Proton Conductance and The Existence of The H3O Ion

Proton Conductance and the Existence of the H3O Ion
B. E. Conway, J. O'M. Bockris, and Hedda Linton

Citation: J. Chem. Phys. 24, 834 (1956); doi: 10.1063/1.1742619
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THE JOURNAL OF CHEMICAL PHYSICS VOLUME 24. NUMBER 4 APRIL, 1956
Proton Conductance and the Existence of the HaO' Ion
B. E. CONWAY, J. O'M. BOCI<:RIS, AND HEDDA LINTON
John Harrison Laboratory of Chemistry, University of Pennsylvania and Department of Chemistry, Imperial College, London, England
(Received July 14, 1955)
Measurements of the conductance of HCl in water, methanol, ethanol, n-propanol, ethylene glycol,
glycerol, 1:4 dioxane, acetone, formic, and acetic acids and the respective aqueous-nonaqueous systems have
been made as a function of concentration of water and Hel. The degree of anomalous proton conductance
decreases with increasing n in C"H2n+10H, and conductance minima occur in aqueous alcoholic HCl solu-
tions of low H
20 content.
Former theories of proton conductance have permitted no quantitative distinction to be made between
the rates of classical proton transfer, quantum-mechanical tunneling transfer, and water rotation as rate
determining stages. If resonance in HaO' is set up sufficiently quickly after arrival of a given proton at a
water molecule, rotation of HaO' cannot be a rate determining step.
Detailed calculations of the rates of classical proton transfer, tunnel transfer, and the rate of rotation of
water are made. Classical transfer is much slower and tunnel transfer much faster than corresponds to the
observed proton mobility; rotation of hydrogen bonded water molecules near the HaO' ion is the rate
determining reaction (preceded and succeeded by fast tunneling of protons). This conclusion is quantitatively
consistent with the OH' mobility in water, and the H'/D' mobility ratio and qualitatively consistent with
pressure and temperature effects and with the absence of abnormal mobility of NH
4
' and NH
2
' in liquid
NHa. A detailed interpretation of the dependence of abnormal conductance upon chain length in ROH gives
fair quantitative agreement with experiment. The conductance minima observed in aqueous alcoholic HCI
are quasi-quantitatively predicted by the theory.
The proton spends about 1 % of its time undergoing tunnel transfers; the effective existence of the HaO'
ion is thus confirmed.
1. INTRODUCTION
T
HE existence of the HaO' ion
l
has been supported
thermodynamically2 and by experiment.3-5 Several
theories of the anomalous conductance of H', D', and
OH' ions in aqueous solution have been proposed6-l0 but
none is consistent with all the facts concerning the
mobilities of these ions and a hiatus exists between these
theories, in which the proton apparently exists in only
momentary association with a given water molecule,
and those concerning the real existence of HaO.
Hitherto, no theoretical investigation of the over-all
rates of proton transfer by various mechanisms6-9 has
been made to determine the rate determining step in the
conductance of H' in water and the lifetime of the HaO'
lOn.
Quantitative examination of such steps is given here
and the theoretical predictions tested by comparison
with experimental results, in particular critical results
obtained on the conductance of HCI in nonaqueous and
aqueous-nonaqueous systems. (Previous work
ll
-
l3
was
1 H. Goldschmidt and O. Udby, Z. physik. Chern. 60, 728
(1907).
2 J. Sherman, Chern. Revs. 11,98 (1932); K. Fajans, Naturwiss.
9, 729 (1921).
a K. Fajans and G. Joos, Z. Physik 23, 1 (1924).
4 M. Volmer, Liebigs Ann. 440, 200 (1924); H. T. Richards and
R. V. Smith, Trans. Faraday Soc. 47, 1261 (1951).
5 R. Suhrmann and F. Breyer, Z. physik. Chem. B20, 17 (1933);
B23, 193 (1933).
6 E. Hiickel, Z. Elektrochem. 34, 546 (1928).
7 J. D. Bernal and R. H. Fowler, J. Chern. Phys. 1,515 (1933).
8 A. E. Stearn and H. Eyring, J. Chern. Phys. 5, 112 (1937).
9 G. Wannier, Ann. Physik 24,545,569 (1935).
10 E. Darmois and D. Sutra, J. phys. radium 2, 577 (1950).
11 H. Goldschmidt and P. Dhall, Z. physik. Chern. 114, 1 (1924).
12 L. Thomas and E. Marum, Z. physik. Chern. 143, 191 (1929).
13 D. M. Murray-Rust, and H. Hartley, Proc. Roy. Soc.
(London) A126, 84 (1929).
insufficient in the range of solvents and solvent compo-
sitions studied.)
II. EXPERIMENTAL
Conductance measurements were carried out using a
conventional conductance cell, equipped with glass side
arms and stopcocks so that nonaqueous solutions could
be introduced and maintained in dry nitrogen. The cell
was thermostatted at 2S0.04C, and the absolute
value of the temperature checked by a recently cali-
brated thermometer. Resistivities were measured by
means of a noninductive Wheatstone bridge using an
audio-frequency ac source. Measurements were accurate
to 0.2%. Water, purified by distillation from acid
permanganate, had a specific conductance of 2X 10-
6
mho. Organic solvents for solutions containing up to
90% nonaqueous component were not dried. All solvents
were of Analar grade except 1: 4 dioxane. "Technical"
dioxane was distilled and the fraction boiling between
101.2 and 101.4C at 760 mm Hg used. For solutions
containing more than 90% nonaqueous component,
solvents were prepared as follows.
M ethanol.-S g Mg and 0.5 g 12 were added per 1 of
dried "absolute" methanol. The Mg was refluxed with
70 ml of MeOH and when converted to the methylate
the remaining 930 ml of MeOH were added and refluxed
for 30 minutes.
14
The methanol was distilled and col-
lected in N 2.
Ethanol.-l 1 of absolute Burnett EtOH was refluxed
for 1 hour with 10 g Ca. After 12 hours standing, it was
distilled and collected in N 2.
n-Propanol.-The n-propanol was distilled twice from
14 H. Lund and J. Bjerrum, Ber. deut. chern. Ges. 64, 210 (1931).
834
PRO TON CON D U C TAN C E AND THE E X 1ST E N CEO F THE H 30' ION 835
FIG. 1. Conductance
of O.IN HCl in organic
solvent-water mixtures.
() methanol, ethanol,
n-propanol, 0 ethyl-
ene glycol, X glycerol,
e formic acid, 0 acetic
acid, A acetone, 6l
dioxane.
o
~
400
o 10 20
Na using enough Na in the first distillation to react with
2.5% of water and in the second, with 1 %.
1:4 Dioxane.-A method based on that of Fuoss and
Kraus
15
was used. For nonaqueous solvent mixtures,
HCI gas was prepared by reaction of Analar H
2
S0
4
on
Analar KCI, and dried and purified by passage through
traps containing glass wool, cooled to -78C. Dry
solvents were kept in an all-glass apparatus and passed
in dry N 2 into a vessel containing dry N 2, into which dry
HCI was passed. Portions of this solution were passed
into a dried, weighed conductance cell containing dry
N
2
Appropriate amounts of pure solvents determined
by weight were then introduced from all-glass solvent
storage vessels. HCI was determined gravimetrically.
Water vapor was excluded by use of silica gel drying
tubes. For 100% nonaqueous systems (glycerol, glycol,
formic and acetic acids, and acetone), a similar proce-
dure was used but the HCI was determined by titration
with standard Na
2
C0
3
solution after tenfold dilution
with water. Mixtures containing less than 90% of
organic solvent were made by dilution of 10 ml of IN aq.
HCI to 100 ml with the required solvent. Corrections for
solvent conductance were significant only for formic and
acetic acid systems. The apparatus and procedure were
tested by measurements on known systems
16
17
and
15 R. M. Fuoss and C. A. Kraus, J. Am. Chern. Soc. 55, 21
(1933).
16 B. B. Owen and G. W. Waters, J. Am. Chern. Soc. 60, 2371
(1935).
17 I. I. Zhukov and G. F. Kneprov, J. Gen. Chern. (U.S.S.R.)
8, 1476 (1938).
30 40 ~ o 60 o 80 90 100
MOL % ORGANIC SOLVENT
results in agreement with published data to 0.2% in
pure and 2.0% in mixed systems were obtained.
III. RESULTS
The conductance of O.IN HCI as a function of solvent
composition in a variety of mixed solvents is shown in
Figs. 1 and 2. In pure nonaqueous hydroxylic solvents,
anomalous proton conductance occurs, but decreases in
the series H20, MeOH, EtOH, n-PrOH; in alcohol-
water mixtures, conductance minima occur at about
20% H20 content (Fig. 3). The effect is almost inde-
pendent of HCI concentration (Fig. 3). "Waldens rule"
is found to be particularly inapplicable.
IV. DISCUSSION
1. Former Theories of Proton Conduction
Any theory of the anomalous mobility of protons in
hydroxylic solvents has to be consistent with (i) an
250
200
o
o 10 20 30 40 50 60 70 80 90 100
MOL % SECOND ORGANIC SOLVENT
FIG. 2. Conductance of O.OIN HCI in methanol-organic solvent
mixtures . ethanol; 0 dioxane.
836 CONWAY, BOCKRIS, AND LINTON
4S0
250
III
~ 200
::IE
~ 150
100
SO
o 10 ~ O 30 40 50 60 70 80 10 100
MOL 'Y. METHANOL
FIG. 3. Conductance of HCI in methanol-water mixtures at various
HCI concentrations.
increase of mobility with pressure
18
; (ii) a low apparent
heat of activation; (iii) a decrease of heat of activation
with increase of temperature
8
; (iv) a ratio of the
mobilities of H' in water to D' in D
2
0 of 1.42
19
at
25C;* (v) addition of small quantities of water to
HCl- ROH systems causes a decrease in conduction
1
;
(see Fig. 3). (vi) a regular decrease of anomalous
mobility in ROH with increasing length of R (see Fig. 1).
The quantum-mechanical tunnel mechanism of Bernal
and Fowler
7
is highly sensitive to width and height
chosen for the energy barrier, but no calculation of the
rate as a function of these factors was originally made.
The rate of rotation of water molecules, necessary for
successive proton transfer, was assumed approximately
18 Glasstone, Laidler, and Eyring, The Theory of Rate Processes
(New York, 1941), p. 570.
19 G. N. Lewis and F. G. Doody, J. Am. Chern. Soc. 55, 3504
(1933).
* The D
2
0 used
l9
contained 3% H
2
0, i.e., the water concentra-
tion was 1.67M, so that the possibility must be considered that
conductance was by protons from the ions HaO', H20D', and
HOD, in addition to that by deuterons from D,O. For
H20+ 2 0 ~ 2 H O D ,
the equilibrium constant at 25 is 3.8, [H. Kirshenbaum, Physical
Properties and Analysis of Heavy Water (New York), p. 28].
Whence the isotopic water molecules would have been present at:
CHOD= 1.658M, cH,o=0.0167M and cD,o=47.77M.
Hence [J. O'M. Bockris, Modern Aspects of Electrochemistry
(Butterworths Scientific Publications, London, 1954), p. 251J,
CHOD=1.658M, cH,o=0.0167M and cD.o=47.77M.
CD,O' CD,O' 15 2 0
CD,O/CD,OH=55.5; --=9.15Xt0
3
; --= . Xl '.
CDOH,' CH,O'
In O.IN acid,
so that
CD,o=0.0981N; CD.OH= l.77XIO-W; CDOH,'= 1.07 X 10-
5
;
and CH.O= 6.5X to-ON. Thus, D
2
0H' is the only significant
source of protons whilst DaO' and D20H' are the main sources of
deuterons. Since the theoretical minimum ratio of the rate of the
quantum-mechanical transfer of protons to that of deuterons
(p. 840) is about six, the main source of protons is at a concentra-
tion 0.0981/0.00177 = 55.4 times less than that of the main source
of deuterons and the concentration of other oxonium ions is
negligible, conductance will proceed about thirty times more by
deuterons than by protons. Hence, the water in Lewis and Doody's
solutions does not invalidate their D' mobility.
equal to that for a structureless liquid like argon. No
attempt was made to distinguish quantitatively between
quantum-mechanical transfer and water rotation as the
rate determining process. The theory applied to deuteron
conductance indicated an absence of anomalous mobility
(see reference 19).
The effect of the applied field on the orientation of the
dipolar HaO' ion was taken by Hiicke1
6
to be the rate
determining process, but the model was proposed before
the four-coordinated model for water was developed
7
and is inadmissible in such a system (see p. 841).
Similar remarks apply to a refinement of this theory.9
Classical proton transfer was discussed by Stearn and
Eyring
8
but the reason for preferring this mechanism to
that of tunneling, namely that, because of the heat of
activation involved is small, the rate would be faster
than that of tunneling, is unsound, for the rate of
tunneling of H or D predominates over that of classical
transfer increasingly as the heat of activation is reduced.
No quantitative calculation of the potential energy-
distance relation during transfer was made and the
initial and final states of the proton were taken as those
determined by the distance between two water mole-
cules in the water structure and not the shorter distance
involving H
2
0 in the solvation sheath of the HaO' ion
(see Fig. 4). If the distance apart of the initial and final
states taken by Stearn and Eyring is used, viz., 0.86 A, a
heat of activation of 45 kcal for classical transfer is
found (see Fig. 5). The rotation of water molecules is
assumed to be faster than the rate of proton transfer,
but no calculation of the rotation rate is given.
Darmois and Sutra
10
assumed the applicability to
proton transport in water of classical metallic conduc-
tion equations. The main support is the correct calcu-
lation of the RiD' mobility ratio (but see the follow-
ing). It is entirely at variance with modern concepts of
the structure of water.
In no former theory have the rates of classical and
tunnel transfers or the rotation of water molecules in an
H-bonded model of water been calculated and distinc-
tion made between these possible rate controlling
mechanisms. No interpretation on the basis of the
mechanisms of previous theories6-l0 is available for the
1..--- -------- d -----------.i , ,
I ,
I :
I
FIG. 4. Model for proton transfer between an H,O+ ion and a
favorably oriented H20 molecule in its solvation sheath.
PRO TON CON Due TAN C E AND THE E X 1ST ENe E 0 F THE H 30' ION 837
experimental facts (ii) , (iii), (iv), and (v) of pp. 835-836.
The two previous calculations of the H"/D' mobility
ratio in which agreement with experiment is reached
involve models which are submitted to be improbable
(see p. 836).
2. Tunneling of Protons
(a) Model
The model chosen is that of a water molecule in the
primary hydration layer of an hydroxonium ion, so
oriented that one of its (2pk)2 orbitals
2o
,21 is in line with
an 0-H bond of a neighboring H30' ion. This model
involves a minimum distance for H+ movement during
transfer to the water molecule. The latter is hydrogen
bonded with both the HaO' ion and the rest of the water
structure
22
and is at a position of maximum stability.
The structure considered in the model is that for H20
molecules H-bonded to the HaO' ion in a tetrahedral
configuration about the HaO' ion. These water molecules
constitute its primary solvation shell and two out of
these four water molecules no longer fit completely into
the water structure outside the primary solvation layer
owing to their reorientation by the H
3
0' ion. This
reorientation which causes breakdown of the water
structure near the ion is the process considered in the
rotation rate calculation on p. 844.
The proton transfer is indicated in Fig. 4. The zero
point energy (Eo) for the vibration of the 0-H bond,
the stretching of which is to be considered, is 5.3 kcal
mole-
1
(calculated from the OH bond stretching fre-
quency of 1.12X 10
14
sec
1
).23 To evaluate the height and
width of this energy barrier the equilibrium positions of
the H before and after transfer for the model in Fig. 4
must be known. The mean distance between the oxygen
nuclei in two nearest neighbor water molecules in the
H-bonded water structure is 2.8 A,24 i.e., the effective
radius of the water molecule is 1.4 A. The OH bond
distance, dOH in the H
3
0' ion is 1.05 N5 and the radius
of the H atom is 0.3 A.26 The distance, d, between the
center of the H30' ion and the 0 atom (radius ro) of
water is hence
(1)
A maximum radius of the 0 atom is 1.4 A (the radius
of water
27
minus the radius of the hydrogen atom, i.e.
ro= 1.10 A in good agreement with the radius 1.12 A, of
the neon atom
27
which is isoelectronic with 0 in H
2
0.
Thus d=2.45 A in agreement with the 0-0 bond
20 E. J. W. Verwey, Rec. trav. chim. 60, 887 (1941); 61, 127
(1942).
21 J. Lennard-Jones and J. A. Pople, Proc. Roy. Soc. (London)
A205, 103, 155 (1951).
22 A. Gierer and K. Wirtz, Ann. Physik 6, 257 (1949).
23 K. Freudenberg and R. Mecke, Z. Physik 81, 465 (1933).
24 L. Pauling, J. Am. Chern. Soc. 57, 2680 (1935).
25 F. Hund, Z. Physik 32, 1 (1925).
28 C. A. Coulson, Valence (Oxford University Press, New York,
1952), p. 302.
27 L. Pauling, J. Am. Chern. Soc. 49, 771 (1927).
..
-2.2,?
~ ...
~
-'
~ -no
i!;
o
,r
c
o
.r:'
.: -2
l's
I
-260
STATf I STATE If
01 0' 10 1,1 12 1.3 I.'
DISTANCE FROM a ATOM IN A
I.' I..
FIG. 5. Potential energy curves for proton transfer from
HaO+ to H20.
distance of 2.5 A in hydrogen-bonded acid salts,28 e.g.,
KH
2
P0
4
The value of ro may also be derived from the
mean molecular radius of the O2 molecule given
29
as
1.68 A from transport and critical volume results. Using
the value of the single-bond radius of 0 which is known
accurately as 0.66 A,sO a second value of ro= 1.02 A is
obtained, so that ro= 1.060.04 A. The distance, 21, a
proton has to travel from the configuration I to II in
Fig. 4 is then given, using d= 2.45 A, by
21=d-2(d
oH
)in H,O'= 2.45-2.10=0.35 A; (2)
the minimum value of 21, using ro= 1.06, i.e., d= 2.41, is
0.27 A.
(b) Potential Energy Curves
Potential energy curves for the energy of the proton
in states I and II are constructed using a Morse equation
U
T
=D
o
[l-e-
a
(r-
T
e)]2, (3)
where Do is the dissociation energy of the hydration
complex H
s
O+'nH
2
0 to give H++(n+l) H
2
0 and a is
given by
(4)
In a series of like molecules, j, the stretching force
constant of a bond is proportional to Do so that a is
28 A. F. Wells, Structural Inorganic Chemistry (Oxford University
Press, London, 1945), p. 252.
29 E. A. Moelwyn-Hughes, Physical Chemistry (Cambridge
University Press, Cambridge, 1947), p. 37.
30 L. Pauling, Nature of the Chemical Bond (Cornell University
Press, Ithaca, 1948).
approximately constant in the series. Hence, in (4) f can
be taken as the force constant of the OH bond viz.,
5.31X 10
5
dyne cm-
1
31 and Do the dissociation energy,2
180 kcal mole-I, of the proton in HaO+ and rein (3) is
the internuclear separation 1.05 N5 of Hand 0 in HaO+.
U r in (3) is then calculated using Do for the total
dissociation energy of H
3
0+ in H
2
0, viz. the mean of the
values 250,20 and 276
7
kcal mole-I, and the value of a
calculated for H
3
0+. The potential energy curves for
states I and II in Fig. 4 calculated from (3) are shown in
Fig. 5.
To obtain the height of the energy barrier involved in
the transfer in Fig. 4, the resonance energy of the
activated complex is required. In an 0-H . 0 hydro-
gen bond, resonance energy would account for half the
hydrogen bond energy if the hydrogen were sym-
metrically situated between 0 ... 0.
26
The hydrogen
bond energy is -5.9 kcal mole-!,2! so that the resonance
energy of the activated state can be taken as - 2.95 kcal
mole-! and this energy must be subtracted from the heat
of activation calculated from the point of intersection
of the Morse curves for the H
2
0-H' vibration for the
proton attached to a water molecule in the initial and
final state respectively. The potential energy curves
intersect at 6.80 kcal above the zero point energy for the
proton in the HaO' ion and hence the heat of activation
for classical proton transfer is 6.80-2.95=3.85. The
value for deuteron transfer is 5.41, the difference from
that for H being due to the lower zero point energy of
the 0-D compared with that of the OH bond.
(c) Rate
For a one-dimensional barrier the Schroedinger equa-
tion for a particle of mass m, potential energy V x, and
total energy W, at a position x approaching the barrier,
IS
iJ2,j; 8rm
-+-. (W - V x)'=O.
iJx
2
h
2
(5)
The commonly given solution to this equation for the
rate of tunneling is invalid for relatively small energy
barriers.3! Eckhardt
32
has given a solution of (5) when
V x has the form in Fig. 5 and V x- W is of the order of
10 kcal.
The probability of tunneling per impact becomes
where
P
w
cosh27r(a+i1) - cosh27r(a-{1)
(
B-C)!
Il=t --
C
and C=h
2
/8 mP.
31 R. P. Bell, Proc. Roy. Soc. (London) A139, 466 (1933).
at G. Eckhardt, Phys. Rev. 35, 1303 (1930).
(6)
(7)
21 is the barrier width (0.35X 10-
8
em), B=4Et where
Et ( = 3.85 kcal mole-I) is the barrier height, and A is the
difference in energy of the initial and final states.
In the absence of an applied field, A = 0; when a field
is applied, A = 2lieO, where CPi is the internal field. CPi is
the field acting at a particular molecule in the liquid due
to the applied field cpo It is
33
3kT+IJ.R* 1 3 ~
3kT
.--.--,
1-ga 2 ~ + 1
(8)
where R* is the reaction field
33
of the dipole of moment
IJ., i.e.,
R*=IJ.F/1-ga. (9)
With ~ = 78 in (8), Pi= 11.2cp. Near the H30' ion, how-
ever, ~ will have its saturation value of about 4/4 so that
for this case CPi= 6.9cp. The uncertainty in the appro-
priate value of thus effects Pi only to a relatively small
extent.
For forward transfer, the height of the barrier is
diminished by a fraction x of leoc/Ji dependent on the
value of W chosen, since W is a function of the electro-
static and molecular potential energy of the particle; in
the reverse direction the barrier height is increased by
the same fraction, since the barrier is symmetrical.
Thus, the energy of the particle is W ,+ XlieO where as
o <W x< IX!, x has values O<x< 1.
Let xlcpieo=px, and 1/h(2m)bK. For an applied
field, let PW(x) become PW(x) and P -W(x) for the forward
and backward transfer across the barrier, respectively;
then for PxW x,
cosh2K(W x)!- cosh (CPx/W x)K(W x)!
PW(x) = (10)
[
4 (Et-cpx) -C]!
cosh2K (W x) L cosh7r C
and
cosh2K(W x)!-cosh(cpxfW x)K(W x)!
l
4(Et+cpx) -C]
cosh2K(Wx)Lcosh7r C
(11)
In the absence of a field, the rate of transfer across the
barrier in each direction is given
3
! by
Nf""
N=- PW(x)exp(-Wx/kT)dW""
kT 0
(12)
where N / N 0 is the fraction of the total number of
particles, No, approaching the barrier, which pass
through. When the field is applied, PW(x) is changed ac-
cording to (10) and (11) and the distribution of particles
with respect to their energies is changed by exp( Px/ kT).
The net rate of transfer across the barrier in the forward
33 C. Bottcher, Theory of Electric Polarization (Elsevier Publish-
ing Company, Inc., New York, 1952), p. 181.
34 T. J. Webb, J. Am. Chern. Soc. 48, 2589 (1926).
PROTON CONDUCTANCE AND THE EXISTENCE OF THE H 3 0' ION
839
direction down the electric potential gradient is then
given by
N-N_=_o r Pw(x)e-(W.,--'h)lkT.dW.,
N [ ""
kT J
o
f
"" P e-(Wx+<I>X)lkT.dTVJ (13)
- _W(x) x
o
i.e., since cf>xkT,
cf>x as a function of distance from the initial state is
measured from the equilibrium position of the trans-
ferring proton. When Wx<Et, cf>x is by the
distance abscissa in Fig. 5 correspondmg to that poten-
tial energy equal to W x' Values of cf>x to
various values of W x were evaluated graphIcally usmg
Fig. 5 and the fact that at x=O, (r=r.) cf>x=O and at
x= 1 (1= 0.35 A/2) i.e., at the activated state, cf>x= 1.93
X 10-
20
erg using = 4 in the calculation of cf>i (see p. 838)
from cf>. As W x varies from 0 with respect to the zero
point energy of state I in Fig. 5 to W z=Eb 10-
13
erg molecule-
1
(=3.85 kcal mole-I), cf>x va:-Ies .from
1.13 X 10-
20
to 1. 93 X 10-
20
erg molecule-
I
and IS a lInear
function of x. For W x> 2.67X 10-
13
erg molecule-I,
cf>z= 1.93X 10-
20
erg molecule-
1
since this is the
energy gained by the proton in going down the potentIal
gradient from x=O to x= 1. In (14), each value. of
PW(x)eWxlkT must be multiplied by the correspondmg
value of lcf>x/kT to evaluate the forward and reverse
rates of transfer across the barrier. Since cf>z/kT is of the
order of 10-
6
and cf>x only varies from 1.13XlO-
20
to
1.93XI0-
20
as Wz varies from O-H>O we can use the
mean value (i>x of 1.53X 10-
20
as approximately a con-
stant in order to evaluate the integrals in(14) graphically.
With (i>z small compared with Et or W x and for a
potential gradient of 1 v cm-
I
, PW(x) and !-W(x) be
calculated and differ only by 1 to 1.5 m the eIghth
decimal place on account of the field. The effect of t?e
field energy on the exponential exp( - W xcf>,jkT) IS,
however, about 5 in the seventh decimal place. In
comparison with this effect, the influence of the field on
PW(x) is negligible so that
(lS)
whence (14) becomes
No 2(i>", f"" W kT
N-N_=-- Pw(x)e- xl dWx,
kT kT 0
(16)
i.e., the net rate of proton transfer is proportional to the
10 20 ,0
WI 10
14
-1'9'
FIG. 6. Pwe-wlkT as a function of W for H' and D' quantulll-
mechanical tunneling.
field strength at low applied fields. The term
(17)
is evaluated graphically by choosing a suitable series of
values of W z from 1 X 10-
14
to 70X 10-
14
erg molecule-
I
which enables the convergent integral (17) to be
evaluated to an accuracy of 0.1%. The functions for H'
and D are plotted in Fig. 6 for various values of W
x
' To
obtain the rate of transfer of particles through the
barrier down the field, No is replaced by the number of
times per second that a particle approaches the barrier,
i.e., the bond frequency of 0-H or 0-D in H
3
0' or
D
3
0' (VOH= l.12X 10
14
; VOD= 1.12/V1X 10
14
sec
l
).
For every successful transfer across the barrier the
proton is transported effectively across the diameter, 0,
of a water molecule since when it arrives at an adjacent
water molecule any of the 3 H (or D) positions in the
resulting H30+ ion are equivalent (see p. 841). The net
frequency of transfers down the field per second are thus
obtained and by multiplying this by 2.8X 10-
8
cm the
limiting absolute ionic mobility is obtained. Transfer
can occur over all angles to the direction of the field, so
that the average value of (i>x, obtained by integrating the
values of (i>x over all angles of the direction of the
proton transfers to the direction of the field, viz., (i>x/3,
must be used in (16). However, 3 protons can be
transferred at each H30+ ion, so that the net rate of
transfer is
vo cf>x f'"
u=-3-- Pw"c-WxlkTdW
x
cm sec-I;
kT 3kT 0
(18)
(18) gives uH=75.8XI0-
2
cm sect; and UD'= 12.3X10-2
cm secI, i.e., UH=73 200; UD =11900 and UH/U
D

=6.1.
Quantum-mechanical transfers are therefore too rapid
to account for the observed anomalous mobility and the
6
,
I
I
0"1-:1
FIG. 7. Rota-
tion of the H
3
0+
ion in the water
structure.
value of the isotope mobility ratio is far too large. t If the
lower value of 2/=0.27 A is taken, the rates of transfer
are larger and the mobility ratio is still far in excess of
the experimental value of 1.42. If the barrier height is
raised to a value (11 kcal mole-I) sufficient to give the
correct order of mobility, the H': D' mobility ratio
becomes 14.2.
Tunneling of protons therefore readily occurs in acid
solutions but it is not the rate determining process in
proton conduction.
3. Classical Proton Transfer
The potential energy curves in Fig. 5 give t : . H o ~ (= 3.85
kcal mole-I) in moderate agreement with the experi-
mental apparent heat of activation.
8
,18 If the rate
determining process were classical proton transfer, its
rate would be,8
2CPi (t:.Hot) (t:.sot)
u=oh
exp
- RT exp R '
(19)
For H' and D', t:.Hot in (19) will differ by 1.56 kcal
mole-
l
since the resonance energy of the activated com-
plex will be the same for 0 HO and 0 D 0.
For H' and D', any difference in t:.sot will depend on a
difference in vibrational frequency between OR and OD
and calculation shows the effect to be negligible. UH'
and UD' will therefore differ approximately by the
factor e1660/RT=13.9=UH/UD, Other parameters af-
fecting UD' compared with UH' are the differences of
force constants for the OH and OD bonds and the
equilibrium distance r e. Neither is significant. Increase
in temperature tends to separate states I and II and
increases 21 and hence t:.Hot, whereas experimentally
t:.Hot decreases with increase in temperature.
8
,2l It is
therefore improbable that classical proton transfer is
rate determining.
The maximum rate of classical proton transfer
process is found from (19) for t:.Hot=O. t:.sot will be
t The calculated mobility ratio is relatively independent of
uncertainties in parameters.
Field
determined by the change of vibrational and solvation
entropy of the system on going from the initial to the
activated state. At ordinary temperatures the former is
negligible and the latter consists of changes in libra tiona I
and translational entropy of the water molecules during
the proton transfer. When proton transfer commences,
the positive charge becomes localized at the transferring
proton. This charge is midway between two water
molecules and can also interact with 4 more water
molecules around the center of the 0-H - 0 axis. In the
initial state in HaO. the proton was interacting with one
H
2
0 in the HaO' ion,and in addition (in analogy to K'),a6
four further water molecules. Hence, the structure
of the activated state will tend to be more ordered than
that of the initial state and t:.s
ot
negative and small. Its
maximum value is probably zero, and with this value in
(19) and t:.Hot=O, the calculated maximum mobility
value for classical proton transfer is 1 2.10a mho cm
2
mole-I, i.e., some 70 times less than the calculated rate
for tunneling. Tunnel transfer is hence the mode of
transport of at least 90% of the protons and deuterons.
4. Rotation of HaO' Ions
Rotation of the HaO' dipole perpendicular to the
dipolar axis was considered by Ruckel
6
to be rate
determining. If the HaO' ion is regarded as being bonded
by three H bonds to the rest of the water structure,
before partial structure-breaking occurs by rotation of
H20 molecules, proton transfers are not facilitated by
any mode of rotation of HaO' unless either of the two
adjacent water molecules (H
2
0)a, and (H
2
0)4 in Fig. 7
each with one of its H atoms nearest to the HaO' ion,
rotates through 120
0
to present a vacant O-orbital to the
HaO' ion. Rotation of RaO' by Ruckel's process is
advantageous only if a proton existed without taking up
resonance in HaO' for a time greater than that for HaO'
rotation. Thus, for H+ at a (Fig. 7) rotation could occur
e.g., to b thus facilitating a transfer having a component
36 B. E. Conway and J. O'M. Bockris, Modern Aspects of
Electrochemistry (Butterworths Scientific Publications, London,
1954), p. 62.
down the field. However, the time required for charge
equilibration by resonance in HaO' after arrival of a
proton is about 10-
16
sec, whereas the minimum time of
rotation of HaO' is about 2.10-!4 sec (see p. 846), so that
charge localization is dissipated before rotation and no
enhanced transfer to b would accrue. Similar remarks
apply to rotation about the dipolar axis of HaO.
Consequently, with the assumed resonance of HaO', fast
proton transfer by quantum-mechanical tunneling
should occur from HaO' to any suitably oriented H20
and this process is much faster (see p. 840) than
corresponds to the observed anomalous conductance.
However, it can only occur successively and rapidly if
there is always a suitably oriented H
2
0 molecule
awaiting the arrival of a proton. In the following section
it is shown that the rate of rotation of water molecules
into orientations such as that of (H
2
0)! in Fig. 7, limits
the rate of the otherwise fast tunnel transfer process.
5. Thermal Rotation of Water Molecules
In Fig. 7 (a) proton transfer could occur from a to
(H
2
0)2 and b to (H
2
0)! without water rotation and
proton transfer will then reoccur from (H
2
0)2 H+ and
(H
2
0)! H+ to other neighboring H20 molecules. Once
this has taken place any further protons arriving at the
positions a and b cannot transfer to (H
2
0)2 or (H
2
0)l
where the orbitals to which transfer occurred in the
previous instance are now occupied. Rapid successive
proton transfers can only take place along the typical
paths a to (H20)2 and b to (H
2
0)! if these water mole-
cules have rotated (see also Fig. 14) before a further
proton arrives at the position designated HaO+ in
Fig. 7 (a). Let N = the number of g' ions CIll
a
of HaO',
then in a lamina of 1 cm
2
cross section and one H20
molecule thick, there are NlYAX2.8XIO-
s
HaO' ions.
Let the protons pass normally down through this
lamina at a rate u; from (12), u= 7.SX 10
5
cm sec
l
. The
protons therefore pass through the lamina in(2.8X 10-
8
)1
(7.SX 10
5
) sec and there are N N A' 2.8X 10-
s
of them
in the lamina. Hence the number passing per second
through the lamina=NN A2.8X 10-
s
X (7.SX 10
5
)/(2.8
X10-S). Now there are SSX10-
a
.'YAX2.8X10-
s
H20
molecules in the lamina, so that per H20 molecule the
number, n, of protons passing per sec is
NN A7.SX10
5
n= 4.9X10l4N. (20)
S5XIo-
a
N AX2.8XlO-
s
In O.liV HCI, (20) gives n= 4.9X lO
lD
protons per mole-
cule sec
l
.
The angular velocity of rotation of free water mole-
cules (not in the vicinity of protons) is
7
2.SX lOla rad
sec
l
. When the water is hydrogen bonded the rate will
be about 2.SXlO!a exp(-llHot/RT), where llHot is the
heat of activation for rotation and consequent H-bond
breakage. Rotation and re-formation of the H-bonds as
they were initially, but with a mirror image configura-
tion of the HOH dipole in the water structure, requires
cooperative rotation of a number of neighboring water
;'
FIG. 8. Distribution of charge in the OH . 0 hydrogen bono.
molecules. A minimum activation energy for this process
will be obtained by using that for rotation of a single
water molecule which is approximately 10 kcal mole-I.
(See the curves in Fig. 15; the value of 8.4 kcal mole-
l
is
obtained
21
for the partial rotation in dielectric relaxation
measurements for H
2
0 in ice at Oe.) The average rate
of thermal reorientation of water molecules will there-
fore be only 2.SX lO
la
Xe-
lO
000/600= 1.4X 10
6
radianssecl,
which is much slower than the rate of arrival of protons
at a given water molecule calculated from (20). Hence
insufficiently rapid thermal rotation of H
2
0 occurs to
receive protons by the fast quantum-mechanical trans-
fer process (see the preceding) from a rotating HaO' ion.
(a) Heat of Activation for Thermal Rotation of H
2
0
The potential energy of an H20 molecule in the water
structure can be calculated by use of the electrostatic
modeP! as a function of angular displacement from the
equilibrium position by computing the distances be-
tween the charges equivalent to the dipoles in two water
molecules (Fig. 8) and summing the Coulombic terms
for each angular displacement. Angular electrostatic
potential energy functionst are then obtained from
which an activation energy for rotation can be derived.
Rotation about one of the H
2
0 H-bonds, e.g., XY in
Fig. 9, involves the least breakage of the H-bonds. For
the calculation of the energy of the H-bond system we
use the model in Fig. 10. XYZ is the H-bonded water
molecule which is to undergo rotation through an angle
f) about the bond XV. YZW is one of the H-bonds which
this H20 makes with another H
2
0 (UWV) having the
center of its 0 atom at W. YH' and YH" are the two
remaining bonds made by H atoms of two other water
molecules with the oxygen, center Y, of the H
2
0 mole-
cule XYZ. Rotation about XY causes YX lZ to trace out
the surface of a right circular cone, center C, radius CZ;
Xl is the position of the negative charge - 2e in the bond
YZ (see Fig. 8). The energies of interaction of the
charges (see Fig. 8) at Y, Xl, and Z with those at X
2
and
Ware required as a function of f). Z' is a typical position
of the H atom at Z for a displacement of f). To calculate
the Coulombic energies we require the distances WZ',
WX/, Z'X2, and X2X1' as a f(f). YWand YX
2
are
constant with varying f), and YX
1
, YZ, ZX2
, ZW are
known when f)= 0 from the model in Fig. 8. From
t See also Magat's curves [Trans. Faraday Soc. 33, 114 (1937)J
where H-bonding and the detailed water structure are neglected.
FIG. 9. Rotation of H20 in the water structure about one OH bond,
or about the bisector of the HOH angle.
Fig. 10, in IlZ'ZP, noting that IlCZZ' is isosceles since
CZ=CZ',
(Z' P)2= (ZZ')2+ (ZW)2 cos
2
{J
-2ZZ'ZW (21)
and in IlWPZ', where WP is the perpendicular dropped
from W to the plane containing the coplanar points
C, Z, Z', and P,
(WZ')2= (Z' P)2+ (ZW)2 sin
2
{J, (22)
w
FIG. 10. Geometrical model for calculation of angular electro-
static potential energy functions for rotation of an H-bonded
water molecule XYZ about the bond XV.
so that from (21) and (22)
(WZ')2= (ZZ')2+ (ZW)2 cos
2
{J
-2ZZ' ZW (ZW)2 sin
2
{J ..
Now in IlCZZ', ZZ'=2CZ'sinl1j2, where CZ'=the
radius of rotation about XY of the charge element
concerned.
-4CZ' cos{J (23)
11
=4(CZ') sinL[CZ'+ZW cos{J]
2
+ (ZW)2. (24)
Other distances WXl ', X 2Z', and X2Xl' are calculated
by equations similar to (24).
Angular potential energy functions are also calculated
similarly for the YH' and YH" hydrogen bonds.
If rotation takes place about XY in Fig. 9, 3 bonds
have to be broken, viz., the 2 H bonds of 0 of (H
2
0)l
with hydrogens c and d and the hydrogen a of (H20)1
with the 0 of (H
2
0)4 in Fig. 9. The bond between
hydrogen b of (H
2
0)l and the 0 of (H
2
0)" remains
unbroken in the rotation about XV. Twice in a 360
0
cycle two H atoms come into opposition, viz. a of (H20)1
with d of (H
2
0)3 and then with c of (H
2
0)2, and give a
repulsive potential energy. The resultant and com-
ponent angular potential energy functions for rotation
are shown in Figs. 11 and 12. The energy of activation
for this mode of rotation is of the order of 40 kcal mole-I.
n rotation takes place about the bisector of HOH in
(H
2
0)1 in Fig. 9, hydrogen atoms do not come into
opposition and twice the angular potential energy func-
tions for the H bond energy of a or b of (H
2
0)1 in
Fig. 9, with the 0 atoms of (H20)4 and (H
2
0)" re-
spectively, and the H bond energy of the 0 atom of
(H
2
0)1 with H atoms c and d in the water molecules
(H
2
0)2 and (H
2
0)3 respectively, determine the activa-
tion energy for rotation. The resultant and component
potential energy functions for this mode of rotation are
shown in Fig. 13 and give a heat of activation of
2S kcal mole-
l
for rotation through 180
0
back to the
initial configuration. On the average, the heat of
activation will be somewhat less than these figures since
rotation of one water molecule lowers the energy of
activation for rotation of each of its neighbours by a
fraction of the energy of formation of one H-bond. At
ordinary temperatures both modes of rotation shown in
PRO TON CON 0 U eTA NeE AND THE E X 1ST ENe E 0 F THE H 30' ION 843
FIG. 11. Angular
electrostatic compo-
nent potential energy
curves for rotation of
one water molecule
in water about one
OH bond.
10
.( TO MAX. OF 411
: AT 120
0 +
,
-
ALL CURVES REPEAT
AS MIRROR IMAGES
FROM 180 TO 380
100 120 150 200 250
ANGLE OF ROTATION IN DEGREES FROM INITIAL POSITION
Fig. 9 would occur only infrequently owing to the high
values of in agreement with Pople's thermo-
dynamic argument
21
that the H bonds in water are bent
but, in distinction to previous indirect evidence,36,37 few
are broken at normal temperatures. The idea of con-
siderable thermal rotation
7
,8 of H
2
0 molecules in the
water structure is therefore probably incorrect and
20
"'0
200 '00
"0
ANGLE OF ROTATION IN DEGREES FROM INITIAL POSITION
FIG. 12. Angular electrostatic total potential energy curves for
rotation of one water molecule in water, from Fig. 11.
36 Cross, Burnham, and Leighton, J. Am. Chern. Soc. 59, 1134
(1937).
37 R. H. Ewell and H. Eyring, J. Chern. Phys. 5, 726 (1937).
since thermal reorientation of water molecules is slow
compared with the rate of arrival of protons, it must
now be considered how a newly arrived proton influences
the rate of rotation of water molecules at the site of its
arrival.
1

ANGLE OF ROTATION IN DEGREES FROM
NORMAL EQUILIBRIUM POSITION
FIG. 13. Angular electrostatic potential energy curves for rota-
tion of one water molecule in water about the axis of the HOH
dipole . Breakage of OHO bond. 0 Breakage of 0 H-O
bond. X Total potential energy curves.
6. Rotation of H20 Molecules Accelerated
by the Field of the H
3
0+ Ion
In the water structure (see Fig. 14) the existence of
each extra proton in excess of H:0=2: 1 causes the
breakage of one H-bond, since at the location of each
extra proton there are now two protons instead of one
between two oxygen atoms. The sequence of events
upon the arrival and transfer of protons in the water
structure is shown in Figs. 14(a) to 14(e). In Fig. 14(a) a
proton has arrived at a water molecule and converted it
to HaO+. Transfer of a proton e.g. d then occurs to
(H
2
0)4 converting the latter to an HaO+ ion (Fig. 14(b.
Further transfer of a proton from this HaO+ ion then
occurs to another water molecule as shown in Fig. 14(c)
and 14(d). Meanwhile, another HaO+ ion has appeared
adjacent to (H
2
0)! and rotated (H
2
0)! through 120
0
and a proton, x, has transferred from this HaO+ ion to
(H
2
0)! converting it to the HaO+ ion containing protons
b, e, and x (Fig. 14(c. Proton b cannot now transfer to
(H
2
0)6 unless the latter rotates through 120
0
to present
a vacant (2pz)2 orbital to b so that transfer can occur.
Rotation readily occurs, however, by the repulsive force
between the HaO+ ion and (H
2
0)6 since (H20)6 is
unstably oriented with respect to the HaO+ ion xbe in
Fig. 14(c), and also since two protons band c are in
opposition and this facilitates the rotation of (H
2
0)6.
Figure 14(d) shows the situation after (H
2
0)6 has
rotated in the field of the HaO+ ion. b can now transfer
to (H
2
0)6 giving the situation shown in Fig. 14(e). The
proton c cannot transfer to (H
2
0)a unless (H20)a rotates
as did (H
2
0)6 in Figs. 14(c) and (d). The transfer of b
in Figs. 14(d) and (e) leaves (H
2
0)! in the same
orientation as it was in Figs. 14(a) and (b) before the
arrival of the proton x. For successive proton transfers
the typical sequence of events of rotation and transfer
described above must always occur, and rotation of a
water molecule left unfavorably oriented by a previous
proton transfer is an essential step for every further
proton transfer in the same direction. Since thermal
reorientation of water molecules is insufficiently rapid
(see p. 841) compared with the rate of arrival of protons
from a given direction, the relevant rotation process is
always that of an H20 molecule in the field of an HaO+
ion newly formed by the arrival of a proton at a water
molecule by the quantum-mechanical tunneling process.
In the rotation process shown in Figs. 14(a) to 14(e)
one H-bond necessarily remains ruptured after rotation,
two others are broken and reformed and the 4th, in the
axis XY in Fig. 14(c) (see Figs. 9 and 10), is unbroken
during the rotation. The potential energy of the
HaO+- (H
2
0)6 system in Figs. 14(c) and 14(d) as a
function of angular position of the (H20)6 with respect
to the HaO+ ion is calculated by the method on pp. 840-
841 and the component curves for the energies of each of
the broken bonds as a function of angular displacement
are shown in Fig. 15. The energy gained by the H20 in
rotating to a more stable position with respect to the
HsO' ion is considerably greater than the increase of
energy of the H20 on account of distortion and breakage
of .the H-bonds that no net activation energy is re-
qUlred for reonentation of a water molecule made
unstable by the arrival of a proton at an H
2
0 molecule
adjacent to it. However, the net force exerted on the
rotating dipole is dependent on the energy required to
break the H bonds binding the rotating H20 molecule.
The rate of rotation is hence determined by the time
taken for the dipole to accelerate and move to its final
position under the influence of the field of the HaO+ ion
the applied field, and the H bonds. '
time of rotation of the dipole (radius r) is de-
termmed by the couple acting on it due to the field of the
HaO+ ion, the component of the dipole of the HaO+ ion
the direction of an OH bond, and the applied field.
16 .shows the change of total potential energy
(mz., lOn-dIpole, H-bond and dipole-dipole) as a function
of (J by summing the component potential
energIes of FIg. 15 at various angular displacements.
The gradient, multiplied by -1, of the total-potentia 1-
curve (Fig. 16) with respect to circumferential
dIstance, x, moved, i.e., r(J, is the force causing rotation.
From (J= 0-10
0
the total force acting on the dipole is
approximately proportional to (J2 and from 10
0
-68
proportional to (J and accelerative; from 68-110 the
forc: is proportional to (J and from 110-120, pro-
portlOnal to fJ2, and retardative.
If
1
P=kfJ=-kx=k'x
rOR
the couple acting on the OH bond of radius rOR is
ProH=k'xrOR
(25)
(26)
for rotation about one OH bond as in Figs. 9 and 10.
By the principle of angular momentum
ax),
at rOR at
(27)
where 1= mRrOR2 for the rotation of the OH bond and
mH is the mass of the H atom. '
a
2
x k'x
.. -
(28)
at
2
mH
so that
(axy k'x
2
- =-+C.
at mH
(29)
Initially the particle is librating in the water structure
with an energy (3/2)kT. Its angular velocity
Wo at zero dIsplacement from the direction of the
0-H - - OH bonds, i.e., when its potential energy due
to angular displacement is zero, is therefore given
7
by
(1/2)kT= (1/2)Iwo2 (30)

,
,
0
' 2,1
(H
2
0)
5
(H
2
0)
6
I
I
I
(a)
0."4-k
(H
2
0)
(e)

d .. l

,
(H
2
0)3
H+

I
I
0
' 21.
(H
2
0
5 .::-1-':]0
(H
2
0)

I
I
D
' (HZO)2
::t._
(H
2
0)5
(b)
(H
Z
O)6

i:,o'
(H
2
0)3
(H
2
0)6
" rl

Cd)
FIG. 14. Successive proton transfer and water rotation
near the HaQ+ ion in the water structure.
Q
,
,
I
0
:
Z0
)2l
'(.
:( .... _."..
(e)
(\0)3
H30+ 0

"0

o
...,
o
z
n
o
z
V
c::
n
...,
>-
Z
n
rr:
>-
Z
V
...,
::x::
rr:
rr:
X
[fJ
...,
tTl
Z
n
tTl
o
'Tj
...,
::x::
tTl
::x::
w
o
o
z
oc
"""
Vl
BREAKAGE: 0'
210"1'10)
FOAMATION 0'
2 (0'''1'101
.
ANGLE OF ROTATION IN DEGREES FRON INITIAL POSITION
FIG. 15. Angular electrostatic potential energy curves for
tion of H
2
0 near the HaO+ ion contribution not
included-see Fig. 16).
for librational motion in one plane, giving Wo= 2X lOla
rad sec
l
.
For the rotation following the arrival of a proton,
(
ax) =2X106 em sec-I = (C)1
at ,,=0
using the value of Wo given above. Integrating (29),
[ (
C )1J"=<10
/
180).-r ( k' )1
In x+ X2+_- =t -
'I ' k mH ,,=0 mH
(31)
where t is the time of rotation from 0=0 to 0= 100. A
similar equation applies to the retardation at the end of
the rotation. From these two expressions the times
taken during the motion where P ex: 0
2
are obtained. The
times taken during the motion through the angles where
the force (P) and the tangential component of the
acceleration are constant can be calculated from
(
ax)! (a2X)
X= - +t - t2
at ,,=0 at
2
'
(32)
where a
2
x/at
2
=p/mH. Summing the four components
of the time taken to rotate from 0
0
to 120
0
displace-
ment, t= 2.4X 1Q-14 sec.
When the external field is applied, rotation is either
slightly hindered or slightly accelerated, depending on
the direction of rotation compared with that of the
applied field. If each rotation enables a proton to be
transferred, the rate of proton transfer is 1/t= 1/2.4
X 10
14
secl.
The times taken in the accelerative or decelerative
motion are in general CEq. (29)) proportional to (m/ P)!
and the rates of rotation (w) hence proportional to (P)t
for a given molecule. Most of the time of rotation is
spent in the regions where P is approximately inde-
pendent of O. When the field is applied, the time for
rotation in the same direction as the field will be pro-
portional to (m/ P+ j)! where j is the extra force on the
dipole due to the applied field, and in the opposite
direction, to (m/ P- j)1. Using the average internal
field, cf>;j3, (see pp. 839-840), the average couple on the
component Ji.' of the HOH dipole in the direction of the
OH bond being rotated due to the integrated average
applied field is
cf>i
j'=Ji.'-,
3
(33)
where Ji.'=Ji.H,O cos(105/2) and 105 is the HOH angle
in degrees in the water molecule. The average tangential
force rotating the dipole of length 21 is
l'
j=-.
I
cf>i= 6.9cf> (see p. 839) and cf> is taken in esu for 1 v
cm-
I
. Now in (33), Ji.'= 1.11X1Q-18 esu and 21= (1.11
X1Q-IS)/eo=0.23 A.:. j=0.74XIQ-ll dyne molecule-I.
From Fig. 16 the forces independent of 0 from 0= 10 to
0= 68 to 0= 110 are found to be both approximately
3.5X 1Q-4 dyne molecule-I. The net rate of rotation
down the field will hence be w+-w_=w=k(P+ j/m)l
-kCP- j/m)! and since j/P1,
W=k(:r (34)
and k(P/m)", i.e., the value of w_ in the absence of the
field, is (1/2.4) X 10
14
sec I evaluated above. Using the
values of j and P calculated above, U H' is then given
from (34) by
1 0.74X1Q-ll
UH = 2.SX1Q-
s
X96500, (35)
2.4X1Q-
1
4 3.5X1Q-4
where 2.SX 1Q-s is the distance in cm a proton is
transported by each transfer and rotation; since w is
proportional to 1/vm, UH =V2 UD', in agreement
with the experimental value of 1.42 U
D
.19
This calculation of U H' is based on the assumption
that a final orientation favorable to proton transfer is
reached from a particular initial configuration of the
HaO' - H20 system.
However, the librative motion of both the HaO' ion
and the rotated H
2
0 molecule diminishes the chance of
proton transfer, since a mutually favorable orientation
for proton transfer occurs only during some fraction of
the periods of libration of HaO' and H20 in its hydration
shell. The librational amplitude is about 15
0
(p. S50)
and during the libration the distance through which
proton transfer has to occur depends on the librational
displacement of HaO' and H
2
0 from the position which
PROTON CONDUCTANCE AND THE EXISTENCE OF THE HaO ION 847
tends to be reached after H20 rotation, where one OH
bond of H
3
0 is in line with the (2pz)2 orbital of the
adjacent H20 molecule. From Fig. 5 and the model in
Fig. 4 it can be calculated by obtaining the heights of
the energy barrier for various displacements, that fast
proton transfers occur for displacements up to 9. If
libration is simple harmonic, the time spent in the
libration beyond the displacement of 9 (i.e., from 9
to 15) is approximately i of the total period of libration
so that the chance of proton transfer is ! for each
libration of H
3
0. However, the adjacent H20 molecule
is also librating and a similar chance of about! for
proton transfer can be calculated. The chance for
mutual favorable orientation leading to proton transfer
is hence t so that, from (35), U
H
=270 in good agree-
ment with the experimental value of 300 for the
anomalous contribution to the conductance.
Let tL be the time taken in librative motion for an
H30 ion to return from an extreme displacement (e.g.
15 as above) where proton transfers are infrequent to a
displacement ( <9) where the proton transfer process
is fast and not rate determining. If tL is long compared
with the time of water rotation in the H
3
0 field or of
proton transfer, then lib ration of H
3
0 is rate de-
termining. The field affects the over-all process through
its effect on the rate of proton transfers by tunneling
which occurs after librative displacement of H
3
0. to a
position favorable to rapid proton transfer.
If t and L are the times for the over-all process
"libration + transfer," in the direction of and against
the field and tQ and LQ are the corresponding times for
the tunneling transfers, then
t=tL+tQ and L=tL+LQ (36)
so that the frequencies of the forward and backward
libration + transfer reaction are
respectively. Here tQ, LQ <tL so that the net frequency
of the proton transport down the field is
w-w_= (t_Q-tQ)/tL
2
,
which gives a conductance
U = of (t-Q- tQ)/tL2,
(38)
(39)
where tQ and LQ are calculated for unit applied potential
gradient (pp. 839-840), and 0= 2.4X 10-
8
cm as in (18).
Equation (39) predicts that the slower the rate of
tunneling proton transfer the greater is the over-all rate
of the lib ration-transfer process. This paradox arises
because a difference of forward and backward reaction
rates is required for the calculation of the rate corre-
sponding to the conductance and the larger the values
A calculation by Bernal and Fowler (reference 7, p. 54) of this
probability was based on complete thermal rotation of HaO and
H20 which does not occur
2a
,39 except at high temperature in water,
and also assumed 12 nearest neighbors for the HaO ion in water
(J. Morgan and B. E. Warren, reference 38).
.20
0
50 lOa 150
ANGLE OF ROTATION IN DEGREES FhOM INITIAL POSITION
FIG. 16. Angular electrostatic total potential energy curves for
rotation of H20 near the HaO+ ion. 0 For a free H
2
0 molecule.
X For an H-bonded H20 molecule . Ion-dipole contribution.
of tQ and LQ the bigger is their difference for a given
applied field and hence the larger the value of U in (39).
Thus, for H and D quantum-mechanical transfers,
(39) gives U less for H than for D conductance by a
factor of 3 since on going from H" in H
2
0 to D in D
2
0,
LQ- tQ increases by a factor 6.1 (pp. 839-840) and t L2 for
the oxonium ions increases by a factor 2. Experimentally
U
H
= 1.42 UD so that librative control of the rate of
proton transfer cannot therefore be rate determing. It
also gives values of U about 10 times those calculated
for the rotation of H
2
0 which must always precede any
proton transfer.
The value of the mobility calculated from (35) for
water rotation is thus considerably less than that
calculated for any other of the possible steps and
rotation of water molecules into the hydration sheath of
H
3
0+ ions as protons pass through the water is the rate
determining step in proton conductance and the
H
3
0 - H20 proton transfer occurs by quantum-me-
chanical tunneling and is fast.
7. Mobility of OH' Ions
Mobility of OH' ions can also occur by a proton
transfer mechanism
7
:
0-+
/
H
+0-
'"
H.
Successive proton transfers require rotation of water
molecules upon formation of an OH' ion before further
transfer can occur. For a water molecule at OH', how-
ever, there is a proton deficiency in the water compared
'0
nPrO
H
;;:;:;::::::=================
.. ;------,-''''
v "'" WATER IN THE ALCOHOL
FIG. 17. Distribution of protons as HaO' and ROH2' ions in
aqueous-alcoholic HCI.
with the normal stoichiometry H: 0= 2: 1 and the
opposition of two OH bonds and their consequent
repulsion which occurs just before rotation in the
HaO' - H
2
0 case does not take place, so that the driving
force for rotation is principally that of the ion-dipole
interaction, since after a proton transfer from a water
molecule to an OH' ion the adjacent water dipole finds
itself unfavorably oriented in the field of the next and
subsequent OH' ions which appear in the same element
of water structure. Successive proton transfer from H20
to OH' cannot occur unless rotation of H
2
0 takes place
as in the HaO' case. From the slope of the potential
energy-distance curves of Fig. 16, the average OH' ion-
dipole force is approximately t times the total force
causing rotation in the HaO' ion case. From (31) and
(32), since the time of rotation is inversely proportional
to the square root of the driving force causing rotation,
the mobility of OH' ions should be vt=0.5 times that
of H+ ions. Experimentally the ratio of anomalous
conductance for OH' to H' is (200-50)/(350-50)
=0.5.
8. Temperature and Pressure
Rise of temperature causes (i) an increasing breakage
of H-bonds in the water structure
a7
and (ii) an increase
of the coordination number of any given H
2
0 molecule.
a8
(i) will facilitate rotation of water molecules by in-
creasing the slope of the curve in Fig. 16 and hence, the
force causing rotation. This effect will increase the
mobilities of H' and OH', in accord with the observed
positive temperature coefficient.
Increase of pressure causes structure breaking and
increases the coordination number of HaO', so that an
increase of mobility, as observed,18 would be expected.
9. Conductance of NH
4
' and NH
2
' in Liquid
Ammonia
In liquid ammonia the analogs of HaO' and OH' are
NH
4
' and NH2'; neither has an anomalous conduc-
38 J. Morgan and B. E. Warren, J. Chern. Phys. 6, 666 (1938).
tance,39 although a proton transfer process similar to
that in water could be formulated. Htickel
6
pointed out
that H
3
0' was dipolar but NH
4
' was not, and if rotation
of HaO' in the applied field was the rate determining
stage, this would explain the absence of anomalous
conductance in NH
3

From the known NH bond distance
40
the radius of the
H atom and the radius of the NH
4
' ion,28 the distance
the H atom has to travel in the transfer process in the
NH
4
'-NH
a
system can be found to be 0.46 A. The
proton affinity of NHa is 25 kcal greater than that of
H
2
02 so that the height of the energy barrier for proton
transfer will be increased. Examination of potential
energy curves analogous to those in Fig. 5 and calcula-
tion of the rate of quantum-mechanical tunneling for the
ammonia case from Eq. (18) for a temperature of
-40C gives a tunneling rate of the order 104 times less
than that for the HaO' case so that this process is slower
than the observed conductance
a9
and no anomalous
conductance would be expected.
10. Existence of the HaO+ Ion
HaO+ exists
41
in crystalline hydrates, e.g., HaO CI04
,
of strong acids and thermodynamically2 it would be
expected to be a stable entity. In water, the rapid
proton interchange precludes any permanent individu-
ality of a given HaO' entity. However, the time taken in
the transfer process is about 10-
11
sec while the time an
HaO' ion has to wait to receive a favorably oriented
water molecule is about lOX 2.4X 10-
14
= 2.4X 1O-
1a
sec.
The effective existence of the HaO' ion is therefore
established since the proton spends a much longer time
with a definite molecule than as a proton migrating, in
agreement with the molecular and thermodynamic
properties, e.g., infrared spectra/ ionic refractivitya and
partial molar heat content
41
ascribed to the HaO' ion in
aqueous solution.
11. Conductance of HCI in ROH Solvents
In alcoholic solvents, proton transfer can occur be-
tween alkoxonium ions and the solvent in the same way
as in water. However, the probability of transfers is
reduced by the ratio 2: 3 since ROH
2
+ contains two
transferable protons compared with three in HaO+.
This factor is insufficient to explain the progressively
decreasing contributions to anomalous conductance in
the ROH series as the chain length is increased (see
Fig. 1). Also the proton affinity of ROH in the bulk, i.e.
the solvation energy of H+ in ROH, decreases
42
in the
series C
n
H
2n
+10H as n tends from Since the
39 V. A. Pleskov, Acta Physicochim. U.R.S.S. 5, 509 (1936).
40 Conway, Bockris, and Lovrocek, Proc. Comm. Int.
Thermodyn. et Cin. electrochim. (Butterworth's, London, 1955),
p.207.
41 Wicke, Eigen, and Ackermann, Z. physik. Chern. 1, 342
(1954).
42 I. M. Kolthoff and L. S. Guss, J. Am. Chern. Soc. 62, 1496
(1940).
Morse constants, a, of closely related molecules are
constant because the force constants increase linearly
with the dissociation energies, the decrease of proton
affinity in the alcohol series should lead to a decrease in
the heat of activation for proton transfer from ROH
2
' to
ROH. Consequently, were the rate determining process
either of the transfer mechanisms the anomalous con-
ductance should increase as n becomes larger. The
results obtained in the present work are thus critical and
do not support either of the transfer processes as being
rate determining.
In pure alcoholic solvents, proton jumps can occur
from ROH
2
+ ions to suitably oriented ROH molecules.
Addition of water provides an alternative path for the
proton which can then jump from ROH
2
+ to H20 giving
HaO+. The equilibrium constant for
HaO' + O H ~ R O H 2 ' + H20
for methanol, ethanol, and n-propanol (interpolated)
are 0.23, 0.059, and 0.037,41 respectively. The distribu-
tion of protons calculated as percent present as HaO' in
solutions of HCI in these aqueous-alcoholic systems is
shown in Fig. 17 as a function of water content of the
solution. As soon as there is more than a trace of water
present, nearly all the protons form HaO+ ions. Proton
transfers from HaO+ to ROH are unlikely since they
now have to gain free energy in the transfer process.
Normal transfers between HaO' and H20 are rare at low
concentrations of water so that the HaO+ entities are
more permanent than when in water, and consequently
have a mobility approximately equal to that of K' ions
(which have a radius near to that of HaO') in the same
solvent. With increasing H20 content, exchanges be-
tween HaO+ and H
2
0 occur more frequently and the
anomalous conductance increases again. At higher
alcohol contents more of the protons are present as
ROH
2
+ from which protons undergo transfers with
ROH molecules and an anomalous alcoholic con-
ductance appears. The depth of the conductance minima
should thus be approximately equal to the anomalous
conductance as is found, (Table I).
If rapid transfers can only occur upon close approach
of H20 and HaO' on the one hand and ROH and ROH
2
'
on the other, the dependence of anomalous conductance
on composition in H20- ROH mixtures can be obtained
by calculating the frequency of collisions of H
2
0 with
HaO' and of ROH2' with ROH as a function of solvent
composition and utilizing the data of Fig. 17 for the
relative concentrations of ROH
2
' and HaO' in the O.lN
HCI-solvent mixture. The anomalous conductance A of
the protons in the solvent mixture is given by
AH,O(ZH,O. H,O) mixture
A=---------------
(ZH,O. H,O-) water
AROH (Z ROH. ROH,) mixture
+ , (40)
(Z ROH. ROH,) alcohol
TABLE I. The equivalent conductance at infinite dilution, of
hydrogen and lithium chlorides in water, methanol, ethanol, and
n-propanol: comparison of anomalous conductance in alcohols
with depth of the conductance minima in mixed aqueous-alcoholic
solvents.
Solvent
Property investigated Water Methanol Ethanol n-Propanol
A of hydrogen chloride 426.2 192 84.3 22
A of lithium chloride 115.0 90.9 38.0 18
[A(HCI)-A(LiCl)]* 311.2 101.1 46.3 4
A(HCI in alcohol) }
-A(HCI at minimum) 83.0 38.8 0
This quantity is taken to be a measure of the abnormal conductance of
the proton.
where AH
2
0 is the anomalous conductance in pure
water, AROH that in pure alcohols (see Table I), and
(ZH,O. H,O')mixture is the collision frequency of H20
and HaO' in the alcohol mixture, (ZROH. ROH,.)mixture
the collision frequency of ROH and ROH2
' in the
mixture, and the Z terms in the denominators are the
collision frequencies of the molecules indicated in the
pure solvents. Equation (40) predicts, e.g., with meth-
anol, a conductance minimum at 95% methanol (see
Fig. 1), and is thus in order agreement with experiment.
Addition of solvents other than ROH to water (Fig. 1)
produces a rapid diminution of anomalous conductance,
owing to breakup of the H-bonded water molecule
chains necessary for rapid successive proton transfers,
and this decrease does not parallel changes in viscosity
or dielectric constant and is hence connected with the
breakdown of the anomalous transfer mechanism.
12. Test of Proposed Model by Application
to Conductance in HCI-ROH
The time, t, for a rotation through an angle (j of a
particle is given
43
in terms of the rotary diffusion
constant e as,
E)= {J2/2t, (41)
where {p is the mean square value of (j for a number of
displaced particles. Now,
(42)
where 1] is the viscosity of the medium, r the radius of
the particle, and T the relaxation time. For anisometric
particles of axial ratio alb, (42) becomes
(43)
When an applied force acts on the dipole causing it to
rotate, the same forces operate to retard its rotation as
those which determine e in (43) since in both cases
there is distortion or breakage of the H bonds during an
angular displacement and the situation near the
hydroxonium ion differs only in that one hydrogen bond
out of four with surrounding H20 molecules is already
broken on account of the extra proton in H
3
0. Rotation
43 J. T. Edsall, Proteins. Amino Acids and Peptides (Reinhold
Publishing Corporation, New York, 1943), p. 506.
TABLE II. Molecular dimensions of H20 and alcohols.
Compound
H20
MeOH
EtOH
nPrOH
2a max
A
1.4
5.0
6.3
7.5
2amin
A
1.4
5.0
5.7
6.4
b
A
1.4
1.5
1.5
1.5
Mean a
A
1.4
2.5
3.0
3.47
rates in the different solvents may thus be compared
approximately from calculations of 1/ ab
2
'1/ for pairs of
solvents, e.g., H20 and an alcohol, and comparing these
ratios with those of anomalous conductance in the same
pairs of solvents, since, according to the theory de-
veloped here, the mobility, U, is proportional to the
reciprocal of the rotation time. The dimensions of the
alcohols, obtained by the use of space-filling models, are
given in Table II; maximum and minimum values for
'a', the semilength, are given since owing to free
rotation around C- C bonds the length is time de-
pendent and has maximum and minimum values. The
theoretical and experimental ratios of anomalous con-
ductance in water to that in alcohols are given in
Table III.
A second check of the theory may be obtained using
experimental relaxation times from dielectric measure-
ments on alcohols. For a relaxation from an average net
angular displacement of 0 of a group of molecules,
dO
--=KO,
dt
(44)
and K = 1/ T. The return of an individual particle to (j= 0
does not correspond to an angular velocity of zero since
the particle has librational energy. From the potential
energy curves for rotation of water molecules the
angular displacement for a librational energy of (1/2)kT
is approximately 15. For a return from a displacement
of 120 to 15, (44) therefore gives for the time t of
this rotational motion, t= 2.08T and t is again dependent
on the molecular properties of the rotating dipole and
the solvent. For rotation assisted by an applied field the
time will be some fraction (about 0.001) of 2.08T, but
will still be determined by the intermolecular forces
which determine T for relaxation in the absence of an
applied field. Thus, the rotation time for a dipole in an
associated liquid having structure is proportional to its
relaxation time. In Table III rotation times for the four
hydroxylic molecules considered, assumed proportional
to the known relaxation times,44 are expressed each as a
44 K. E. Slevogt, Ann. Physik 36, 141 (1939).
TABLE III. Ratios of anomalous mobilities calculated according to
a slow rotation model compared with experiment.
H20
MeOH
EtOH
nPrOH
1.0
0.48
0.164
0.077
1.0
0.154
0.08
0.03
Value of
mobility
ratio from
Mean the present
from work (ex-
theory peri mental )
1.0 1.0
0.32 0.32
0.12 0.15
0.05 0.01
ratio of the rotation time for water. These ratios are
compared with the experimentally determined ratios of
anomalous proton conductance in water and each of the
alcoholic solvents. The order agreement with experi-
ment is good, in support of the slow water rotation
process as the rate determining step in proton con-
ductance.
13. Conclusions
Five processes whlch could be rate determining in
proton conductance in hydroxylic solvents are con-
sidered. Proton transfer between H30+ and H20 by
quantum-mechanical tunneling is faster than corre-
sponds to the experimental anomalous conductance and
faster than the maximum possible rate by classical
proton transfers. Both transfer processes give too high a
value for the H,/D' mobility ratio. Rotation of H
3
0'
ions is not advantageous for proton transfers and
reorientation of H
2
0 molecules is always necessary for
successive proton transfers. Slow libration of H20 and
H
3
0' molecules, followed by proton transfer is con-
sidered, but this process gives the wrong direction of
change of mobility from H' in H
2
0 to D' in D20, and
also leads to a conductance faster than that corre-
sponding to water rotation. Reorientation of H20 mole-
cules in the field of the H
3
0' ion is shown to be rate
determining and the theory is supported by results of
critical experiments on proton conductance in a series of
alcohols and their mixtures with water.
ACKNOWLEDGMENTS
The authors are indebted to Professor Charles C.
Price and Professor H. V. A. Briscoe for the facilities of
the laboratories at the John Harrison Laboratory of
Chemistry, University of Pennsylvania and at Imperial
College, London, respectively. They also wish to thank
Dr. C. Bergh and Dr. H. Schwarz for a number of
penetrating discussions.

Proton Conductance and The Existence of The H3O Ion

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Proton Conductance and the Existence of the H3O Ion

B. E. Conway, J. O'M. Bockris, and Hedda Linton

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