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You are on page 1of 71

Background

A

B (1)

forward and backward reactions

2

Reaction rates

Rate of the forward reaction is given by:

Rf = kf * CA (2)

Rate of the backward reaction is given by:

Rb = kb * CB (3)

The net rate of reaction is given by:

Rnet = Rf Rb

Thus, Rnet can be written as:

Rnet = kf * CA - kb * CB (4)

Equilibrium

Equilibrium is defined as the point at which the

net reaction rate is zero

From equation 4, we obtain an equilibrium

concentration ratio

kf / kb = K = CB /CA (5)

K is a constant, and is called the equilibrium

constant (K)

Requirement

Every kinetic theory requires that the

kinetic equations collapse to

thermodynamic relations at equilibrium

Equation similar to (5) required of any

kinetic theory

Thermodynamics provides a description of

the behaviour at equilibrium

Predicts whether a reaction is feasible

(spontaneous),

Information about the reaction rates is

provided by kinetic equations

For a kinetic expression to be valid,

reduction to thermodynamic equations at

equilibrium is essential

7

Rate constants vary with temperature

(generally increase with T)

Most common relationship between rate

constant (k) and temperature is of the form:

k = A e -Ea/RT (6)

Ea - activation energy

R - gas constant.

A - pre exponential factor

8

Activation energy

Above relationship - called Arrhenius

relationship

Activation energy : Energy barrier that has

to be surmounted by the reactants before

they can be converted to product

Larger the activation energy - more energy

needed by reactants to surmount barrier

Significance

k = A e -Ea/RT (6)

Exponent term (e -Ea/RT ) - a probabilistic

feature - represents the probability that the

energy barrier will be surmounted.

Pre exponential factor (A) - represents the

number of attempts made at surmounting

the barrier - also called the frequency factor

10

Activation energy

E

Energy

11

Consider the general reversible electrode reaction

O + ne = R (7)

with kf and kb as the forward and backward

reaction rate constants

This is a typical redox reaction

Note that O and R stand for Oxidized state and

Reduced state respectively

12

governed by the Nernst equation - See

section on thermo:

Eeq = E - RT / nF [ln (CR * / CO*)] (8)

Relates the equilibrium potential of the

electrode (Eeq ) to the concentration of the

reactants and products (O and R)

13

to the Nernst equation when equilibrium

conditions are placed upon it - 1st

requirement of an electrode kinetic

theory

14

E vs. i

Electrode kinetic theory - must provide

information about the dependence of current

on electrode potential

When a current is passed, some

electrochemical change occurs at the

electrode

15

Overvoltage

Due to irreversibility - sustaining a given

current requires that a penalty be paid in

terms of electrode potential penalty called

overvoltage

= Eeq - E (9)

Eeq - expected (equilibrium) electrode potential

E - actual electrode potential

16

Tafel equation

Experimental observation: At low currents, the

current is exponentially related to the

overpotential

= a + b log i (10)

a and b are constants , i is the current density

Called the Tafel equation

Any successful electrode kinetic theory must also

explain Tafel behaviour 2nd requirement of an

electrode kinetic theory

17

Recap

1. Any electrode kinetics theory must reduce

to the Nernst equation when equilibrium

conditions are placed upon it

2. Any electrode kinetic theory must also

explain Tafel behaviour

3. Rate equations must reduce to the Nernst

and Tafel equations when the appropriate

conditions are introduced.

18

19

O + ne = R (7)

For the above reaction, the rate of the forward reaction is given

by:

Rf = kf CO (0, t) = ic /nF (11)

Where CO (0, t) is the surface concentration of O

Similarly the rate of the backward reaction is given by:

Rb = kb CR (0, t) = ia /nF (12)

Recall that reaction rate and current are interlinked also

recall that reduction occurs at the cathode and oxidation at

the anode

20

The net reaction rate (and hence the net

current) is given by

Rnet = Rf Rb = i/ nF = [ic ia]/ nF

= [kf CO (0, t) - kb CR (0, t)] (13)

21

Both kf and kb are potential dependent

functions

The forward reaction (a reduction) is an

electron accepting process - the rate

increases as the electrode potential becomes

more negative

This is because the electrode can give away

electrons more easily

22

(oxidation) reaction - the rate increases as

the electrode potential becomes more

negative

This potential dependence needs to be

qualified to obtain a true picture of

electrochemical kinetics

23

Value of k

kf

kb

More positive E

24

At equilibrium

It is possible to adjust the electrode

potential and O and R concentrations make

net reaction rate zero. At this point:

ic = ia ; Rf = Rb (14)

In other words:

kf CO (0, t) = kb CR (0, t) (15)

25

Rearranging equation 15, and taking logarithms on both

sides :

ln (kb) ln (kf) = ln [CO (0, t)/ CR (0, t)] (16)

Equation 16 is stated under conditions of equilibrium

(zero net current)

Therefore, invoking the Nernst equation:

ln (kb) ln (kf) = ln [CO (0, t)/ CR (0, t)]

= F/RT (E E) (17) 26

(first and last terms only) yields:

RT/F [d/dE {ln (kb)} + d/dE {ln (1/kf)}] = 1 (18)

1-

=1

The two terms on the left sum up to one are called symmetry factors in the case of

an one electron transfer reaction

27

Symmetry factors

dashed lines show the shift in the curve for O + e (reactants)

as the potential is made more positive

28

factors

The reductive symmetry factor - associated with

the forward reaction - represented by the Greek

alphabet

The oxidative symmetry factor therefore becomes

1-

29

Significance

The term is a measure of the symmetry of

the energy barrier

If the effect of changing the potential is

identical on both sides of the barrier, then

= 0.5 = 1- .

Any asymmetry results in other (fractional)

values of .

30

Influence on kinetics

understanding of kinetic expressions

31

Equation 19 on integration gives:

If kf = kf @ E = E

Similarly:

32

conditional) rate constants

If the concentrations of O and R are equal, ,

and the potential is maintained at E to

prevent current flow:

from equation 15, kf = kb

Can be replaced by a single symbol k.

33

Significance of ko

k - very important parameter in electrode

kinetics.

Measure of the kinetic facility of the

redox couple

The larger the value of k, the faster

equilibrium will be attained.

Systems with small standard rate constants

are typically sluggish

34

simple redox couples

e.g. : reactions involving a single electron

transfer such as:

H2 = 2 H+ + 2e

in a PEM fuel cell.

The largest measured values of these

constants are on the order of 1-10 cm/s.

35

reaction complexity, and can be as lower as

10 9 cm/s in certain cases.

O2 + 4 H+ + 4e = H2O

The oxygen reduction reaction - a 4 electron

process - has a lower value of k than the

hydrogen oxidation reaction increased

complexity

36

k for oxygen reduction << k for hydrogen oxidation

Note however that forward and backward rate constants

can still be large

kb = k e{[(1-)F/RT][(E-E)} (22-b)

maintain a given k

Larger overpotential lower net cell voltage - less

efficient fuel cell

Urgent need to improve oxygen reduction kinetics

increase k

37

38

End Result

i = nF k [CO (0, t) e{- [nF/RT] (E-E)}

- CR (0, t) e{[(1-)nF/RT](E-E)}] (25)

(n stands for no. of electrons transferred)

This formulation is called the Butler Volmer

formulation of electrode kinetics

Note two components (anodic and cathodic)

of current

Note exponential dependence on potential

39

Typical V- I relationship

40

Derivation

Writing an expression for net reaction rate:

Rnet = i/nF = [kf CO (0, t) - kb CR (0, t)] (23)

Thus:

i = nF [kf CO (0, t) - kb CR (0, t)] (24)

41

23:

i = nF k [CO (0, t) e{- [nF/RT] (E-E)}

- CR (0, t) e{[(1-)nF/RT](E-E)}] (25)

This formulation is called the Butler Volmer

formulation of electrode kinetics

42

B-V Theory

parameters:

- Faradaic current

- Electrode potential

- Concentration of reactant

- Concentration of product.

43

At equilibrium

Equation 25 can be rewritten (after some

arithmetic) as:

CO (0, t) - CR (0, t) e{[nF/RT][(E-E)} =

[i/nF k] [e{[nF/RT] (E-E)}] (26)

At equilibrium, i = 0

Right hand side (R.H.S) = 0

L.H.S. rearranges to give the Nernst equation

44

Tafel kinetics

For very large overpotentials ( = E - E),

one or the other of the exponents on the

R.H.S. of equation 25 goes to zero

Depending on whether the overpotential is

positive or negative, either the cathodic or

anodic component vanishes

B-V formulation reduces to the form:

= a +b log i (27)

45

following requirements:

- Reduces t the Nernst equation at

equilibrium

- Explains Tafel behaviour

Has the makings of a good electrode

kinetics theory

46

Current that flows (equal magnitude in opposite

directions) at equilibrium

Recall - at equilibrium -net current is zero

Also- surface concentrations of O and R = bulk

concentrations

i = nF k [CO (0, t) e{- [nF/RT] (E-E)}

- CR (0, t) e{[(1-)nF/RT](E-E)}] (25)

Now becomes:

nFkCO* e{- [nF/RT] (Eeq-E)}

= nFkCR* e{[(1-)nF/RT](Eeq-E)} (28)

47

e (nF/RT)[Eeq-E] = CO* /CR* (29)

Though the net current is zero, faradaic

activity is still in progress at the electrode

surface

An equal magnitude of anodic and cathodic

current flows

48

exchange current (io)

Thus the exchange current may be written

as:

io = nFkCO* e{- [nF/RT] (Eeq-E)} (30)

49

Raise both sides of equation 29 to the power ,

substitute for the term e{- [nF/RT] (Eeq-E)} to yield:

io = nFkCO*(1-) CR* (31)

In the case where CO* = CR* = C:

io = nFkC (32).

50

Significance of io

io is directly proportional to the standard

rate constant k

Frequently used as an important kinetic

parameter in place of k

Ideally, one would like to have as high an

exchange current density as possible for

fast kinetics

51

kinetics

Const. (0.5);

(a) io= 10 3 A/cm2; (b) io= 10 6 A/cm2); (c) ) io= 10 9 A/cm2

52

Especially convenient - provides direct

relationship between current and

overpotential (E - Eeq)

Unlike earlier formulation (B-V), where the

relationship was between the current and

the quantity (E E )

Uses io instead of ko

53

Dividing the current density (eqn. 25) by the exchange

current density (eqn. 31), we have:

i/io = [CO (0, t) / CO *]e{- [nF/RT] (E-E)}[ CO * / CO *]

- [CR (0, t)/ CR*] e{[(1-)nF/RT](E-E)}[ CO * / CO *] -(1-) (33)

using equation 29 to substitute for [ CO * / CO *] and

[ CO * / CO *] -(1-) :

i/io = [CO (0, t) / CO *]e{- [nF/RT] }

- [CR (0, t)/ CR*] e{[(1-)nF/RT] }] (34)

Where = E - Eeq

54

55

Const. (0.5);

(a) io= 10 3 A/cm2; (b) io= 10 6 A/cm2); (c) ) io= 10 9 A/cm2

56

io = const. = 10 6 A/cm2

57

Limiting cases

No mass transport effects - surface and bulk

concentrations are identical - their ratio equals unity

The current overpotential eqn. (34) becomes:

Known as the Butler - Volmer equation

Used as a good approximation to eqn. 34 i is smaller

than 10% of the smaller of the anodic or cathodic

limiting currents

58

Limiting cases

For very small values of x, the exponent ex is

approximately equal to 1+x.

For very small values of the B-V equation can be

written in a linear form as:

i = - io F /RT (36)

Linear relation between current and overpotential

Ratio of the two - units of resistance - called the charge

transfer resistance (Rct).

59

Limiting cases

Very large values of :

One of the exponents in eqn 35 goes to 0

For large positive :

i = io[e{[(1-)nF/RT] }] (38)

which becomes:

60

= [RT/(1-)nF] ln i - [RT/(1-)nF] ln io (40)

Fits the Tafel formulation (eqn. 10), with

a = - [RT/(1-)nF] ln io and b = [RT/(1-)nF]

Such an approximation is only valid for a given

oxidation or reduction component when the

other component contributes 1% or less to the

total current.

61

Tafel plots

A plot of log i vs. is called a Tafel plot

Shown in Fig.

Comprises an anodic branch and a cathodic

branch

Slopes of (1- )nF/2.3 RT and nF/2.3 RT

respectively

Sharp deviation from linearity as

approaches zero due to breakdown of

assumptions

62

Tafel plot

63

Equations (35 40) assumed no mass

transport effects

Mass transport effects are frequently present

in electrochemical systems

Need for corrections to account for mass

transport effects

64

C(x=0)/C* = [1 (i/il)]

Where il is the limiting current

65

- [CR (0, t)/ CR*] e{[(1-)nF/RT] }] (34)

i/io = [1 (i/il,c)] e{- [nF/RT] }

- [1 (i/il,a)] e{[(1-)nF/RT] }] (41)

for mass transfer effects

66

Limiting cases

Very small overpotentials, this equation can be

linearized

Need to apply Taylor's series expansion

This yields (derivation omitted):

Transport corrected analog of linearized B-V eqn.

67

charge transfer (37)

Thus, eqn. 42 can be re written as:

= - i (Rct + Rmt,c +Rmt,a) (43)

Rmt,c +Rmt,a are mass transfer resistances at

the cathode and anode

68

Interpretation of eqn. 43

When io >> il,c and il,a:

- Overpotential occurs mainly due to

mass transport effects even at very

close to equilibrium

- Kinetics of the system are very fast

- Kinetics of the reaction is very slow

- The overpotential close to equilibrium

is due to poor charge transfer.

69

Limiting cases

For very large overpotentials a Tafel like

expression can be obtained

For insignificant anode overpotentials:

i/io = [1 (i/il,c)] e{- [nF/RT] } (44)

70

= [RT/nF] ln (io/il.c) +

[RT/nF] ln [(il.c - i)/i] (45)

corrected Tafel plot

Can be used to obtain kinetic parameters in

systems having mass transport effects.

71

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