Kwame Nkrumah University of

Science & Technology, Kumasi, Ghana

CHAPTER 3:
KINETICS OF ELECTRODE
REACTIONS

Daniel Adjah Anang

Department of Chemical Engineering

 Overview
In this unit, we will first review the kinetics of homogeneous
reactions and extend to electrode reactions. The unit will focus
on Butler-Volmer model of electrode kinetics, its implications
and how it is used to estimate the kinetic parameters of
electrochemical systems.

Content
1. Review of homogeneous kinetics.
2. Essentials of electrode reactions.
3. Butler-Volmer model of electrode kinetics.
4. Implications of the Butler-Volmer model.

www.knust.edu.gh
 Learning outcomes
By the completion of this unit, student should be able to;
 Understand Tafel equation and its implication.
 Derive the Butler-Volmer equation.
 Use the Butler-Volmer model to estimate the kinetic
parameters of electrochemical systems.

Student’s activities
1. Assignment.

www.knust.edu.gh
 3.1 Review of Homogeneous Kinetics
3.1.1 Dynamic equilibrium
Consider the unimolecular elementary reaction below
kf
A B 3.1.1
kb
where kf and kb are the rate constants of the forward and backward
reactions. Their unit is s-1.

Rate of forward reaction: ʋf = kf.CA 3.1.2

Rate of backward reaction: ʋb = kb.CB 3.1.3

www.knust.edu.gh
The net conversion rate from A to B:
ʋnet = ʋf - ʋb

ʋnet = kfCA - kbCB 3.1.4

At equilibrium, the net conversion rate is zero.

𝑘𝑓 𝐶𝐵
=𝐾= 3.1.5
𝑘𝑏 𝐶𝐴
K is equilibrium constant.

The kinetic theory therefore predicts a constant concentration ratio at

equilibrium, just as thermodynamics does.

Requirement for kinetic models: Every kinetic theory require that the
kinetic equations collapse to thermodynamics relations at equilibrium.
www.knust.edu.gh
The new kinetic model must behave like equation 3.1.5.

Thermodynamics versus Kinetics

1. Thermodynamics predicts whether a reaction is feasible
or not.
2. It provides a description of the behavior at equilibrium.
3. Information about the reaction rates is provided by
kinetic equations.
4. For a kinetic expression to be valid, it must reduce to
thermodynamic equations at equilibrium.

The conversion rates at equilibrium are called exchange velocity (ʋ0)

ʋ0 = 𝑘𝑓 𝐶𝐴 𝑒𝑞 = 𝑘𝑏 𝐶𝐵 𝑒𝑞 3.1.6
www.knust.edu.gh
3.1.2 The Arrhenius Equation and Potential Energy
Surfaces
 Rate constants vary with temperature (increase with temperature).
 Arrhenius was the first to recognize this behavior and proposed
that rate constants be expressed in the form:

𝑘 = 𝐴𝑒 −𝐸𝐴/𝑅𝑇 3.1.7

where EA is activation energy, R is gas constant and A pre-exponential

factor.

Activation energy: Energy barrier that has to be surmounted by the

reactant to be converted to products. The higher the EA, the more
energy is needed by reactants to surmount the barrier.

www.knust.edu.gh
Physical meaning of Arrhenius equation

𝑘 = 𝐴𝑒 −𝐸𝐴/𝑅𝑇

 Exponential 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.

Potential energy changes

during a reaction

www.knust.edu.gh
Activation Energy and Standard Free Energy of Activation
EA can also be described as the standard internal energy moving from
one minima to the maximum, which is called the transition state or
activated complex.
We know ∆𝐸 ‡ = ∆𝐻 ‡ + ∆ 𝑃𝑉 ‡
but ∆ 𝑃𝑉 ‡ is negligible for liquid phase reaction, so that ∆𝐸 ‡ = ∆𝐻 ‡
Thus, the Arrhenius equation can be recast as
−∆𝐻 ‡ /𝑅𝑇 3.1.8
𝑘 = 𝐴𝑒

The frequency factor (A) is also related to the standard entropy of

activation by
∆𝑆
𝐴= ′
𝐴𝑒 𝑅
Hence,
𝑘 = 𝐴′ 𝑒 − ∆𝐻 ‡ −𝑇∆𝑆 ‡ /𝑅𝑇 3.1.9

www.knust.edu.gh
Or
′ −∆𝐺 ‡ /𝑅𝑇
𝑘=𝐴𝑒 3.1.10

where ΔG‡ is standard free energy of activation.

Equations 3.1.8 and 3.1.10 are derived from 3.1.7, but only by
interpretation we apply to the phenomenological constant EA.

3.1.3 Transition State Theory

Not covered in this course!

www.knust.edu.gh
3.2 Essentials of Electrode Reactions
Consider the general reversible electrode reaction,
kf
O+ ne- R 3.2.1
kb
kf and kb are the rate constants for the forward and backwards
reactions.
For this reaction, the equilibrium state is governed by the Nernst
equation
∗
′ 𝑅𝑇 𝐶𝑂 3.2.2
E = 𝐸0 + 𝑙𝑛 ∗
𝑛𝐹 𝐶𝑅
which relates the potential of the electrode (E) to the bulk
concentrations of the reactants and products (O and R).
Any valid theory of electrode kinetics must predict this result at
equilibrium. (First requirement of any electrode kinetic theory!)
www.knust.edu.gh
3.2.1 Current vs. Potential
 Any proposed electrode kinetic theory must provide information
about the dependence of current on electrode potential.
 When current is passed, some electrochemical changes must occur
at the electrode.
 At low currents, the current is related exponentially to the
overpotential η. That is,
′ 𝜂/𝑏′
𝑖=𝑎𝑒 3.2.3
Or as given by Tafel in 1905,
𝜂 = 𝑎 + 𝑏 log 𝑖 3.2.4
where a and b are constants and i is current. Equation 3.2.4 is known
as Tafel equation.

Any successful electrode kinetic theory must also explain Tafel

behavior. (2nd requirement of electrode kinetic theory!)
www.knust.edu.gh
Summary of electrode reaction kinetic theory

1. Any electrode kinetic model must reduce to the Nernst

equation when equilibrium conditions are imposed.

2. Any kinetic model must also explain Tafel behavior.

3. Rate equations must reduce to the Nernst and Tafel

equations when the appropriate conditions are introduced.

www.knust.edu.gh
Recall the general reaction,
kf 3.2.1
O + ne- R
kb
- The concentration of O at distance x from the electrode surface and
time t is CO(x,t)
- Hence, the surface concentration is CO(0,t).

𝑖𝑐 3.2.5
- Rate of forward reaction, ʋ𝑓 = 𝑘𝑓 𝐶𝑂 0, 𝑡 =
𝑛𝐹𝐴

𝑖𝑎
-Rate of backward reaction, ʋ𝑏 = 𝑘𝑏 𝐶𝑅 0, 𝑡 = 3.2.6
𝑛𝐹𝐴

where ic and ia are the cathodic and anodic components to the total
current, i.
www.knust.edu.gh
Thus, the net reaction rate is
𝑖
ʋ𝑛𝑒𝑡 = ʋ𝑓 − ʋ𝑏 = 𝑘𝑓 𝐶𝑂 0, 𝑡 − 𝑘𝑏 𝐶𝑅 0, 𝑡 = 3.2.7
𝑛𝐹𝐴

and we have overall

𝑖 = 𝑖𝑐 − 𝑖𝑎 = 𝑛𝐹𝐴 𝑘𝑓 𝐶𝑂 0, 𝑡 − 𝑘𝑏 𝐶𝑅 0, 𝑡 3.2.8

3.3 Butler–Volmer model of Electrode Kinetics

3.3.1 Effect of Potential on Energy Barrier
Consider the reaction
Hg
Na(Hg) Na+ + e- 3.3.1

www.knust.edu.gh
www.knust.edu.gh
3.3.2 One Step, One-Electron Process
Let us consider species O and R engaged in one-electron transfer at
the interface without being involved in any other chemical step.
kf
O+ e- R 3.3.2
kb
Let the electrode be polarized from the reference potential, EO’. The
cathodic and anodic activation energies are then ΔG‡0c and ΔG‡0a at
EO’.
If the potential is changed by ΔE to a new value, E, the relative
energy of the electron resident on the electrode changes by
-FΔE = -F(E – E0’)
Hence, the O + e- curve will reduce by F(E – E0’) amount.

www.knust.edu.gh
www.knust.edu.gh
-The barrier for oxidation, ΔG‡a is
‡ ‡ 0,
∆𝐺𝑎 = ∆𝐺0𝑎 − 1 − 𝛼 𝐹 𝐸 − 𝐸 3.3.3
where α is the transfer coefficient and (1-α) is the fraction of FΔE lost
by ΔG‡0a due to polarization.

-From the figure, the cathodic barrier, ΔG‡c is

‡ ‡ 0,
∆𝐺𝑐 = ∆𝐺0𝑐 + 𝛼𝐹 𝐸 − 𝐸 3.3.4

We can write expressions for the rate constants in Arrhenius form

∆𝐺𝑐‡
𝑘𝑓 = 𝐴𝑓 𝑒𝑥𝑝 − 3.3.5
𝑅𝑇
∆𝐺𝑎‡
𝑘𝑏 = 𝐴𝑏 𝑒𝑥𝑝 − 3.3.6
𝑅𝑇

www.knust.edu.gh
Inserting the activation energies (3.3.3) and (3.3.4), we have
‡
∆𝐺0𝑐 0,
𝑘𝑓 = 𝐴𝑓 𝑒𝑥𝑝 − 𝑒𝑥𝑝 −𝛼𝑓 𝐸 − 𝐸 3.3.7
𝑅𝑇
‡
∆𝐺0𝑎 0,
𝑘𝑏 = 𝐴𝑏 𝑒𝑥𝑝 − 𝑒𝑥𝑝 1 − 𝛼 𝑓 𝐸 − 𝐸 3.3.8
𝑅𝑇

where f = F/RT.

-At equilibrium, E = E0’ and

‡
∆𝐺0𝑐
𝑘𝑓 = 𝐴𝑓 𝑒𝑥𝑝 −
𝑅𝑇
‡
∆𝐺0𝑎
𝑘𝑏 = 𝐴𝑏 𝑒𝑥𝑝 −
𝑅𝑇

www.knust.edu.gh
Now, let us consider the situation where the interface is at equilibrium
with the solution in which C0* = CR*. Therefore, E = E0’ and
kfCO* = kbCR*, so that kf = kb.
Thus, E0’ is the potential where the forward and reverse rate constants
have the same value. This value is called standard rate constant, k0.

The rate constant at other potentials can be expressed in terms of k0:

0 0,
𝑘𝑓 = 𝑘 𝑒𝑥𝑝 −𝛼𝑓 𝐸 − 𝐸 3.3.9
0 0,
𝑘𝑏 = 𝑘 𝑒𝑥𝑝 1 − 𝛼 𝑓 𝐸 − 𝐸 3.3.10
Insertion of these into (3.2.8) yields the complete current-potential
characteristics:
0 , 0,
𝑖 = 𝐹𝐴𝑘 0 𝐶𝑂 0, 𝑡 𝑒 −𝛼𝑓 𝐸−𝐸 − 𝐶𝑅 0, 𝑡 𝑒 1−𝛼 𝑓 𝐸−𝐸

This equation is called Butler-Volmer formulation. It or variation

derived from it is used in the treatment of almost every problem
requiring an account of heterogeneous kinetics.
www.knust.edu.gh
3.3.3 Standard Rate Constant
k0 is an important kinetic parameter for a redox couple.
-A system with a large k0 will achieve equilibrium on a short
time scale, but a system with small k0 will be sluggish.

-The largest measured standard rate constants are in the range of 1 to

10 cm/s and are associated with particularly simple electron-
transfer processes.
-Values of k0 significantly lower than 10~9 cm/s have been reported
recently.
- Note that kf and kb can be made quite large, even if k0 is small, by
using a sufficiently extreme potential relative to E°'. In effect, one
drives the reaction by supplying the activation energy electrically.

www.knust.edu.gh
3.3.4 Transfer Coefficient
The transfer coefficient, α, is a measure of the symmetry of the energy
barrier.
Using the figure below, α can be obtained from the geometry of
intersection region.

www.knust.edu.gh
-If the curves are locally linear, then the angles θ and ϕ
are defined by
𝛼𝐹𝐸 3.3.12
tan 𝜃 =
𝑥
1 − 𝛼 𝐹𝐸 3.3.13
tan ∅ =
𝑥
Hence,
tan 𝜃 3.3.14
𝛼=
tan ∅ + tan 𝜃
-If the intersection is symmetrical, ϕ = θ and α = ½. Otherwise 0 ≤ α ˂
½ or ½ ˂ α ≤ 1 as show below

www.knust.edu.gh
3.4 Implications of the Butler-Volmer Model for
the One-Step, One-Electrode Process.
3.4.1 Exchange Current
First requirement of any electrode kinetic theory-Any valid theory of
electrode kinetics must collapse to Nernst equation at equilibrium.

Let us see if the kinetic model yields that thermodynamic relation as a

special case.
The net current is zero at equilibrium. From 3.3.11, we have
′ ′
−𝛼𝑓 𝐸𝑒𝑞 −𝐸 0 1−𝛼 𝑓 𝐸𝑒𝑞 −𝐸 0
𝐹𝐴𝑘 0 𝐶𝑂 0, 𝑡 𝑒 = 𝐹𝐴𝑘 0 𝐶𝑅 0, 𝑡 𝑒
Since equilibrium applies, the bulk concentrations of O and R are
found at the surface; hence
𝑓 𝐸𝑒𝑞 −𝐸 0′ 𝐶𝑂∗
𝑒 = ∗ 3.4.2
𝐶𝑅
www.knust.edu.gh
which is an exponential form of the Nernst relations:
∗
0′ 𝑅𝑇 𝐶𝑂
𝐸𝑒𝑞 = 𝐸 + ln ∗ 3.4.3
𝐹 𝐶𝑅
Thus, the theory passes its first test of compatibility.

-Also, at equilibrium, inet = 0 but ic = -ia = i0 ≠ 0. (i0 = exchange current).

That is,
0′
0 ∗ −𝛼𝑓 𝐸𝑒𝑞 −𝐸 3.4.4
𝑖𝑂 = 𝐹𝐴𝑘 𝐶𝑂 𝑒

-If both sides of 3.4.2 are raised to the –α power, we obtain

∗ −𝛼
−𝛼𝑓 𝐸𝑒𝑞 −𝐸 0
′ 𝐶𝑂
𝑒 = 3.4.5
𝐶𝑅∗
Substitution of 3.4.5 into 3.4.4 gives
∗ 1−𝛼 ∗𝛼
𝑖𝑂 = 𝐹𝐴𝑘 0 𝐶𝑂 𝐶𝑅 3.4.6

www.knust.edu.gh
The exchange current is therefore proportional to k0 and can often be
substituted for k0 in kinetic equations.
-For the particular case where CO* = CR* = C,
𝑖𝑂 = 𝐹𝐴𝑘 0 𝐶 3.4.7
Often the exchange current is normalized to unit area to provide the
exchange current density, j0 = i0/A.

3.4.2 The Current-Overpotential Equation

If we divide 3.3.11 by 3.4.6, we eliminate k0 and work with i0.
′ ′
−𝛼𝑓 𝐸−𝐸 0 1−𝛼 𝑓 𝐸−𝐸 0
𝑖 𝐶𝑂 0, 𝑡 𝑒 𝐶𝑅 0, 𝑡 𝑒
= ∗ 1−𝛼 ∗𝛼
− ∗ 1−𝛼 3.4.8
𝑖0 𝐶𝑂 𝐶𝑅 𝐶𝑂 𝐶𝑅∗𝛼
Or
𝛼 − 1−𝛼
𝑖 𝐶𝑂 0, 𝑡 −𝛼𝑓 𝐸−𝐸 0
′ 𝐶𝑂∗ 𝐶𝑅 0, 𝑡 1−𝛼 𝑓 𝐸−𝐸 0
′ 𝐶𝑂∗
= ∗ 𝑒 − 𝑒
𝑖0 𝐶𝑂 𝐶𝑅∗ ∗
𝐶𝑅 𝐶𝑅∗
www.knust.edu.gh
The ratios (CO*/CR*)α and (CO*/CR*)-(1-α) can be evaluated from
equations 3.4.2 and 3.4.5 and by substitution we obtain
𝐶𝑂 0, 𝑡 −𝛼𝑓𝜂 𝐶𝑅 0, 𝑡 1−𝛼 𝑓𝜂
𝑖 = 𝑖0 ∗ 𝑒 − ∗ 𝑒 3.4.10
𝐶𝑂 𝐶𝑅
where η = E – Eeq. This equation is known as current-overpotential
equation.
For large negative η, the
anodic component is
negligible and the total
current merges with that
of ic.
At extreme η, the current
levels off. In these
regions, the current is
limited by mass transfer
and not heterogeneous
kinetics.

www.knust.edu.gh
3.4.3 Approximate forms of the i-η Equation
(a) No mass transfer effect
If the solution is well stirred, or currents are kept so low such that CO
≈ CO* and CR ≈ CR*, then
𝑖 = 𝑖0 𝑒 −𝛼𝑓𝜂 − 𝑒 1−𝛼 𝑓𝜂 3.4.11
The inflection at Eeq depends on the
exchange current density, j0.
The lower the exchange current
density, the more sluggish the kinetics
and hence large activation
overpotential must be applied.
In case (a), system can supply large
current with insignificant overpotential
because of the large current density, j0.
In case (c), because of the small
current density j0, no significant
current will flow unless a large
activation overpotential is applied.
www.knust.edu.gh
(b) Linear characteristics at small η
Recall, for small values of x, ex ≈ 1 + x. Hence, for sufficiently small
values of η, equation 3.4.11 will become
𝑖 = −𝑖0 𝑓𝜂 3.4.12

⇒ Charge-transfer-resistance, Rct is
𝑅𝑇
𝑅𝑐𝑡 = 3.4.13
𝐹𝑖0
This parameter is the negative reciprocal slope of the i-η curve where
the curve passes through the origin (η = 0, i = 0).

(c) Tafel behavior at large overpotential

For large values of η (either -ve or +ve), one of the terms in (3.4.11)
becomes negligible.
For example, at very large (-ve) η, exp(-αfη) ˃˃ exp[(1-α)fη]
www.knust.edu.gh
(3.4.11) becomes
𝑖 = 𝑖0 𝑒 −𝛼𝑓𝜂 3.4.14
Or
𝑅𝑇 𝑅𝑇
𝜂= ln 𝑖0 − ln 𝑖 3.4.15
𝛼𝐹 𝛼𝐹

Thus, the kinetic treatment yields a relation of Tafel form.

(d) Tafel plots

A plot of log i vs. η, known as Tafel plot is useful in evaluating kinetic
parameters.
Typical Tafel plot is shown below.

www.knust.edu.gh
www.knust.edu.gh
Problem 3.1
Overpotential measurements at 25oC for the dissolution of a
certain metal in a well-mixed electrolyte yields the following
results:

i (mA/m2): 0.166 0.163 0.158 0.140 0.121 0.100 0.093 0.060 0.0333
ηc (mV): 1.5 3.0 6.0 9.0 18 30 35 60 104

Determine i0 and α.

www.knust.edu.gh
Solution
1. Analytical method
𝑖 = 𝑖0 𝑒 −𝛼𝑓η − 𝑒 1−𝛼 𝑓η

For Cathodic polarization,

𝑖 = 𝑖0 𝑒 −𝛼𝑓η

ln 𝑖 = ln 𝑖0 − 𝛼𝑓η

-Plot ln i vs. η

www.knust.edu.gh
 -8.6 Equation y = a + b*x
Weight No Weighting
Residual Sum of 0.0128
-8.8 Squares
Pearson's r -0.99724
Adj. R-Square 0.9937
-9.0
Value Standard Error
Intercept -8.7059 0.01947
B
-9.2 Slope -15.92142 0.44814

-9.4
ln i

-9.6

-9.8

-10.0

-10.2

-10.4

0.00 0.02 0.04 0.06 0.08 0.10 0.12

η(V)

www.knust.edu.gh
Slope:
−15.92142 = −𝛼𝑓

15.92142 × 8.314 × 298

𝛼= = 0.41
96500

Intercept:
−8.7059 = ln 𝑖0

𝑖0 = 1.656 × 10−4 A/m2

Calculated model:
𝑖 = 1.656 × 10−4 ∗ 𝑒 −15.97η

www.knust.edu.gh
2. Computer method (Matlab)
>> clear all
>> close all
>> cftool
>> eta=[0.0015 0.003 0.006 0.009 0.018 0.03 0.035 0.06 0.104];
>> i=[0.000166 0.000163 0.000158 0.000140 0.000121 0.00010
0.000093 0.000060 0.0000333];

a. Fit name: type “electrokinetics”

b. Select,
X data: eta
Y data: i

www.knust.edu.gh
The system will generate a plot with linear fit as default. You can
change it to any model. Here, we will use exponential model.

Results
General model Exp1:
f(x) = a*exp(b*x)
Coefficients (with 95% confidence bounds):
a = 0.0001677 (0.000162, 0.0001734)
b= -16.28 (-18.01, -14.56)

Goodness of fit:
SSE: 1.191e-10
R-square: 0.9933
Adjusted R-square: 0.9924
RMSE: 4.125e-06
www.knust.edu.gh
Parameter a:
𝑎 = 𝑖0 = 1.677 × 10−4 A/m2

Parameter b:
𝑏 = −16.28 = −𝛼𝑓

16.28 × 8.314 × 298

𝛼= = 0.42
96500

Calculated model:
𝑖 = 1.677 × 10−4 ∗ 𝑒 −16.36η

www.knust.edu.gh
Tabulated results

η (mV) 1.5 3.0 6.0 9.0 18.0 30.0 35.0 60.0 104.0

imea
(mA/m2) 0.166 0.163 0.158 0.140 0.121 0.100 0.093 0.060 0.0333
iCal,Ana
(mA/m2) 0.162 0.156 0.151 0.143 0.124 0.103 0.0947 0.0635 0.0315
iCal,Comp
(mA/m2) 0.164 0.160 0.152 0.145 0.125 0.103 0.0946 0.0628 0.0306

www.knust.edu.gh