University of Bucharest Faculty of Chemistry

Electron Transfer in Electrochemistry

Fundamental Mechanisms Cyclic Voltammetry
Constantin MIHAILCIUC Department of Physical-Chemistry
1

FUNDAMENTAL MECHANISMS
O + neOOHP + neR ROHP

ELECTRODE REACTIONS
G < 0 ~ G ?

R1 + O2
O1 R1

G o < 0

O1+R2
O2 R2

Heterogeneous electrode reaction

Has no effect ! Homogeneous redox chemical reaction + Eo

No adsorption !
IHP OHP

ze-

OOHP

OBulk

Diffusional only!
ROHP RBulk

the reactants must collide with one another to be able to change the electrons the path of the electron movement is very small, of the same size with the dimensions of the reacting particles the electron carries a negative charge so a current may be associated with the electron change the collisions may occur at any point of the reaction space with equal probability all the directions of the space are equally probable for the electron transfer summing up all the electron changes over the all directions of the space the current is zero

the energy effect of the redox chemical reaction wastes as reaction heat inside the solution

FUNDAMENTAL MECHANISMS
O + neR
G < 0 ~ G ?
Catalysis? Has effect ! Heterogeneous electrode reaction Kinetically

ELECTRODE REACTIONS
G < 0 ~ G ?
Has no effect !

R1 + O2

G o < 0

O1+R2

Overall cell reaction R A V

salt bridge

activation energy depends upon the nature of the reactants (electroactive species, solvent, metal) the temperature the applied electrode potential

Thermodynamically
Gibbs energy of the overall cell reaction (essentially the same as for redox chemical reaction) can be turned into electric energy electrochemical Gibbs energy (which can be modified at will) can drive the uphill reaction itself without using chemical ways

Pt
R1 O2

Pt

O1 + ne-

R1

O2 + ne-

R2

FUNDAMENTAL MECHANISMS
Has effect ! Reversible electron transfer Heterogeneous electrode reaction

ELECTRODE REACTIONS
~ G

O + ne-

~ G

O + ne-

Has no effect !

Irreversible electron transfer Heterogeneous electrode reaction

Secondary battery Primary battery

R1 + O 2

G < 0
o

O1+R2

G < 0 ~ G ?
Has effect !

R1 + O 2

G o < 0

O1+R2

G < 0 ~ G ?

Overall cell reaction On recharging process!

Has no effect ! Overall cell reaction There is no recharging proce 4

FUNDAMENTAL MECHANISMS
No adsorption !
IHP OHP

ELECTRODE REACTIONS
HOMO LUMO intervention Adsorption !
IHP OHP

O + nezeOOHP OOHP + neOLUMO + neOLUMO + neO + neE

o F

R ROHP RHOMO RHOMO R O + neE F , < 0 E LUMOO < 0 Eo F e R zeOIHP

ROHP

RIHP

E LUMOO

spontaneous anodic electrode reaction in a galvanic cell

non-spontaneous anodic electrode reaction in an electrolysis cell

FUNDAMENTAL MECHANISMS
IHP OHP

ELECTRODE REACTIONS
HOMO LUMO intervention

eg

e-

Fe

3+ OHP

Fe3+ + eFe
3+ OHP

Fe2+ Fe
2+ OHP

eg t 2g t 2g

+e

Fe

2+

OHP

Fe3+LUMO + e-

Fe2+HOMO Fe3+ Fe2+

In contrast, for K+ and Cl-, ions generated by indifferent electrolyte dissociation, the large gap between LUMO (4s) and HOMO (3p), makes the transfer of electron between the electrode and the species to appear as very difficult to be realized. So it is too difficult to reduce K+ and almost impossible to oxidize it and respectively it is too difficult to oxidize Cl- and almost impossible to reduce it.

FUNDAMENTAL MECHANISMS
Diffusion of the reactant species to the Outer Helmholtz Plane Rearrangement of the ionic atmosphere (10-8 s) Reorientation of the solvent dipoles (10-11 s) Alterations in the central ion-ligand bonds (10 Electron transfer (10-16 s) Relaxation in the inverse sense cathodic process
-14

CHARGE TRANSFER STEPS of ELECTRODE REACTIONS

Time scale of different steps
Diffusion

Charge transfer step: all of them,

s) including adsorption of the reactant and the desorption of the product if necessary, are included in the potential dependent rate constants

Franck-Condon principle

O+ze
IHP OHP

R
thermodynamics pre-equilibria diffusion to electrode diffusion from electrode

kinetics

ze-

OOHP

OB
OB

O*

charge transfer

ROHP

RB

diffusion ionic solvent bonds atmosphere dipoles alterations rearrangement reorientation

charge transfer

FUNDAMENTAL MECHANISMS
electrode
1 =0.1 nm 1 nm 10 nm 0.1 m 1 m 10 m 0.1 mm 1 mm HyL( xHy) Well-stirred bulk of solution

SEVERAL LANDMARKS IN ELECTROCHEMISTRY

2H + + 2e H 2 xER
IHP (x1) OHP (x2) DDL (xDL)

electrode

diffusion1 =0.1 nm of H+ HA H + A
Stagnant diffusion layer diffusion diffusion of HA of H+ + 1 nm 10 nm 0.1 m 1 m equilibrium in balance + 10 m xD 0.1 mm 1 mm xR

HA H+ + A

DifL (xD)

HA H + A

RDE summary of different layers

Intervention of a chemical reaction

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FUNDAMENTAL MECHANISMS
Thermodynamic way
O R OOOHP + ze Pt R R OHP

NERNST EQUATION

Kinetic way slow (irreversible) electrode reaction

(1 )zF zF Erev E o RT RT rev ) io = zFk o a e = zFk a e a R c O + (1 )zF zF Erev E o RT RT rev ko a e = k a e a R c O +

~ + z ~ O O

~ = R R

Oz O z = R z R

RT aOO Erev = E + ln zF a R
o R

Erev = Eo +

RT aO ln zF a R

Eo = ( Erev )a O = a R =1 =

O o O + z

R o R

zF

Eo = (Erev )aO = a R =1 =

RT k o ln c zF k o a

Standard electrode potential dependences: nature of the electroactive species nature of the solvent nature of the electrode material

Applications: only at equilibrium state in the rapid (reversible) electrode reactions for charge transfer step even under a nonzero current density 9

FUNDAMENTAL MECHANISMS
Potential window dependences: nature of the solvent nature of the supporting electrolyte nature of the electrode material

STATIONARY POLARIZATION CURVES

Potential window Electroactive species

Ia

O2 + 2H 2O + 4e 4HO 2H + + 2e H 2
Ec E 'c

O2 + 4H + 4e 2H 2O

regions of redox stability for H 2O, H + and HO

E 'a

Ea

2H 2O + 2e H 2 + 2HO

10

FUNDAMENTAL MECHANISMS
Fast (reversible) electrode reactions
i=
zF e RT

STATIONARY POLARIZATION CURVES O+zeE = E1 / 2 + 2,303 E1 / 2

o

R
RT i dlc i lg zF i i dla

1 1 i dlc

1 i dla

zF RT e

1e 1 i dla

zF RT

1 i dlc

zF RT

No kinetic parameters! Only diffusional parameters!

/2 RT D1 R =E + ln / 2 zF D1 O

O+ze-

Erev i dla i= i dla + i dlc 2 E1 / 2

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i dlc
O+ze-

FUNDAMENTAL MECHANISMS
Slow (irreversible) electrode reactions O+zeE = E1 / 2,a + 2,303

STATIONARY POLARIZATION CURVES R

Butler Volmer equation

i = i (e

(1 ) zF RT

zF RT )

E1 / 2 , a

RT i lg (1 )zF i dla i /2 RT k ot1 o max = E + 2,303 lg(1.349 1 / 2 ) (1 )zF DR RT i dlc i lg zF i /2 k ot1 RT o max = E 2,303 lg(1.349 1 / 2 ) zF DO
R

Kinetic parameters! No diffusional parameters!

E = E1 / 2,c + 2,303 E1 / 2 , c
O+ze-

i=

i dla 2 i i = dlc 2
R

i dla

E1 / 2,c
i dlc
O+ze-

E1 / 2,a
12

FUNDAMENTAL MECHANISMS
Slow (irreversible) electrode reactions
i = i o (e
+ (1 ) zF RT

STATIONARY POLARIZATION CURVES O+ze=

zF RT )

High field approximation (Tafel)

Kinetic parameters! No diffusional parameters!

Low field approximation

RT 1 = i zF i o

Ohm law!

2.3RT 2.3RT lg i o + lg( i ) (1 )zF (1 )zF 2.3RT aa = lg i o (1 )zF vs. lg( i ) 2.3RT ba = (1 )zF
O+zeR

RT 1 = R ct = i zF i o i =
o

i o R ct 0 i o 0 R ct
i= i dla 2 i i = dlc 2
R

1 i ooa Oa R

i dla

ln i o = ln i oo + ln aO + (1 ) ln a R ln i
o

E1 / 2,c
i dlc
O+ze-

E1 / 2,a

vs. ln a R

n = ln i oo + ln a O

m = 1

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FUNDAMENTAL charge transfer step MECHANISMS diffusion step

overvoltage) slope dI/dE effect of Erev around Erev reactions Nernst law perturbation-response relationship region When the perturbation position polarisability

Fast (reversible) fast slow (rds) (pure diffusion overvoltage) high slow I high well-defined settles down quickly both partial electrode reactions coexist holds a small perturbation of the equilibrium, keeps the equilibrium in the reversibility region, the equilibrium returns to the initial position less

Slow (irreversible) COMPARISON slow (rds) fast (pure charge transfer low large I small ill-defined settles down slowly partial electrode do not coexist does not holds a large perturbation of the equilibrium, sends the equilibrium in the irreversibility the equilibrium does not return to the initial 14 more

CYCLIC VOLTAMMETRY
Two-step assembly: charge/electron transfer step/reaction mass transport by diffusion step Perturbation

PHENOMENOLOGY

Potential scan rates: from 0.02 V/s to 50 V/s + Different potential ranges Different directions

fast (reversible) electrode reactions

Response

slow (irreversible) electrode reactions

Response

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CYCLIC VOLTAMMETRY
FUNDAMENTAL MECHANISMS O+neR
denoted as

FAST (REVERSIBLE) ELECTRODE REACTIONS

Er

Randles-Sevcik equation
/ 2 * 1/ 2 i pc = 2.69 105 An 3 / 2 D1 O cO v

i pc : cathodic peak current ( A ) n : number of electron exchanged

increasing t

A : area of the electrode (m 2 ) DO : diffusion coefficient of O (m 2 / s ) c* O : concentration of O (mol / L ) v : potential scan rate ( V / s ) 16

CYCLIC VOLTAMMETRY
FUNDAMENTAL MECHANISMS Features
Potential scan rates: from 0.02 V/s to 50 V/s

FAST (REVERSIBLE) ELECTRODE REACTIONS

Essential for judging the chemical reversibility of any electrode reaction: Expression for this ratio:

i pb i pf

i pb i pf

(i pb )o i pf

0.485(i sp )o i pf

+ 0.086

for a graphical estimation; useful when the forward peak is accompanied by successive peak not allowing a good estimation of the baseline.

i pf : forward peak current ( A )

i pb : backward peak current ( A )

( i pf )o : backward peak current not corrected for the baseline ( A ) ( i pf )o : forward peak current at the swithching potential not corrected for the baseline ( A) 17

CYCLIC VOLTAMMETRY
FUNDAMENTAL MECHANISMS Diagnostic criteria
Epf independent of the scan rate; Ep = Epf Epb , peak-to-peak separation, is equal to

FAST (REVERSIBLE) ELECTRODE REACTIONS

59 mV at 25 oC; n 59 mV at 25 oC; n

Ep / 2 = Epf Epf / 2 , peak-to-halfpeak separation, is equal to i pf v i pb

1/ 2

, the current function, is constant with the scan rate;

i pf , the peak current ratio, is constant and equal to 1.0;

1 / 2 I proportional to t after the Epf .

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CYCLIC VOLTAMMETRY
FUNDAMENTAL MECHANISMS

FAST (REVERSIBLE) ELECTRODE REACTIONS

Chemical Meaning of the Reversibility

geometrical reorganization accompanying the electron transfer is of no importance (only slight elongation of some bonds, only slight modification of some angles but inside the same original geometry).

Interpretation
n from the peak-to-peak separation or from the peak-to-halfpeak separation at 25 oC;
o EO / R =

Epf + Epb 2

from the two peak potentials;

DO or DR from the Randles-Sevcik equation if every other quantity is known; 19

CYCLIC VOLTAMMETRY
FUNDAMENTAL MECHANISMS O+neR
denoted as

SLOW (IRREVERSIBLE) ELECTRODE REACTIONS

Ei

Epc

/2 RT D1 n F 1 / 2 O =E [0.780 + ln o + ln( v) ] n F RT k o

Randles-Sevcik equation
/ 2 * 1/ 2 i pc = 2.99 105 An(n )1 / 2 D1 O cO v

allowing to calculate ko if Eo and DO are known; i pc =

n F ( Ep Eo ) * o RT 0.227nFAc Ok e

i pc : cathodic peak current ( A ) n : number of electron exchanged n : number of electron exchanged in the rate det er min ing step : coeficient of symmetry A : area of the electrode (m 2 ) DO : diffusion coefficient of O (m 2 / s ) c* O : concentration of O (mol / L ) v : potential scan rate ( V / s ) 20

allowing to calculate and ko if Eo is known;

o the plot is ln i pc vs. (Ep E ) which give rise to a straight line with

a slope

n F RT
o ln( 0.227nFAc* Ok )

and an intercept

CYCLIC VOLTAMMETRY
FUNDAMENTAL MECHANISMS

SLOW (IRREVERSIBLE) ELECTRODE REACTIONS

Features
Forward peak potential is more negative than if it were reversible. The forward peak current is equals to 78.6% of the reversible one considering = 0.5 . Formal standard electrode potential, Eo, can not be calculated from CV experiment.

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CYCLIC VOLTAMMETRY
FUNDAMENTAL MECHANISMS Diagnostic criteria

SLOW (IRREVERSIBLE) ELECTRODE REACTIONS

30 Epc dependent of the scan rate and shifts about for a tenfold increase of n the scan rate; there is no reverse peak so that the peak-to-peak separation has no meaning; Ep / 2 = Epf Epf / 2 , peak-to-halfpeak separation, is equal to mV at 25oC; i pf , the current function, is constant with the scan rate; v1 / 2 there is no peak current ratio. 1.857RT 47.7 = mV n F n

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CYCLIC VOLTAMMETRY
FUNDAMENTAL MECHANISMS

CHEMICAL MEANING of ELECTROCHEMICAL REVERSIBILITY

the degree of reversibility depends upon the high of the electrochemical barrier of the charge transfer reaction the lower the barrier the higher the reversibility the high of the electrochemical barrier depends upon the extent of the geometrical reorganization accompanying the electron transfer the smaller the geometrical reorganization the lower the barrier

the degree of reversibility depends upon the extent of the geometrical reorganization of the molecule subjected to the electron transfer

23

CYCLIC VOLTAMMETRY
FUNDAMENTAL MECHANISMS Fast (reversible) electrode reactions
no significant geometrical reorganization

CHEMICAL MEANING of ELECTROCHEMICAL REVERSIBILITY

Slow (irreversible) electrode reactions

framework destroying reorganization

Electrochemical criterion? Peak-to-peak separation Ep

Quasireversible electrode reactions

in between There is some important structural reorganization accompanying the electron transfer but the molecular framework does not undergo fragmentation.

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CYCLIC VOLTAMMETRY

MODEL of STUDYING
Using a large sweep rates interval

FUNDAMENTAL MECHANISM COUPLED E&C MECHANISMS O+neR

I (A)
-3.0x10 -2.0x10 -1.0x10
-4

R Y

denoted as

Er Cr

-4

-4

O+e =R R=Y ks=10 cm/s kch= 2.5 cm

-1

0.0 1.0x10 2.0x10 3.0x10 4.0x10

-4

v=0.1 V v=0.5 V v=1 V v=10 V

-4

-4

-4

-1.0

-0.5

0.0

0.5

E (V)

25

CYCLIC VOLTAMMETRY

MODEL of STUDYING
Using different ranges of potential

FUNDAMENTAL MECHANISM COUPLED E&C MECHANISMS

BC+eAB+e
-

CD+e-

D+e-C B+e-A C+e-B

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CYCLIC VOLTAMMETRY

MODEL of STUDYING
Using known compounds

FUNDAMENTAL MECHANISM COUPLED E&C MECHANISMS

A P
NH2 H2N NH

B
H2N NH2

A + B + P

27

CYCLIC VOLTAMMETRY

MODEL of STUDYING
Using differences between the second and the first cycle

FUNDAMENTAL MECHANISM COUPLED E&C MECHANISMS

I (A)
-2.0x10
-5

O1+n1eR1 O2+n2e
-

R1 O2 R2
0.0

O1+e =R1
2.0x10
-5

E 1=-0.4 V kch=0.1 s
o -1

R1=O2 O2+e =R2

-

E 2=0.0 V

denoted as

ErCrEr

4.0x10

-5

first cycle second cycle v=0,1 V/s

-0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4

E (V)

28