the carbo xylate layer is always in co ntact with
the catho lyte for effective hydro xide rejectio n. A third type is related
to the seco nd in that a carbo xylate layer is co mbined with a sulfo nate
layer to yield high current efficiency and strength but low electrical
resistance. Here tho ugh, the layer is created by chemical treatment
of a sulfo nate film so that the carbo xylate layer is now very thin
(o n the o rder of 2-10 ^m). This type shows o ptimum perfo rmance
at so mewhat lo wer caustic co ncentratio ns than the first and seco nd
types.
Thus all successful chlo r-alkali membranes currently employ
a perfluo ro carbo xylate po lymer to lower the rate of hydro xide io n
transpo rt. The sulfo nate po rtio n of some of these membranes is
present mainly to add strength to the thinner carbo xylate barrier
layer. Fabric backing is also used in some cases to impro ve physical
strength.
Ho mo geneo us o r bilayer membranes of only sulfo nate func-
tio nality can yield reaso nably high current efficiencies if a high-EW
po lymer faces the catho lyte. Unfo rtunately, large electrical resist-
ances also result with such materials. Surface treatment of a sulfo-
nate membrane to yield a layer of sulfo namide exchange sites
187
also pro duces a membrane with impro ved current efficiency.
However, these sites are slowly hydro lyzed in an o perating cell, so
that this appro ach is no t co mmercially viable.
2. M embrane P ermselectivity in a C hlor-A lkali C ell
The ability of these perfluo rinated io no mer membranes to limit
migratio n of hydro xide io n into the ano lyte is of co urse a central
feature of their success in this new techno lo gy. However, this
pheno meno n is a functio n of many membrane and cell variables,
and a satisfacto ry theo retical descriptio n of the nature of this
permselectivity has no t yet emerged. Certain features of hydro xide
rejectio n are understo o d tho ugh. First, membrane water co ntent
shows a stro ng co rrelatio n with permselectivity; tho se membranes
with lower weight percentages of so rbed water under cell o perating
co nditio ns invariably show higher current efficiencies. Seco nd,
membrane current efficiency shows a pro no unced and co mplicated
dependence on so dium hydro xide catho lyte co ncentratio n. Finally,
brine co ncentratio n, current density, and temperature also influence
membrane perfo rmance in a co mplex manner, but their effects are
generally less pro no unced than that of catho lyte co ncentratio n.
Some of these features are illustrated in Figures 14-18. A rather
typical literature plo t of current efficiency vs. so dium hydro xide
co ncentratio n for perfluo ro sulfo nate membranes is shown in Fig.
14.
62
Nafion 427 is a 1200-EW sulfo nate membrane with fabric
reinfo rcement. Po o r hydro xide rejectio n o ccurs at catho lyte co n-
centratio ns abo ve 10 wt % but a minimum is seen at higher co n-
centratio ns, wtih increasing current efficiency from 28 to 40%
caustic (9-14 M). The current efficiency of a 1200-EW
ho mo geneo us perfluo ro sulfo nate film is sho wn in mo re detail over
this co ncentratio n regio n in Fig. 15.
170
So dium io n transpo rt number
(f
Na
+, mol F"
1
), which is equivalent to caustic current efficiency, is
plo tted vs. bo th brine ano lyte and caustic catho lyte co ncentratio n.
These values were determined using radio tracer techniques, which
have pro ven to be rapid and accurate metho ds for the determinatio n
of membrane perfo rmance.
24137
'
149
'
164
'
167168
A rather sharp
maximum is seen at 14 M NaOH, and the influence of brine co n-
20 30
NaOH, WEIGHT %
40
Figure 14. Current efficiency vs. catho lyte co ncentratio n for
Nafion 427 perfluo ro sulfo nate membrane. (Ref. 62; reprinted by
permission of the publisher, The Electro chemical Society, Inc.)
474 Richard S. Yeo and H oward L. Yeager
O.8-1
Nafio n 120 90C 2 kA/m
2
Figure 15. So dium io n transpo rt number fo r Natio n 120 us. brine ano lyte
and caustic catho lyte co ncentratio ns (Ref. 170).
centratio n o n the maximum is rather mino r. Figure 16 shows results
for the same membrane at a higher current density and lower
temperature. These parameters affect the maximum value of f
Na
+
and the o verall shape of the surface.
In Figure 17, so dium io n transpo rt number is plo tted vs.
catho lyte co ncentratio n for a ho mo geneo us perfluo ro carbo xylate
film. The current efficiency is now higher than 90% over the entire
caustic co ncentratio n regio n studied, altho ugh a minimum and
maximum in perfo rmance is again o bserved. These features are
shifted to lo wer co ncentratio n co mpared to perfluo ro sulfo nate
behavio r tho ugh. Finally, the perfo rmance of a sulfo nate-carbo x-
ylate bilayer membrane, Nafion 901, is plo tted in Fig. 18. Fo r such
Na fi o n 120 85 C 4 k A/m
2
475
Figure 16. Sodium ion transpo rt number for Nafion 120 vs. brine anolyte
and caustic catho lyte co ncentratio ns (Ref. 170)
a material, the mo re permselective carbo xylate layer faces the
catho lyte so lutio n. Perfo rmance in this co nfiguratio n sho uld be very
similar to that of the carbo xylate film alo ne, acco rding to the
treatment by Krishtalik.
77
Similarities are evident in Figures 17 and
18, in suppo rt of this co nclusio n.
3. Interpretation of P ermselectivity as a Function of M embrane
P roperties and C ell P arameters
Several appro aches to the understanding of membrane permselec-
tivity can be taken; these include the use of the Nernst-Planck
transpo rt equatio ns,
72117
'
212
irreversible thermo dynamics,
35
and
0.8 -
0 2 4 6 8 10 12
NaOH CONCENTRATION, mol L"
1
Figure 17. Sodium ion transpo rt number vs. caustic catho lyte
so lutio n for a perfluo rinated carbo xylate membrane: ()
ano lyte is 5 M NaCl; and (O) ano lyte and catho lyte are
identical co ncentratio ns of NaOH. (Ref. 149; reprinted by
permission of the publisher, The Electrochemical Society,
Inc.)
theo ries which inco rpo rate mo rpho lo gical and chemical pro perties
of these perfluo rinated io no mers to explain perfo rmance. Emphasis
is placed on the latter type here, for these pro vide some insight
into the mo lecular basis of permselectivity.
The dependence of current efficiency on po lymer structure was
first analyzed by Gierke,
45
based on his cluster-channel mo del
(Sectio n II. 4). The current efficiency is given as the ratio of catio n
flux to to tal io nic flux. The flux is determined by the io n mo bility
and the io n co ncentratio n in the membrane, and the po tential
barrier. He calculated the size of the electro static po tential energy
barrier from the Po isso n-Bo ltzmann equatio n. This barrier energy
is added to the activatio n energy for migratio n. He emplo yed
abso lute rate theo ry to describe the relative reductio n in anio n
mo bility. The mo del co rrelates well the increase of current efficiency
with increase of po lymer EW by co nsidering the relative mo bilities
as a semiempirical and adjustable parameter. Reiss and Bassig-
nana
117
have, ho wever, po inted o ut many sho rtco mings of Gierke's
appro ach.
Several new develo pments in interpreting the transpo rt pro per-
ties, based o n the structural parameters, have been repo rted by Ko h
477
Na fi o n 901 90C 2 k A/m
2
1.00
n
0.95 -
0.90-
0.85 -
Figure 18. Sodium ion transpo rt number for Nafion 901 vs. brine ano lyte and
caustic catho lyte co ncentratio ns. (Ref. 168; reprinted by permissio n of the
and Silverman,
72
Reiss and Bassignana,
117
and Yeo .
183
These results
generally suggest that the high lo cal co ncentratio n of fixed io n (o r
surface charge density) in these perfluo rinated io no mer membranes
is the primary facto r in pro viding the extrao rdinary permselectivity
in co ncentrated so lutio ns.
Mauritz and co -wo rkers
60
'
74
'
75
'
93
'
94
and Ho pfinger
61
have repo r-
ted spectro sco pic and so rptio n studies of perfluo ro sulfo nate mem-
branes. Several co nclusio ns drawn in these studies are useful in the
interpretatio n of current efficiencies as a functio n of caustic so lutio n
co ncentratio n. So rptio n measurements of an 1100-EWfilm in equili-
brium with NaOH so lutio ns from 7.5 to 18 M show that the
NaOH/SO
3
Na ratio remains virtually co nstant at abo ut 0.27. Mem-
brane water co ntent decreases with increasing so lutio n co ncentra-
tio n tho ugh, so that a steadily decreasing water-to -io n ratio results.
This ratio indicates that even the primary hydratio n requirements
of Na
+
, OH~, and sulfo nate io n-exchange sites are no t met within
the membrane over most of this co ncentratio n range. A co ntinuo us
infrared abso rbance belo w 3500 cm"
1
is assigned to pro to n tunnel-
ing events in the H3O2 gro uping. Fo r a 1500-EW membrane, this
co ntinuo us abso rbance initially rises with caustic co ncentratio n
but goes thro ugh a maximum at abo ut 10 M. A sharp minimum in
abso rbance is o bserved at 14 M so lutio n co ncentratio n, followed
by an abrupt increase. Thus, the co ncentratio n dependence of this
infrared abso rbance is no tably similar to that of current efficiency
for a perfluo ro sulfo nate film (Figs. 14-16). If the magnitude of
co ntinuo us abso rptio n is indicative of the extent of hydro xide
transpo rt by a type of Gro tthus chain mechanism, then a qualitative
explanatio n for the co mplicated co ncentratio n dependence of cur-
rent efficiency co uld be pro vided.
As discussed by Mauritz and Gray,
94
the initial rise in infrared
abso rbance at lo wer caustic co ncentratio n is simply due to the o nset
of NaOH so rptio n into the po lymer. With increasing so lutio n co n-
centratio n and membrane dehydratio n, ho wever, pro to n tunneling
events decrease. In this co ncentratio n regio n, the remaining water
mo lecules wo uld be present mainly in so lvent-separated io n pairs.
Here the electro static field of the io n pair wo uld serve to lo calize
pro to n po sitio n and reduce the frequency of tunneling events. At
the highest external so lutio n co ncentratio ns, pro to n transfer pro ces-
ses are suspected to o ccur between sulfo nate gro ups and the remain-
ing water mo lecules in the po lymer, yielding the final increase in
abso rbance. Thus the co mplicated co ncentratio n dependence of
current efficiency for perfluo ro sulfo nate membranes, referred to
abo ve, may be a reflection of the dependence of vario us pro to n
tunneling mechanisms o n the amo unt of hydratio n water in the
membrane.
An impo rtant questio n is why the perfluo rinated carbo xylate
po lymer presents a much mo re effective barrier to hydro xide io n
transpo rt co mpared to the sulfo nate analo gue, for any caustic
co ncentratio n used. There may be several facto rs invo lved. First, a
mo re co mplete phase separatio n of the io n-clustered regio ns for
the carbo xylate, as inferred from vario us types of measurements,
wo uld be expected to increase the degree of rejectio n in terms of
the cluster-netwo rk mo del. Smaller cluster sizes, larger numbers of
interco nnecting channels, and less uninco rpo rated exchange sites
and water wo uld all lead to mo re effective hydro xide blo ckage.
Also , the lo wer inherent water co ntent and higher exchange-site
charge density for the carbo xylate po lymer pro duce a greater extent
of io n pairing. As co ncluded from infrared studies, this disco urages
pro to n tunneling events which enhance hydro xide io n migratio n.
Ultimately tho ugh, carbo xylate-water interactio ns wo uld be expec-
ted to reduce permselectivity at highest caustic strengths, in analo gy
to sulfo nate-water interactio ns. Thus a co mbinatio n of differences
in mo rpho lo gy and water so rptio n are seen as central facto rs in the
relative permselectivities of perfluo rinated carbo xylate and sulfo -
nate po lymer membranes.
Electro o smo tic effects also influence current efficiency, no t
only in terms of co upling effects on the fluxes of vario us species
but also in terms of their impact on steady-state membrane water
levels and po lymer structure. The effects of electro o smo sis on
membrane permselectivity have recently been treated thro ugh the
classical Nernst-Planck flux equatio ns,
213
and water transpo rt num-
bers in chlo r-alkali cell enviro nments have been repo rted by several
wo rkers.
35
"
37
'
73
'
86149164
'
213
'
214
Even with classical appro aches, the
relatio nship between electro o smo sis and permselectivity is seen to
be quite co mplicated.
213
Treatments which include mo lecular trans-
po rt of water can also affect membrane permselectivity, as seen in
Fig. 17. The different results for the two types of experiments here
can be attributed largely to the effects of o smo sis. A slight impro ve-
ment in current efficiency results when o smo sis o ccurs from ano lyte
to catho lyte. Ano ther frequently o bserved co nsequence of water
transpo rt is higher membrane co nductance,
133146
'
214
which is an
impo rtant facto r in the o verall energy efficiency of an o perating cell.
V. C O N DUC T I VI T Y A N D P E R M E A B I L I T Y
I N M E M B R A N E S
The perfluo rinated io no mer membranes are widely used as
separato rs in electro lytic and fuel cells. A primary co nsideratio n
in such applicatio ns is the membrane co nductivity, because o hmic
lo sses due to membrane resistance can significantly increase energy
co nsumptio n of the electro lytic cell and energy lo ss of the fuel cell.
Extensive studies of the co nductivities of co nventio nal Nafio n
membranes in vario us industrially impo rtant electro lytes have been
carried o ut in several labo rato ries in recent years. The co nductivity
of the carbo xylate membranes has been studied o nly in alkaline
electro lytes because of its primary applicatio n in the chlo r-alkali
industry.
1. C onductivity in P ure W aterS olid P olymer E lectrolyte S ystems
In the dry state Nafio n behaves like an insulato r.
63183
Ho wever,
the membrane beco mes co nductive when hydrated. Figure 19 sho ws
the co nductivity of hydrated Nafio n,
183
alo ng with that of several
po lymers co ntaining sulfo nic acid gro ups,
8116
'
215
as a functio n of
water co ntent. The Nafio n po lymer beco mes co nductive when it is
expo sed to the atmo sphere and abso rbs ~6H
2
O/SO^ of mo isture.
It has been sho wn that membranes with this amo unt of hydratio n
have sufficient co nductivity for use as a semiso lid pro to n co nducto r
in WO
3
-based electro chro mic displays.
116
The water co ntent o f the
membrane further increases after immersio n in water, resulting in
higher co nductivity. This membrane co nductivity is regarded as the
intrinsic co nductivity because it stems from the stro ng acidity of
the materials [Sectio n II. 5(iv)]. The so lid curve is calculated from
the Bruggemann equatio n
216
:
K=0.54K
e
(l-V
p
)
15
(11)
where V
p
is the vo lume fractio n of po lymer and K
e
is co nsidered
as the co nductivity of sulfuric acid with co ncentratio n equal to that
of the sulfo nic acid gro up of the membrane. Equatio n (11) implies
that K is a stro ng functio n of V
p
. This is suppo rted by the fact that the
co nductivity of the E-fo rm membrane is higher than that of N-fo rm
samples, despite the fact that the latter has a higher value of K
e
.
lS3
Table 6 co mpares the co nductivity of vario us po lymers and
electro lytes co ntaining sulfo nic acid gro ups. The intrinsic co nduc-
tivity of Nafio n is high and is very similar to o ther po lymers
co ntaining sulfo nic acid gro ups. The activatio n energy of pro to n
co nductio n of Nafio n is lo w in co mpariso n with o ther po lymers,
481
O
o
'e 6
Q
O
O
<
Q:
GD
2 -
10 20 30
Figure 19. Co nductivity of io n-co ntaining polymers as a
function of water co ntent: (O) Nafion; ( ) calculated
from Eq. (11); ( ) po lystyrene sulfonic acid; ( )
po ly-2-acrylamido -2-methylpro pane sulfonic acid;
( ) po lyethylene sulfo nic acid. (Ref. 182; reprinted
by permissio n of the publisher, The Electrochemical
Society, Inc.)
presumably because the water in Nafion is no t stro ngly hydro gen
bo nded [Sectio n II. 5(iii)]. This high intrinsic co nductivity, to gether
with the stro ng hydro philicity [see Sectio n II. 5(ii)], makes Nafion
an excellent "electro lyte" for many electro chemical applicatio ns.
At present, this po lymer is emplo yed as the SPE in many
electro chemical cells.
217
Besides, many new ideas of using this
po lymer as electro lyte have been suggested. It has been shown that
Nafion has po tential for use as a so lid "superacid" catalyst for
many electro o rganic syntheses
67103
"
107
as well as a co nductive po ly-
mer co ating for electro des.
26
'
27
'
58
'
89126157
In SPE cells, electro catalyst particles are bo nded to the mem-
brane surfaces. It is impo rtant to mentio n that go o d bo nding
T able 6
C onductivity for S ome I on-C ontaining P olymers in W ater
0
Po lymers
Nafio n
AMPS*
PESA*
PSSA
/
PSA
g
IEC
b
0.83
1.97
2. 00
K
(O"
1
cm"
1
)
0.06
0.03
0.08
0.09
0.04
E
a
c
9. 41
19.25
19.25
References
183
116
116
8
8
a
Fro m Reference 182.
b
IEC is the io n-exchange capacity (meqg-po lymer"
1
).
c
E
a
is the activatio n energy (kJ mo P
1
).
d
AMPS is po ly-2-acrylamido -2-methylpro pane sulfo nic acid (water so luble).
e
PESA is po lyethylene sulfo nic acid (water so luble).
f
PSSA is po lystyrene sulfo nic acid.
g
PSA is pheno l sulfo nic acid.
between electro de and membrane is essential, because any water
film and gaseo us pro ducts which exist between the electro de and
membrane surface can pro duce an extremely high co ntact resist-
ance. Altho ugh deio nized water is the only fluid circulated thro ugh
the SPE water electro lyzer, the enviro nment that the electro des
enco unter is highly acidic. The sulfo nic acid gro ups at the membrane
surfaces pro duce an acidity equal to 20 wt % sulfuric acid [Sectio n
II. 5(iv)]. Because of this acidic medium, acid-resistant no ble metals
o r their o xides are utilized as ano de materials,
156
'
218
while platinum
serves as the catho de material.
79
The perfluo rinated carbo xylic acid membrane exhibits a higher
resistance than Nafion membranes in SPE water electro lyzers.
219
This is primarily due to small membrane swelling and slight disso ci-
atio n of the carbo xylic acid gro up in water o r acid electro lyte with
a pH < 2.
178181
2. C onductivity in A cidic E lectrolytes
The co nductivities of Nafion in HC1 and HBr have been studied
extensively by Yeo et a/.
174175
Results for E-form Nafion in HBr
are given in Fig. 20. There are several features no tewo rthy. First,
membrane co nductivity is abo ut o ne o rder of magnitude less than
the electro lyte co nductivity due to the large vo lume fractio n of
14 | 1 14
483
10 20 30 40
HBr CONCENTRATION wt %
LL)
f -
>
uJ
- 2
50
Figure 20. Membrane ( ) and free-acid ( ) co nduc-
tivity as a function of HBr co ncentratio n: () H
2
O and (O)
HBr. (Ref. 175; reprinted by permissio n of the publisher,
The Electro chemical Society, Inc.)
no nco nductive material in the membrane. Seco nd, the membrane
has a maximum co nductivity at lo wer acid co ncentratio n as o ppo sed
to the co nductivity maximum for the acids. This maximum co nduc-
tivity o ccurs because the hydro gen io n co ncentratio n decreases at
low acid co ncentratio ns and the water co ntent of the membrane
decreases with increasing acid co ncentratio ns. Ano ther salient
feature is that, for electro lytes of less than 0.3 in mo larity, the
membrane co nductivity is higher than the electro lyte co nductivity
because the intrinsic co nductivity of the membrane beco mes
18^
impo rtant.
If o ne co nsiders that the mo bility for diffusion is the same as
that for co nductance, which is particularly true for the cases of
water and dilute so lutio ns, then the diffusivity can be related to the
484 R ichard S . Yeo and H oward L . Y eager
conductivity by the Nernst-Einstein equatio n
220
:
1000K RT
l
~ D F
2 (12)
where K is the equivalent co nductance and C, is the co ncentratio n
of the mo bile io ns; R, T, and F have their usual meanings. The
co nductivity of Nafion in varying HCl electro lytes has been repo rted
previo usly,
174
while the diffusivity data was shown in Table 3.
Hence, the co ncentratio n of mo bile io ns in Nafion in equilibrium
with vario us HCl co ncentratio ns can be calculated from Eq. (12)
and the results are shown in Table 7. The co ncentratio n of fixed
io ns calculated from Eq. (8), based on the io n-cluster mo del are
also included in Table 7 for co mpariso n. It is clear that the transpo rt
data suppo rt the io n-cluster mo rpho lo gy suggestio n for Nafion
[Sectio n II. 3(ii)].
As expected, the membrane co nductivity is impro ved at ele-
vated temperatures
174
due to the increase in electro lyte uptake and,
to a lesser degree, the increase of the electro lyte co nductivity. An
impro vement in the perfo rmance of HCl cells by the better mem-
brane co nductivity at elevated temperatures has been o bserved.
221
This is an excellent example since the electro de kinetics of the
hydro gen and chlo rine reactio ns are fast and the only "o verpo ten-
tial" is o hmic.
The co nductivity of these perfluo rinated membranes has been
fo und to be affected stro ngly by the histo ry of treatment of the
membrane.
174175
As shown in Table 8, the co nductivity increases
in the o rder S-form <N-fo rm < E-form. It is apparent that elec-
T able 7
C omparison of I onic C harge C oncentrations Derived from
T ransport and Uptake M easurements
0
Electro lyte Calculated fro m Calculated fro m
co ncentratio n Eq. (8) Eq. (12)
0% HCl 5.21 mo l dm"
3
8.08 mo l dm"
3
10% HCl 7.13 12.05
20% HCl 9. 40 11.52
25% HCl 11.21 12.76
a
T able 8
E ffect of P retreatment on C onductivity
of N ation M embrane in 24% HB r"
Sample
E-fo rm
N-fo rm
S-fo rm
b
a
Fro m Reference
b
Dried in vacuum
W
e
25. 9
17.8
11.4
175.
at 140C.
K
0.098
0.076
0.035
tro lyte uptake is an impo rtant facto r in determining membrane
co nductivity and the vo ltaic efficiency of many membrane cells.
Yeo and Chin
175
have o bserved that the membrane hysteresis
effect o ccurs when the change of electro lyte co ncentratio n is faster
than the change of co ncentratio n in the membrane, which is co ntro l-
led by the diffusion of electro lyte in the membrane. The electro lyte
co ntent in the membrane do es no t reach its equilibrium value under
this co nditio n. The autho rs have thus suggested vario us metho ds
for co ntro lling this hysteresis effect and the electro lyte co ntent of
the membrane, so that a higher cell efficiency can be o btained.
3. C onductivity in A lkaline E lectrolytes
Most studies of membrane co nductivity in alkaline electro lytes have
been carried o ut in co ncentrated so lutio ns.
63
'
77
'
96133
'
142
'
146
'
176
'
222
The
co nductivity of Nafion in co ncentrated alkaline so lutio ns is gen-
erally o ne o rder of magnitude smaller than that in pure water o r
in acid electro lytes, because the membranes abso rb far less elec-
tro lyte when in neutralized form, as sho wn by Eq. (6).
The effect of NaOH co ncentratio n and temperature on the
swelling and co nductivity of Nafion has been recently studied by
Men'shako va et al.
96
The influence of NaOH co ncentratio n on the
membrane co nductivity is rather similar to the case of acid elec-
tro lytes in that a co nductivity maximum o ccurs. The autho rs fo und
that the co nductivity maximum of the membrane is at 20% NaOH,
i.e., close to the co ncentratio n where o ne o bserves the co nductivity
maximum of the free electro lyte.
96
Ho wever, the co nductivity
decrease fo llo wing the maximum is mo re drastic in the membranes
than in so lutio ns of the same co ncentratio n. The low co nductivity
of co ncentrated so lutio ns is ascribed to the less hydrated state of
the membrane. It has been po inted o ut that this is evidence for
stro nger binding of the mo bile io ns by the matrix at lower water
co ntents in the matrix.
It has been recently repo rted
142
that Nafion membranes show
an o hmic behavio r in 5 M NaOH, while in 10 M NaOH so lutio n
the specific co nductance of the membranes increases with increasing
current density. It is suggested that the passage of high currents at
a severely dehydrated membrane may pro duce mo rpho lo gical
changes that alter the character of the io nic co nductio n paths in
the po lymer. Hsu et al
63
have o bserved that the membrane co nduc-
tivity of Nafion in alkaline electro lyte exhibits io n perco latio n
behavio r and can be described by
* = i c
e
(l - V
P
- V
T
)
1 5
(13)
where V
T
is the thresho ld vo lume fractio n of the aqueo us phase
and K
e
is the electro lyte co nductivity. There is an (io nic) insulato r-
to -co nducto r transitio n in Nafion aro und V
T
. Based o n the perco la-
tio n theo ry, V
T
is 0.15 whereas an experimental value of 0.10 for
Nafion in NaOH electro lyte is o bserved. It is interesting to no te
that Eq. (13) resembles the Bruggeman equatio n and Eq. (11) if
V
T
= 0.
The Flemio n membrane behaves so mewhat differently in that
the co nductivity maximum appears at a co ncentratio n of less than
12 wt % NaOH.
146
The membrane co nductivity decreases with
increasing caustic co ncentratio n; this is ascribed to the decrease in
io nic mo bility which is caused by the loss of water in the membrane.
The very low value of the co nductivity and the high value of the
activatio n energy in a 40% caustic so lutio n implies that there exists
a stro ng interactio n between co unterio ns and fixed io ns in the
membrane. Figure 21 co mpares the co nductivity of the sulfo nate
and carbo xylate membranes in NaOH. Fo r the same IEC and
electro lyte co ncentratio n, the sulfo nate membrane is mo re co nduc-
tive than the carbo xylate membranes,
133146
primarily because sul-
fo nate samples abso rb mo re electro lyte. Ho wever, the carbo xylate
membranes of high IEC exhibit higher co nductivity than the sulfo-
nate samples because the IEC of the carbo xylate materials can be
higher than that of the sulfo nate po lymer in membrane forms.
487
ACID TYPE
I I I
J_
0 8 10 12 14 16 18
ION EXCHANGE CAPACITY, meq/g
2 0
Figure 21. Dependence o f membrane co nductivity o n io n-
exchange capacity fo r perfluo ro sulfo nate and carbo xylate
membranes, in 35% NaOH, at 90C. (Ref. 146; reprinted by
permissio n o f the publisher, The Electro chemical So ciety, Inc. )
Yeo et al. have repo rted
176
an analysis of the co nductivity of
Nafion in different alkaline electro lytes, based on the co rrelatio n
of membrane co nductivity with water co ntent. The analysis reveals
that larger co nductivities arise when the membranes are equilibrated
with NaOH so lutio ns than with KOH so lutio ns of equal mo larity.
Also , it is sho wn that better co nductivity can be realized with thinner
and lo wer-EW membranes. These effects have been pro ven in an
alkaline-water electro lyzer
176
and in relatio n to the co nductivity
T able 9
E ffect of P retreatment on C onductivity of N afion
M embrane in 40% K O H
a
Temperature
(C)
100
150
150
175
200
Pressure
(atm)
1.0
4.9
35. 2
35. 2
703. 0
(wt %)
28. 2
38.8
86. 4
116.2
370. 0
K
( I T
1
cm"
1
)
1.15 x 10"
4
0.011
0.046
0.071
0. 200
a
488
R ichard S . Y eo and Howard L . Y eager
results of Bratin and To mkiewicz.
23
It has been repo rted
142
'
222
that
the co nductivity of Nafion membrane can be increased co nsiderably
by so aking the membrane in water at temperatures above 100C
and at elevated pressure, as shown in Table 9. The membrane is
fully swo llen and the electro lyte uptake is high with such pretreat-
ments. In general, membrane co nductivity exhibits Arrhenius
behavio r: the activatio n energy data for io n co nductio n of Nafion
in vario us electro lytes are summarized in Table 10, whereas in Table
11 data are co mpared for carbo xylate and sulfo nate membranes.
T able 10
C onductivity of N afion M embrane of 1200 EW in Various
E lectrolytes"
Electro lyte
co ncentratio n
H
2
O
H
2
O
H
2
O
5% HC1
10% HC1
15% HC1
22% HC1
26% HC1
30% HC1
37% HC1
4. 5% KC1
25% NaCl
5.4% KOH
0. 4% NaOH
5% NaOH
10% NaOH
20% NaOH
30% NaOH
40% NaOH
17% NaOH
30% NaOH
Electro lyte
uptake
7.8
17
30
12.9
11.9
10.5
8.8
7.8
6.8
4.8
7
10
6.0
12.8
12.1
9.6
8.4
8.1
Co nductivity
at 25C
( xl 0
3
f t "
1
cm"
1
)
22. 8
52.2
68. 0
58.8
62. 5
46
23
14.3
6.8
3.9
3.93
5.3
1.7
5.7
6.0
9.3
9.7
6.0
1.0
F
b
9.46
9.46
9.37
10.33
11.59
10.75
11.59
16.95
13.47
15.69
12.07
17.74
25. 02
15.43
14.86
13.08
15.43
17.79
10. 0
c
10. 0
c
References
183
183
183
174
174
174
174
174
174
174
49
49
82
77
96
96
96
96
96
142
142
a
b
E
a
is the activatio n energy (kJ mo P
1
).
c
Fo r Nafio n o f 1150 EW and a temperature range o f 100-180C.
T able 11
C onductivity of P erfluorinated Ionomer M embranes in
35% N aO H
fl
Membrane
Sulfo nate
Carbo xylate
Io n-exchange
capacity
(meqg"
1
)
0.82
0. 91
1.23
1.48
1.70
1.88
Co nductivity
at 25C
1.6
21
2.3
8.5
87
300
Activatio n
energy
(kJ mo P
1
)
38
40. 6
64
60
50
43. 5
a
4. C onductivity of N afion in P rotic S olvents
The membrane co nductivity of Nafion in vario us pro tic so lvents
has been measured in a recent study
179
and the results are given in
Table 12. The ratio of the membrane co nductivity (K) to the so lvent
co nductivity (K
C
) is listed in the last co lumn of the table. A plo t of
the co nductivity ratio (K/K
) VS. the so lubility parameter of the

so lvent is sho wn in Fig. 22. The membrane co nductivity is higher
than the so lvent co nductivity in all so lvents except fo rmamide,
T able 12
C onductivity of N -form N afion in P rotic S olvents"
So lvent
Water
6
Fo rmamide
Glycero l
Ethylene clyco l
Methano l
Ethano l
1-Pro pano l
2-Pro pano l
i-Amyl alco ho l
So lubility
parameter
c
23. 4
19.2
16.5
14.6
14.5
12.7
11.9
11.5
10.0
(I T
1
cm"
1
)
1.6 x 10"
6
4. 3 x 10~
4
4. 4 x 10~
6
1.6 x 10"
6
2. 3 x 10"
5
1.66 x 10~
6
1.72 x 10~
6
2.7 x 10"
6
1.9 x 10"
6
K
((T
1
cm"
1
)
6.8 x 10~
2
1.6 x 10"
4
7.5 x 10"
6
1.1 x 10~
5
6.8 x 10"
5
1.94 x 10~
5
1.88 x 10~
5
1.17 xlO"
5
2. 9 x 10"
6
K/K
4 xl O
4
0.4
1.7
6.9
2.2
11.7
10.9
4. 3
1.5
a
b
E-fo rm.
c
Units: (cal/cc)
1/ 2
.
490
R ichard S . Y eo and H oward L . Y eager
6 10 14 18 22
SOLUBILITY PARAMETER OF SOLVENT,
(cal/ccV'a
Figure 22. Co nductivity ratio ( K / K
e
) o f Nafio n vs. so lubility
parameter o f so lvents. (Ref. 179; reprinted by permissio n
o f the publisher, The Electro chemical So ciety, Inc. )
presumably because of the high disso ciatio n of the io nic gro ups in
these pro tic so lvents and the appearance of the intrinsic co nduc-
tivity. Also , the membrane exhibits an extrao rdinarily high co nduc-
tivity in water. This is the reaso n why this material is used as an
"electro lyte" layer in SPE cells (see Sectio n V. I).
5. P ermeation of M olecular S pecies
The passage of a gas thro ugh a membrane takes place via a diffusion
mechanism. The gas disso lves in the membrane on the high-pressure
side, and deso rbs o ut of the membrane o n the lo w-pressure side.
The electro lyte uptake of the membrane plays an impo rtant ro le in
gas diffusion since it is primarily in the aqueo us phase that the gas
disso lves. The co ulo mbic lo ss in the cell is related to the membrane
diffusion current, which is determined by the permeatio n of the
gases and is given by
i
D
= nFDcjL (14)
where D is the diffusion coefficient, c
0
the co ncentratio n of the
491
species in the membrane, and L the thickness o f the membrane; n
and F have their usual meanings.
(i) Diffusion of Hydrogen and Oxygen in Nafion
The permeability o f hydro gen and o xygen thro ugh the mem-
brane co ntributes to parasitic po wer lo ss and may affect lo ng-life
perfo rmance o f cells such as water electro lyzers and hydro gen-
o xygen fuel cells. The permeatio ns o f hydro gen and o xygen thro ugh
Nafio n have been studied by LaCo nti et al
19
The permeabilities o f
bo th hydro gen and o xygen increase with increasing temperature
and with increasing membrane water co ntent, as sho wn in Figures
23 and 24. Furthermo re, the permeatio n rates o f these mo lecular
species also increase with increasing cell o perating pressure
223
and
with thinner membranes.
e
"5
1600
1200
C D
< 800
<r
i?i 400
cr
Q
>
80C
I I
0 10 20 30
WATER CONTENT, wt % dry polymer
Figure 23. Hydrogen permeability of Nafion as a
function of membrane water co ntent. (Ref. 79;
reprinted by permissio n of the publisher, The
Electro chemical Society, Inc.)
800
o
I 600
400
CD
<
LU
rr
LJ
a.
z
UJ
X
o
200
0
8OC
0 10 20 30
WATER CONTENT, wt % dry polymer
Figure 24. Oxygen permeability of Nafion as a func-
tio n of membrane water co ntent. (Ref. 79; reprinted
by permission of the publisher, The Electrochemical
Society, Inc.)
(ii) Diffusion of Chlorine and Bromine in Nafion
Nafion membranes have been used as separato rs in the hydro -
gen-chlo rine cell,
174
hydro gen-bro mine cell,
175
and zinc-bro mine
cell
158
because of their excellent chemical inertness in these
aggressive enviro nments. The functio n of the separato r in these
cells, similar to that in a water electro lyzer, is the separatio n of the
mo lecular species, such as hydro gen, chlo rine, bro mine, and metal-
lic zinc, which cause self-discharge and efficiency loss when they
migrate acro ss the separato r.
Yeo and McBreen
174
measured the diffusion coefficients of
hydro gen and chlo rine in Nafion immersed in HCl so lutio ns, and
that of bro mine in HCl and HBr so lutio ns as a functio n of electro lyte
co ncentratio n and temperature. In co ncentrated HCl so lutio ns, the
o rder of diffusion coefficients is hydro gen > chlo rine > bro mine,
as expected from the mo lecular sizes. Activatio n energies for
diffusion of hydro gen and chlo rine in 4.1 M HCl were fo und to be
21.6 and 23.3 kJ mo l"
1
, respectively, over the temperature range of
25-50C. These values are very similar to tho se for water diffusion
in the same membrane in dilute so lutio ns (see Section III. l). Figure
25 shows the diffusion coefficients of chlo rine and bro mine in
Nafion for varying acid co ncentratio n. The diffusion rate decreases
with increasing acid co ncentratio n. This is due to the decrease of
the electro lyte co ntent, as shown in Fig. 5.
Table 13 presents data for permeatio n of vario us diffusants
and electro lytes in Nafio n. At atmo spheric pressure, the permeatio n
rate of chlo rine is higher than that of hydro gen even tho ugh hydro -
gen has a much higher diffusivity. This is due to the higher c
0
value
for chlo rine. In the case of chlo rine and bro mine in HCl, the c
0
Figure 25. Diffusion coefficients of
chlo rine and bro mine in Nafion of
1200 EW as a function of acid con-
centratio n. Diffusant/so lvent com-
binatio ns are: (x) C1
2
/HC1; (A)
Br
2
/HCl; and ( ) Br
2
/HBr. (Ref.
174; reprinted by permissio n of the
publisher, The Electro chemical
Society, Inc.)
2 4 6
ELECTROLYTE
8 10
MOLARITY
12
T able 13
P ermeation of H alogens in N afion M embrane
0
Diffussant/
Electro lyte
H
2
Br
2
Cl
2
(sat. )/15% HC1
Br
2
/15% HC1
Br
2
(sat. )/12% HBr
Br
2
/3% HBr
Br
2
/24% HBr
Br
2
/36% HBr
Br
2
/48% HBr
Electro lyte
15% HC1
12% HBr
15% HC1
15% HC1
12% HBr
3% HBr
24% HBr
36% HBr
48% HBr
(mAcm )
0.125
3.57
0.2
0.26
1.60
0.05
0.25
0.03
0. 0135
(mo l dm~
3
)
0. 11
0.138
2.32
0.148
0. 114
0.095
0. 114
C
0
/Coo
1.0
0.99
0.27
0. 14
0.11
0.23
0.22
a
b
i
D
is the steady-state diffusio n current [see Eq. (14)].
value is very much equal to the measured co ncentratio n in the
electro lyte (Coo). Ho wever, in the case o f bro mine in HBr, c
0
is less
than Coo. Figure 26 sho ws a plo t o f c
0
vs. Coo fo r 12% HBr at 25C.
Fo r this case, c
0
is abo ut 40% o f c^. These pheno mena o ccur
because o f the fo rmatio n o f co mplex Br^ and Br^ io ns in bro mide
0.01
0.01
o, mo le/liter
Figure 26. A plo t o f c
0
us. c^ fo r bro mine in 12% HBr diffusing
thro ugh Nafio n 120 membranes at 25C. (Ref. 174; reprinted
by permissio n o f the publisher, The Electro chemical So ciety,
Inc. )
electro lytes. In HBr, the equilibria (Refs. 224-226) involved are
Br
2
+ Br ~^ Br
3
" K - 16
2Br
2
+ Br" ^ Br^ K - 40
whereas for Cl
2
in HC1,
227
'
228
it is
Cl
2
+ Cr^Cl
3
" K=0.2
The Do nnan effect in the catio n-exchange membrane inhibits the
migratio n of the negative co mplex io ns. Hence, halo gen permeatio n
in Nafion is lo wer than what might be expected from so lubility
co nsideratio ns. In the case of chlo rine, the increase of the so lubility
in HC1 at elevated pressures o ccurs by the fo rmatio n of CIJ io ns
so the self-discharge rate of hydro gen/chlo rine cells is no t expected
to increase linearly with chlo rine pressure. The co ulo mbic efficiency
of the halo gen-type cells is over 98%.
174
'
175
The effect of the co mplex tribro mide io n on bro mine per-
meatio n is also o bserved in o ther electro lytes. Will
158
has studied
bro mine diffusion in Nafion membranes for varying po lymer
equivalent weight, membrane pretreatment, and so lute co ncentra-
tio n. The electro lytes used in these experiments were either
2 M ZnBr
2
o r 4 M NaBr so lutio ns. The Br^ io n is the predo minant
bro mine species in such media, altho ugh mo lecular bro mine wo uld
appear to be respo nsible for transpo rt acro ss the membrane.
Measured diffusion coefficients of Br^ varied from 1 x 10~
8
to
5 x 10~
7
cm
2
s"
1
at ro o m temperature. Values increased significantly
with decreasing po lymer equivalent weight, increasing valency of
the catio n, and decreasing electro lyte co ncentratio ns. The per-
meatio n data exhibit a maximum i
D
in 35% ZnBr
2
so lutio n. This
maximum i
D
o ccurs because the Br^ co ncentratio n (c
0
) decreases
at low ZnBr
2
co ncentratio ns and the Br^ diffusion coefficient (D)
decreases with increasing ZnBr
2
co ncentratio ns [see Eq. (14)]. Fur-
ther, the coefficients for diffusion of Br^ in the sample pretreated
with acid, prio r to bo iling in water, is higher than that for the
sample that was subjected to bo iling in water alo ne (E-fo rm). The
E-form sample, in turn, exhibits better diffusivity behavio r than
that of the N-form samples. This again suppo rts the view that
membrane water co ntent is an impo rtant facto r in determining
membrane diffusion coefficients, even for diffusing species that are
uncharged.
496 Richard S. Yeo and H oward L . Y eager
(Hi) Diffusion of Sulfur Dioxide and Sulfides
Kimmerle and Breault
69
have studied the diffusion of SO
2
in
Nafion membranes, co nsidering the po ssible applicatio n in Li/SO
2
cells. Diffusion of SO
2
increases with lower-EW membranes and
with thinner samples. D
SOl
also varies with residual water co ntent.
Diffusion coefficients for aceto nitrile-bo iled (1 h) membranes were
up to twice as great as tho se (1-2 x 10~
7
cm
2
s~
1
) o bserved for
membranes bo iled o vernight. Also , aceto nitrile co ntaining 0.5%
H
2
O yields D
SO2
values abo ut twice tho se o bserved in dried CH
3
CN
so lutio n. This is because aceto nitrile can replace the water mo lecules
in the membrane, given sufficient time, and subsequent diffusion
within the po res is slowed do wn appreciably. The activatio n energy
of diffusion for SO
2
in Nafion of EW 1100 was fo und to be
23 kJ mo l"
1
o ver the temperature range of 20-60C.
Bratin and To mkiewicz
23
have investigated a three-electro de
pho to electro chemical sto rage cell. They studied the transpo rt
pro perties of sulfide and polysulfide thro ugh Nafion in Na
2
S/ NaOH
so lutio ns. The diffusion coefficients for sulfide varied from 3 x 10~
9
to 1 x 10~
7
cm
2
s"
1
, depending on the equivalent weight and thick-
ness of the membrane, and the pH of the so lutio n. The pH of the
so lutio n affects the equilibrium between different sulfide species
(H
2
S, HS~, and S
2
~) in the Na
2
S so lutio n. It is difficult to determine
the actual species diffusing thro ugh the membrane. The measured
flux and diffusion coefficients of sulfide species include the diffusion
of H
2
S, HS~, and S
2
~, which is the to tal sulfide. Diffusion coefficients
for po lysulfide are o ne o rder of magnitude lower than tho se for
simple sulfide species, due to the larger size of the diffusing species
and to the higher charges on polysulfide io ns.
VI. C O N C LUS IO N
The develo pment of perfluo rinated io no mers for use as membranes
has been no tewo rthy bo th in techno lo gical and scientific terms. A
significant new directio n has been given to the electro lytic industries
due to the energy savings and enviro nmental impacts that are
realized when these membranes are used for electro synthetic appli-
catio ns. As the leading example, membrane cells can now pro duce
chlo rine-so dium hydro xide at less than 2000 kWh per metric to n,
which is no t attainable with mercury-cell o r diaphragm tech-
no lo gies.
143
With their co st effectiveness assured, further impro ve-
ments in membrane co nductivity and permselectivity co ntinue to
be repo rted.
143
'
211
Also , the use of these po lymers as so lid po lymer
electro lytes, and the design of cells which will o perate at current
densities up to 10,000 A m~
2
, are further inno vatio ns on the ho rizo n
in chlo r-alkali techno lo gy.
211
With these and o ther applicatio ns
which explo it the vario us unusual and no vel pro perties of these
materials, they are rapidly beco ming a techno lo gically impo rtant
class of po lymers.
In scientific terms, the unusual io n-clustered mo rpho lo gy of
the perfluo rinated io no mer po lymers has pro vo ked much interest.
Clearly, the micro phase-separated structure that is revealed thro ugh
vario us types of experiments is stro ngly related to their unusual
transpo rt pro perties. It is impo rtant to refine o ur understanding of
this relatio nship in o rder to explo it these materials in vario us
electro chemical applicatio ns.
Nafion is the o nly co mmercially available perfluo rinated
io no mer membrane. Altho ugh several o ther perfluo rinated catio n-
exchartge membranes have been manufactured by several Japanese
firms (as sho wn in Table 1), these membranes are no t custo marily
so ld witho ut the cell techno lo gies. Thus, the availability of perfluo ri-
nated io no mer membranes is rather limited and du Pont is currently
the sole so urce. The relatively high cost of these perfluo rinated
io no mer membranes precludes their applicatio ns in many
electro chemical cells where co st effectiveness is a major co ncern.
Besides, the synthesis and fabricatio n of a co rrespo nding perfluo ri-
nated anio n-exchange membrane has no t been repo rted yet. Kno wl-
edge of the relatio nship between the unusual io n-cluster mo r-
pho lo gy and the many unusual pro perties will be useful for the
develo pment of o ther, less expensive po lymer materials for an even
wider range of applicatio ns. This o bjective is therefo re related to
a central go al of membrane science itself: to design po lymer mem-
branes with specific dynamic pro perties from first principles.
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Index
Acceleratio n requirements, fo r electric ve-
hicles, 379
Activatio n energy, Fermi level effect o n,
111
Adso rptio n, o f no n-io nic mo lecules, 84
Adso rptio n effects, with io ns, 64
Agar, po tential dependence o f entro py o f
activatio n, 132
Aluminum-air system, 422
Anio n adso rptio n
at mercury, 157
at nickel, 159
Anio ns
adso rptio n at go ld faces, 73
specific adso rptio n effects o n transfer
co efficient, 156
Anio n effects, at single-crystal silver
faces, 69
Ano dic pho to deco mpo sitio n, pro tectio n
against, 231
Apparent activatio n energy, and Tafel
equatio n, 172
Apparent and real heats o f activatio n, 175
Apparent heat o f activatio n, 168
Back reflectio n pho to s, chart fo r, 14
Band edges, pinning of, 206
Barrierless discharge, 155
Batteries
fo r vehicular pro pulsio n, 371
high-temperature, 409
lithium-sulfur, 409
metal-air, 420
nickel-iro n, 396
Batteries (cont.)
with co nducting po lymer systems, 418
zinc, 399
zinc-halo gen, 402
Battery, lead/acid, 391
Battery classificatio n, 374
Battery materials, supply co nstraints of,
385
Battery requirements, fo r electric vehi-
cles, 373
j8 (symmetry facto r), 113
BDM theo ry o f so lvent o rientatio n, 139
Brine ano lyte, and so dium io n transpo rt
number, 477
Bro mine evo lutio n, at carbo n, 127
Br$nsted linear free-energy relatio ns, 112
b, Tafel slo pe parameter, 106
Butler, energy pro files, 109
Butler-Vo lmer equatio n, 108
Cadmium sulfide, as pho to electro de, 224
Capacity curves
and gro wth steps, 79
fo r no n-io nic adso rptio n, 85
Carbo xylate membranes, 468
Catio n-exchange membranes, perfluo ri-
nated, 439
Charge transfer mo del, o f SERS, 332
Chemiso rptio n energy, in po tential pro -
files, 109
Chlo r-alkali cell, membrane selectivity
fo r, 472
Clean co nditio ns, fo r interface studies, 2
Clo se-packed structures, 18
505
506 Index
Co inage metals, and SERS, 308
Co llo idal systems
excitatio n spectra fo r, 317
SERS effect fro m, 263
surface preparatio n in, 282
Co mpariso n o f electric vehicle batteries,
423
Co ncentrated so lutio n, diffusio n behavio r
in, 465
Co nducting po lymer systems, 418
Co nductivity
of membranes in pure water, 480
in membranes, 479
Co o rdinatio n numbers, in unit cells, 18
Co st facto rs, in battery develo pment, 384
Co verage effects, in multistep pathways,
161
Crystal cutting, 32
Crystallo graphic o rientatio n, 10
Crystallo graphy, o f metals, 4
Crystal po lishing, 33
Crystal structures, defects in, 27
Crystal surfaces
and stereo graphic pro jectio n, 6
mo dels of, 15
Cubic crystals, stereo graphic pro jectio n
of, 9
Cubic system
principal index faces of, 5
stepped surfaces in, 22
Cyanide, adso rptio n and SERS effect, 279
Cycle life and depth o f discharge, 388
Cyclic-vo ltammetry, fo r single-crystal
surfaces, 40
Defects, 27
Depth o f discharge and cycle life, 388
Diffusio n behavio r, in co ncentrated so lu-
tio ns, 465
Do nnan effect, and io n-exchange mem-
branes, 457
Do uble-layer
at semico nducto r interface, 201
at single crystals, 1
Do uble-layer capacity
at go ld surfaces, 54
at silver surfaces, 52
curves fo r, 46
Dye effects in SERS, theo retical, 344
Dyes, surface Raman scattering of, 297
Eisenberg, theo ry o f membranes, 442
Electrical energy term, in rate equatio n,
110, 135
Electric field enhancement mechanism, in
SERS, 336
Electric vehicle batteries
co mpariso n of, 423
near term and advanced, 424
Electric vehicle battery requirements, 373
Electro chemical po lishing, 34
Electro chemical po tential, of electro ns in
so lutio n, redo x systems, 191
Electro chemical systems
excitatio n pro files in, 314
SERS in, 259
surface preparatio n fo r SERS in, 273
Electro chemistry, o f semico nducto rs, 189
Electro de po tentials, scale of, 196
Electro de pro cesses, linear free energy re-
latio ns fo r, 111
Electro des
preparatio n o f single-crystal, 28
semico nducto r, new applicatio ns of,
236
semico nducto r, surface states at, 205
Electro de surfaces, characterizatio n of, 37
Electro lysis, with io n-exchange mem-
branes, 470
Electro lyte systems, so lid po lymer, 480
Electro n affinities, and flat-band po ten-
tials, 215
Electro n and particle transfer, Ulstrup
treatment, 147
Electro ns, electro chemical po tential of,
195
Energy efficiency, o f vehicular batteries,
388
Enhancement facto r, in SERS, 256
Enhancement, surface electro magnetic
wave, 337
Enhancement mechanism, o f SERS, elec-
tric field, 336
Entro py o f activatio n, 133
Agar's co mments o n, 132
and so lvent dipo le o rientatio n, 138
Index
507
Entro py o f activatio n (cont.)
fo r hydro gen evo lutio n reactio n, 180
fo r redo x reactio ns, 180
po tential dependence of, 133, 181
Entro py o f libratio n, at electro des, 140
Exchange capacity o f io n membranes, 445
Exchange currents, and Tafel slo pes, 164
Exchange sites, acidity o f in membranes,
455
Excitatio n pro files in SERS, 312
Excitatio n pro files o n films, 319
Excitatio n pro files, summary o f SERS,
321
Excitatio n spectra, in co llo idal systems,
317
FCC structure, unit stereo graphic triangle
fo r, 20
FCC system
higher index faces, 21
mo dels of, 17
FCC systems, 18
Fermi-Dirac statistics, in rate equatio n,
136
Fermi level effects, at electro des, 111
Fermi level pinning, 206
Field effect transisto r, io n selective, 243
Flat-band po tential, 210
and electro n affinity, 215
Fo rd, so dium-sulfur cell, 413
Gassing, o vercharge, 395
Gibbs energy o f activatio n, fo r electrode
pro cesses, 110
Go ld
anio n adso rptio n at, 73
hydro gen o xidatio n at, 42
Go ld electro de, SERS effect at, 308
Go ld surfaces, do uble-layer capacity at, 54
Gro wth of single-crystals, 28
Gro wth steps and capacity curves, 79
Gurney energy pro files, 109
Halides, and SERS effect, 292
Halo gen, zinc battery, 402
Halo gens, permeatio n in Nafio n, tabu-
lated, 494
Harmo nic po tential effects, 150
H C P systems, 18
Heat o f activatio n, apparent, 168
Heats o f activatio n, apparent and real, 175
Helmho ltz layer and temperature, 155
High-perfo rmance membranes, 438
High-temperature, batteries, 409
Histo rical aspects
o f io n-exchange cells, 437
o f single-crystal studies, 3
Hydro gen diffusion in Nafio n, 491
Hydro gen evo lutio n
at mercury, 117
at nickel, 120
Hydro gen evo lutio n reactio n, entro py o f
activatio n fo r, 180
Hydro gen o xidatio n, at go ld, 42
Industrial electro lysis, io n-exchange mem-
branes in, 470
Inner-layer capacity, 60
Interactio n, o f io ns with metal, 62
Interactio ns, o f neutral mo lecules at met-
als, 81
Interfaces, clean, 2
Inversio n layer, in semico nducto rs, 227
Io n and water diffusio n, in membranes,
459
Io n clustering, in membranes, 446
Io n-exchange capacity, 445
Io n-exchange membrane cells, histo rical
backgro und of, 437
Io n-exchange membranes, 437
acidity o f exchange sites, 455
and io n diffusio n, 459
and water diffusio n, 459
clustering in, 446
co nductivity of, 479
Do nnan effect in, 457
Eisenberg's theo ry, 443
industrial co nditio ns, 470
io nic cro ss-linking in, 447
micro structure of, 441
permeability of, 479
self-diffusio n in, 463
so lvatio n pheno meno n in, 450
so rptio n o f io ns and water, 468
Io nic cro ss-linking in membranes, 447
508 Index
Io ns
adso rptio n of, 64
facto rs in adso rptio n of, 64
Io n-selective field-effect transisto r, 243
Iro n sulfide, lithium battery, 410
Iso electric po int, 205
Laser etching o f semico nducto rs, 239
Laue metho d
for crystal o rientatio n, 12
X-ray go nio meter, 13
Lawrence Livermo re aluminum-air sys-
tem, 422
Lead/acid batteries, behavio r of, 387
Lead/acid battery, characteristics, 391
Levich mo del, fo r pro to n transfer, 145
Libratio n, entro py of, at electro des, 140
Lightening ro d effect in SERS, 337
Linear free-energy relatio ns, Br^nsted,
112
Linear free-energy relatio nship, fo r elec-
tro de pro cesses, 111
Liquid junctio n so lar cell, 225
Literature, o n semico nducto r electro des,
247
Lithium batteries, rechargeable, 417
Lithium iro n sulfide battery, 410
Lithium-sulfur batteries, 409
Mechanisms, o f SERS effect, 348
Membranes
co nductivity in acids, 482
co nductivity in alkali, 485
high perfo rmance, 438
io n-exchange, 437
permeability of, 479
permeatio n o f mo lecular species, 490
Membrane selectivity, in chlo r-alkali cells,
472
Mercury
hydro gen evo lutio n at, 117
Metal-air, batteries, 420
Metal/io n interactio ns, 62
Metals
crystallo graphy of, 4
exhibiting SERS, 307
structure of, 4
Metal surfaces
electro nic aspects, 24
structure of, 23
Mo dels
fo r |3, 113
o f crystal surfaces, 15
o f FCC system faces, 17
Mo lecules, permeatio n in membranes, 490
Mo tt-Scho ttky plo t, 211
Mo tt-Scho ttky plo ts, frequency depen-
dence of, 213
Multistep pathways
co verage effects in, 161
Tafel slo pes fo r, 160
Multistep reactio ns, Tafel slo pes for, 115
Nafion
applicatio ns of, 440
co nductivity in pro tic so lvents, 489
co nductivity of, 487
diffusion o f chlo rine and bro mine in,
492
diffusion o f sulfur dio xide and siilfides
in, 496
hydro gen and o xygen diffusio n in, 491
permeatio n o f halo gens in, tabulated,
494
so dium io n transpo rt number in, 474
state of water in, 455
structural mo dels of, 447, 450
Nafio n membranes, water uptake in, 451
Near term and advanced E. V. batteries,
424
Neutral mo lecules, metal interactio ns with,
81
Nickel
hydro gen evo lutio n at, 120
Nickel-iro n battery, 396
Nickel-zinc battery, as o ptimum system,
426
Nitro -co mpo unds, reductio n of, 130
No n-io nic adso rbates, 85
Organic co mpo unds, and SERS effects,
280
Orientatio n
crystallo graphic, 10
o f single-crystals, 13
Index
509
Overcharge, gassing o n, 395
Oxygen diffusio n in Natio n, 491
Oxygen evo lutio n, at platinum, 127
Oxygen reductio n, at platinum, 129
Particles, pho to electro lysis at, 222
Peak po wer, specific energy balance, 381
Perfluo rinated io n-exchange membranes,
437
Perfluo rinated membranes, develo pment
of, 439
Perfo rmance requirements, fo r vehicle
batteries, 375
Permeability, o f membranes, 479
Pho to ano de, fo r water splitting, 223
Pho to assistance, of water electro lysis, 238
Pho to cell, fo r electro lytic water splitting,
223
Pho to chemical pro cesses, at semico nduc-
to rs, 216
Pho to co rro sio n, 228
Pho to electro chemical co nversio n, o f so lar
energy, 236
Pho to electro chemical reactio ns, impo rtant
types of, 218
Pho to electro lysis, o f water at particles,
222
Pho to po tentials, o pen circuit, 226
Pinning o f band edges, 206
Platinum
o xygen evo lutio n at, 127
o xygen reductio n at, 129
Po lishing, electro chemical, 34
Po lymer systems, co nducting, 418
Po tential, flat-band at semico nducto rs, 210
Po tential dependence
o f activatio n entro py, 133
of entro py of activatio n, 181
of reactio n rates, 107
of SERS, 277
o f transfer co efficient, 148
Po tential distributio n, at semico nducto r
interfaces, 206
Po tentials o f zero charge, at single-crys-
tals, 45
Preparatio n o f single-crystal electro des, 28
Principal index faces, symmetries, 11
Pro tectio n o f semico nducto r interface, 231
Pro tic so lvents, co nductivity o f Nafio n in,
489
Pro to n transfer
Bell mo del of, 146
Levich mo del of, 145
Pro to n tunneling, 143
Purity requirements, fo r do uble-layer
studies, 2
Quadratic effects, in Tafel relatio n, 152
Quasi-Fermi levels, 216
Rago ne plo ts fo r specific po wer versus en-
ergy, 382
Raman reflectivity in SERS, 334
Raman scattering, see SERS effect, 297
surface enhanced, 253
Rate equatio n
Butler-Vo lmer, 108
Fermi-Dirac statistics in, 136
Reactio n rates, po tential dependence of,
107
Real and apparent heats o f activatio n, 175
Rechargeable batteries, co mmercially
available, tabulated, 373
Rechargeable lithium batteries, 417
Redo x co uple, electro chemical po tential
o f electro ns fo r, 191
Redo x reactio ns at electro des, 124
Redo x reactio ns, entro py of activatio n
fo r, 178
Relative surface energy, at single-crystal
surfaces, 48
Reo rganizatio n energy, o f a so lvent, 199
Reso nance mo dels, of SERS, 325
Ro ughness facto r, at surfaces, 94
Russian wo rk, o n electro chemistry o f
semico nducto rs, 189
Self-diffusio n in io n-exchange mem-
branes, 463
Semico nducting materials, characteriza-
tio n of, 245
Semico nducto r electro chemistry, litera-
ture o n, 247
Semico nducto r electro des
new applicatio ns of, 236
surface states at, 205
thermo dynamic stability of, 229
510 Index
Semico nducto r interface, do uble-layer at,
201
Semico nducto r interfaces, po tential distri-
butio n at, 206
Semico nducto rs
and pho to co rro sio n effects, 228
electro chemistry of, 189
flat-band po tential of, 210
laser etching of, 239
pho to electro chemical pro cesses at, 216
tunneling o f ho t electro ns fro m, 235
SERS, 253
and halides, 292
and surface preparatio n, 271
at metals, 307
co ntro versy o n o rigin of, 254
electric field enhancement mechanism,
336
electro de po tential dependence of, 277
enhancement facto r in, 256
excitatio n pro files in, 312
experimental studies, 255
from UHV systems, 264
image mo del, 325
in electro chemical systems, 259
lightning ro d effect in, 337
of water, 295
Raman reflectivity in, 334
reso nance mo dels of, 325
uses of, 350
SERS effect
from co llo idal systems, 263
o f adso rbed cyanide, 279
theo retical mo dels of, 322
with o rganic co mpo unds, 280
SERS enhancement facto r, values of, 256
SERS excitatio n pro files, o n films, 319
SERS mechanisms, 348
SERS mo del, charge transfer, 332
SERS studies, surface preparatio n fo r, 285
Silver
SERS effect at, 308
single-crystal surfaces, do uble-layer ca-
pacity at, 52
Silver surfaces, inner-layer capacity at, 60
Single-crystal faces
iso latio n of, 34
preparatio n of, 32
Single-crystal go ld surface, do uble-layer
capacity at, 54
Single crystals
do uble-layer at, 1
gro wth from metal vapo r, 30
gro wth fro m so lutio ns, 31
gro wth of, 28
o rientatio n pro cedure fo r, 13
po tentials o f zero charge at, 45
specificatio n o f principal index faces of,
11
Single-crystal studies, histo rical aspects,
3
Single-crystal surfaces
cyclic-vo ltammetry of, 40
do uble-layer capacity at, 46
electro chemical results, 43
surface energy of, 48
Smo o th surfaces, SERS effect, 269
So dium io n diffusio n, in membranes, 466
So dium io n transpo rt number in Nafio n,
474
So dium-sulfur cell, Fo rd, 413
So lar cell, liquid junctio n, 225
So lar energy, pho to electro chemical use of,
236
So lid po lymer electro lyte systems, 480
So lids, exhibiting SERS, 307
So lutio ns, electro chemical po tential o f
electro ns in, 195
So lvatio n pheno meno n, in io n-exchange
membranes, 450
So lvent
interactio n with metals, 59
reo rganizatio n energy of, 199
So lvent dipo le libratio n entro py, 140
So lvent dipo le o rientatio n, and tempera-
ture, 138
So lvent o rientatio n, BDM theo ry of, 139
So rptio n o f io ns and water, in io n-ex-
change membranes, 468
Specific adso rptio n, o f anio ns, 62
Specific adso rptio n, o f anio ns, and transfer
co efficient, 156
Index 511
Specific energy, fo r vehicle batteries, 376
Specific energy peak po wer balance, 381
Specific energy versus po wer, Rago ne
plo ts, 382
Specific po wer versus energy, Rago ne
plo ts, 382
Stepped faces, 19
Stepped surfaces, cubic system, 22
Stereo graphic net, Wulff type, 8
Stereo graphic pro jectio n, 6
fo r cubic crystals, 9
Stereo graphic triangle, 9
Structural aspects, o f io n-exchange mem-
branes, 437
Structure o f metals, 4
Structure o f metal surfaces, 23
Sulfo nate membranes, 468
Surface electro magnetic wave enhance-
ment, 337
Surface energy, 26
Surface enhanced Raman scattering
(SERS), 253
Surface preparatio n
and SERS effect, 271
fo r SERS in electro chemical systems,
273
Surface Raman scattering, o f dyes, 297
Surface Raman signals, distinctio n of, 258
Surfaces
ro ughness facto r of, 94
wave functio ns at, 25
Surface states
at semico nducto r electro des, 205
Fermi level pinning of, 206
Symmetries, o f principal index faces, 11
Symmetry facto r, /3, 113
independence o n temperature, 131
relatio ns fo r, 113
relatio n to a, 115
Tafel equatio n, 105
and temperature effects, 103
real fo rm of, 103
fo r co mplete tunneling co ntro l, 144
Tafel slo pe parameter, b, 106
Tafel slo pes, and electro de area, 167
and exchange currents, 164
Tafel slo pes, and electro de area (cont.)
and pro to n tunneling, 143
and temperature, 103
expenmental data as functio n of tem-
perature, 116
fo r hydro gen evo lutio n, 118
fo r multistep pathways, 160
fo r multistep reactio ns, 115
Temperature dependence
co nventio nal behavio r o f Tafel relatio n,
107
o f Tafel slo pes, experimental results fo r,
116
Temperature dependence o f a,
co nclusio ns o n, 182
theo retical, 132
Temperature effect, o n o xygen reductio n,
129
Temperature effects
o n Helmho ltz layer, 155
o n so lvent dipo le o rientatio n, 138
o n Tafel slo pes, 103
Terraces, 19
Theo retical, dye effects in SERS, 344
Theo retical mo dels, o f SERS effect, 322
Thermo dynamic stability, o f semico nduc-
to r electro des, 229
Transfer co efficient, a, 115
independence o n temperature, 127, 131
po tential dependence of, 148
relatio n to j3, 115
Temperature dependence o f /5 o r a
co nclusio ns o n, 182
theo retical, 132
Transpo rt pro perties
in io n-exchange membranes, 470
o f io n-exchange membranes, 437
Tunneling
o f ho t electro ns at semico nducto r, 235
o f pro to ns, 143
Ulstrup treatment, o f electro n and particle
transfer, 147
Ultrahigh vacuum
preparatio n o f surfaces fo r SERS, 285
SERS effects in, 264
512 Index
Unit cells
co o rdinatio n numbers fo r, 18
number o f surface ato ms in, 18
Vehicle and battery characteristics, 375
Vehicle batteries
perfo rmance requirements, 375
range between recharge, 375
co st facto rs, 384
energy efficiency of, 388
enviro nmental facto rs, 389
review o n, 371
safety facto rs, 389
specific energy requirements, 376
Vehicular pro pulsio n, batteries fo r, 371
Vo lumetric energy density, o f batteries,
379
Water electro lysis, pho to assistance of, 238
Water
SERS effect o n, 295
state of, in Nafio n, 455
Wave functio ns, at surfaces, 25
Well defined surfaces, results at, 3
Wulff stereo graphic net, 8
Zinc battery, 399
Zinc-halo gen battery, 402

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