Chapter 3: Charge Transfer Kinetics

The purpose of this chapter is to establish the expression of the rate law of the charge
transfer which occurs in electrochemical reactions.
What does the rate of charge transfer depend on?
Which kinetic parameters should be involved and what is their significance?

3.1 Introduction
3.2 Reminders of Homogeneous Kinetics
3.3 Definition and Measurement of Rates
in Electrochemistry
3.4 Butler-Volmer Equations
3.5 Marcus Theory of Electron Transfer
Equilibrium and Non-Equilibium of the Interface

When the switch is opened, no current

flows through the circuit (i = 0) and both
electrodes are at electrochemical
equilibrium. The cell voltage (∆Ecell or
emf) is determined by the thermodynamics
of the system (∆rG):
∆rG
∆Ecell = emf = EH+/H2 – EZn2+/Zn = −
2𝐹𝐹

When the switch is closed, a current i

flows through the circuit. This current is
not controlled by thermodynamics but by
resistance and kinetic parameters
(activation barriers, efficiency of transport
of species in solution, ...). The cell voltage
is also different from the emf:

∆Ecell < emf

Influence of the Electrode Potential on the Reaction

The energy of the electrons in the metal depends on the potential applied to the electrode. By
modifying the potential from the equilibrium value, the electrochemical reaction can therefore
be carried out in the anodic (if E>Eeq) or cathodic (if E>Eeq) direction. It can therefore be
expected that the kinetic parameters (in particular the activation energies of the reactions
involved) depend on the potential applied to the electrode.
 Basic Mechanism of Electrochemical Reactions
Charge
Transfer Mass Transfer
M
Oel Obulk
e-
Rel Rbulk

0 1-10 nm 1-10 µm distance

Double-layer
Diffusion Layer

Even the simplest electrochemical reaction consists of several steps:

1) transport of the reactant to the electrode in the diffusion layer
2) charge transfer in the electrochemical double-layer
3) transports of the product away from the electrode in the
diffusion layer
 More Complicated Mechanisms
In addition, some chemical reactions and adsorption phenomena can
occur before or after the charge transfer
 Chapter 3: Charge Transfer Kinetics

The purpose of this chapter is to establish the expression of the rate law of the charge
transfer which occurs in electrochemical reactions.
What does the rate of charge transfer depend on?
Which kinetic parameters should be involved and what is their significance?

3.1 Introduction
3.2 Reminders of Homogeneous Kinetics
3.3 Definition and Measurement of Rates
in Electrochemistry
3.4 Butler-Volmer Equations
3.5 Marcus Theory of Electron Transfer
 Rates of Chemical Reactions
The rate v of a homogeneous chemical reaction in a perfectly agitated closed reactor is
generally defined as follows:

1 𝑑𝑑ξ
v( mol.L-1.s-1)= where V is the volume of the reactor and ξ the extent of the reaction
𝑉𝑉 𝑑𝑑𝑑𝑑

Example: S2O82- + 3I- = I3- + 2SO42-

1 𝑑𝑑𝑑𝑑𝑆𝑆2𝑂𝑂82− 1 𝑑𝑑𝑑𝑑𝐼𝐼 − 1 𝑑𝑑𝑑𝑑𝐼𝐼3− 1 𝑑𝑑𝑑𝑑𝑆𝑆𝑆𝑆42−
v=− −= − −= + − =+ −
𝑉𝑉 𝑑𝑑𝑑𝑑 3𝑉𝑉 𝑑𝑑𝑑𝑑 𝑉𝑉 𝑑𝑑𝑑𝑑 2𝑉𝑉 𝑑𝑑𝑑𝑑

If we assume that the volume V remains constant, then :

𝑑𝑑𝑑𝑑𝑆𝑆2𝑂𝑂82− 1 𝑑𝑑𝐶𝐶𝐼𝐼 − 𝑑 C I3 − 1 𝑑CSO42−

v=− −= − −= + − =+ −
𝑑𝑑𝑑𝑑 3 𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑 2 𝑑𝑑𝑑𝑑

Chemical methods (titrations) or physical methods (chromatography,

spectrophotometry, conductimetry,...) can be used to measure chemical reaction rates.
 Elementary Steps
The mechanism of a reaction consists of a series of elementary steps. A reaction step is
considered as an elementary step if no reaction intermediate can be detected between
the reactants and the products.

The molecularity of a reaction is defined as the number of molecules or

ions that collide simultaneously to result in a chemical reaction In an
elementary step, the molecularity is low (1, 2, exceptionally 3) and the number of
chemical bonds that are created or broken is also low (1 or 2 max).

Orders of the reaction:

Elementary steps have reaction orders equal to the stoichiometric coefficients for each
reactant.

Example: CH3Br + OH- CH3OH + Br- (SN2 reaction)

𝑑𝑑𝐶𝐶𝐶𝐶𝐶𝐶3 𝐵𝐵𝐵𝐵 𝑑𝑑𝐶𝐶𝐶𝐶𝐶𝐶3 𝑂𝑂𝐶𝐶

v=− =+ = 𝑘𝑘𝐶𝐶𝐶𝐶𝐶𝐶3 𝐵𝐵𝐵𝐵 𝐶𝐶𝑂𝑂𝐶𝐶 − where k is the rate constant
𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑
of the reaction
 Arrhenius Equation
It is observed that the rate constant k of a reaction varies with temperature T(K)
according to the following relation:

𝐸𝐸𝑎𝑎 where A is the pre.exponential (or frequency) factor and Ea (or

𝑘𝑘 = A 𝑒𝑒𝑒𝑒𝑒𝑒 − ∆G≠) the activation energy (or Gibbs free energy of
𝑅𝑅𝑅𝑅 activation).

Reaction energy profile

 Chapter 3: Charge Transfer Kinetics

The purpose of this chapter is to establish the expression of the rate law of the charge
transfer which occurs in electrochemical reactions.
What does the rate of charge transfer depend on?
Which kinetic parameters should be involved and what is their significance?

3.1 Introduction
3.2 Reminders of Homogeneous Kinetics
3.3 Definition and Measurement of Rates
in Electrochemistry
3.4 Butler-Volmer Equations
3.5 Marcus Theory of Electron Transfer
 Electrode Reaction Rate
M
νO O
νO O + n e- = νR R
ne-
νR R

Electrochemical reactions are heterogeneous reactions occurring only at the metal/

electrolyte interface. The larger the surface area of the electrode, the higher the
quantity of O consumed per unit of time. For this reason, the rate is usually
normalized to the electrode surface area (S)

1 𝑑𝑑ξ 1 𝑑𝑑𝑑𝑑𝑅𝑅 1 𝑑𝑑𝑑𝑑𝑂𝑂 1 𝑑𝑑𝑑𝑑𝑒𝑒 − 1 𝑑𝑑𝑑𝑑

v (mol.s-1.cm-2) = = =− =− =
𝑆𝑆 𝑑𝑑𝑑𝑑 ν𝑅𝑅 𝑆𝑆 𝑑𝑑𝑑𝑑 ν𝑂𝑂 𝑆𝑆 𝑑𝑑𝑑𝑑 𝑛𝑛 𝑑𝑑𝑑𝑑 𝑛𝑛𝑛𝑛𝑛𝑛 𝑑𝑑𝑑𝑑

where Q is the electric charge involved in the reaction and F the Faraday constant
(F = 96485 C.mol-1)
How to Measure Electrode Reaction Rates?
The electrode where the electrochemical reaction occurs
is included in an electric circuit

Electrons are exchanged at the interface, so an electric

current flows in the circuit:
𝑑𝑑𝑄𝑄 𝑖𝑖
i= (current) j= (current density)
𝑑𝑑𝑑𝑑 𝑆𝑆

1 𝑑𝑑𝑄𝑄 𝑖𝑖 𝑗𝑗
Working vsurf (mol.s-1.cm-2) = = =
electrode 𝑛𝑛𝑛𝑛𝑆𝑆 𝑑𝑑𝑑𝑑 𝑛𝑛𝑛𝑛𝑆𝑆 𝑛𝑛𝑛𝑛

The rate of the reaction ocurring at the electrode

νO O can be simply determined by measuring the
electric current flowing in the circuit.
νR R
Whereas the redox potential E serves to predict the feasibility
of redox reactions (thermodynamics), the electric current i
provides information on the rate of electrochemical reactions
(kinetics).
 Sign of the Electric Current i
The current can flow in both directions of the circuit, depending if a reduction or
oxidation process occurs at the working electrode. The current is thus an algebraic
quantity.
In the following sections, we will use the European convention for the electric
current sign:

- i > 0 if an oxidation process occurs at the working electrode.

- i < 0 if a reduction process occurs at the working electrode.

Cathodic reaction: νO O + n e- → νR R
𝑖𝑖 𝑗𝑗
vc (mol.s-1.cm-2) = − c = − c (𝑖𝑖c < 0)
𝑛𝑛𝑛𝑛𝑛𝑛 𝑛𝑛𝑛𝑛

Anodic reaction: νR R → νO O + n e-
𝑖𝑖 𝑗𝑗
va (mol.s-1.cm-2) = + a = + a (𝑖𝑖a > 0)
𝑛𝑛𝑛𝑛𝑛𝑛 𝑛𝑛𝑛𝑛

If the reaction occurs in both direction: νO O + n e- = νR R

𝑖𝑖 𝑖𝑖 𝑖𝑖 Current are
v (mol.s-1.cm-2) = vc − va = − c − a = − with 𝑖𝑖 = 𝑖𝑖 a + 𝑖𝑖 c
𝑛𝑛𝑛𝑛𝑛𝑛 𝑛𝑛𝑛𝑛𝑛𝑛 𝑛𝑛𝑛𝑛𝑛𝑛 additive!
 Chapter 3: Charge Transfer Kinetics

The purpose of this chapter is to establish the expression of the rate law of the charge
transfer which occurs in electrochemical reactions.
What does the rate of charge transfer depend on?
Which kinetic parameters should be involved and what is their significance?

3.1 Introduction
3.2 Reminders of Homogeneous Kinetics
3.3 Definition and Measurement of Rates
in Electrochemistry
3.4 Butler-Volmer Equations
3.5 Marcus Theory of Electron Transfer
 Rate Law Equations
M νO O
νO O + n e- = νR R
ne- νR R

If we assume that the charge transfer at the electrode is an elementary step, the
reaction orders are equal to the stoichiometric coefficients:

𝑖𝑖a 𝑒𝑒𝑒𝑒 ν 𝑅𝑅 où 𝐶𝐶𝑅𝑅𝑒𝑒𝑒𝑒 et 𝐶𝐶𝑂𝑂𝑒𝑒𝑒𝑒 sont les concentrations respectives du

va = + = 𝑘𝑘𝑎𝑎 𝐶𝐶𝑅𝑅
𝑛𝑛𝑛𝑛𝑛𝑛 réducteur et de l’oxydant à l’électrode; 𝑘𝑘𝑎𝑎 et 𝑘𝑘𝑐𝑐 sont les
constantes de vitesse respectives de la réaction anodique
𝑖𝑖c 𝑒𝑒𝑒𝑒 ν 𝑂𝑂
vc = − = 𝑘𝑘𝑐𝑐 𝐶𝐶𝑂𝑂 et cathodique.
𝑛𝑛𝑛𝑛𝑛𝑛
𝑒𝑒𝑒𝑒 ν 𝑂𝑂 𝑒𝑒𝑒𝑒 ν 𝑅𝑅
v = vc − va = 𝑘𝑘𝑐𝑐 𝐶𝐶𝑂𝑂 − 𝑘𝑘𝑎𝑎 𝐶𝐶𝑅𝑅
𝑒𝑒𝑒𝑒 ν 𝑅𝑅 𝑒𝑒𝑒𝑒 ν 𝑂𝑂
𝑖𝑖 = 𝑖𝑖a + 𝑖𝑖c = 𝑛𝑛𝑛𝑛𝑛𝑛 𝑘𝑘𝑎𝑎 𝐶𝐶𝑅𝑅 − 𝑘𝑘𝑐𝑐 𝐶𝐶𝑂𝑂
NB: there are some restrictions on the stoichiometric coefficients νO, νR and n for elementary
steps. Often νO = νR = n = 1 ! So from now, only electrochemical reactions of the O + e- = R
type will be considered.
 Arrhenius Law

∆𝐺𝐺𝑎𝑎≠
𝑘𝑘𝑎𝑎 = 𝐴𝐴𝑎𝑎 . exp (− )
𝑅𝑅𝑅𝑅

∆𝐺𝐺𝑐𝑐≠
𝑘𝑘𝑐𝑐 = 𝐴𝐴𝑐𝑐 . exp (− )
𝑅𝑅𝑅𝑅

where 𝐴𝑎 , 𝐴𝑐 are the frequency

factors and ∆G 𝑎≠, ∆G𝑐≠ the Gibbs
free energies of activation of the
anodic and cathodic reactions
respectively.

the peculiarity of electrochemistry: the Gibbs free energies of

activation of the anodic and cathodic reactions depend on the
potential E applied to the electrode : ∆Ga≠(E), ∆Gc≠(E).
 Influence of the Electrode Potential on the Gibbs
Free energies of Activation
In the Butler-Volmer model, it is assumed that the Gibbs free energies of activation depend
linearly on the potential applied to the electrode.

Anodic transfer coefficient:

1 𝜕𝜕∆𝐺𝐺𝑎𝑎≠
𝛽𝛽 = − = 1 − 𝛼𝛼 > 0
𝐹𝐹 𝜕𝜕𝜕𝜕

(dimentionless)

When E↗ ∆𝐺𝐺𝑎𝑎≠↘
 Influence of the Electrode Potential on the Gibbs
Free energies of Activation

Cathodic transfer coefficient:

1 𝜕∆𝐺𝑐≠
𝛼= >0
𝐹 𝜕𝐸

(dimentionless)

When E ↘ ∆𝐺𝑐≠↘

NB: these simple relations between the Gibbs free energy of activation and the
applied potential are verified experimentally if the entire potential drop occurs in the
compact layer and if the reactants are not specifically adsorbed on the electrode.
About the Transfer Coefficient α

α accounts for the symmetry of the energy barrier

 Anodic and Cathodic Rate Constants

Lets use the linear approximation for ∆𝐺𝐺𝑎𝑎≠(E) and ∆𝐺𝐺𝑐𝑐≠(E) in the expression of the rate constants:

∆𝐺𝐺𝑎𝑎≠ (𝐸𝐸) ∆𝐺𝐺𝑎𝑎≠ ° 1−𝛼𝛼 𝐹𝐹(𝐸𝐸−𝐸𝐸𝐸)

𝑘𝑘𝑎𝑎 = 𝐴𝐴𝑎𝑎 . exp (− ) = 𝐴𝐴𝑎𝑎 . exp (− ). exp
𝑅𝑅𝑅𝑅 𝑅𝑅𝑅𝑅 𝑅𝑅𝑅𝑅

∆𝐺𝐺𝑐𝑐≠ (𝐸𝐸) ∆𝐺𝐺𝑐𝑐≠ ° 𝛼𝛼𝐹𝐹(𝐸𝐸−𝐸𝐸𝐸)

𝑘𝑘𝑐𝑐 = 𝐴𝐴𝑐𝑐 . exp (− ) = 𝐴𝐴𝑐𝑐 . exp (− ). exp −
𝑅𝑅𝑅𝑅 𝑅𝑅𝑅𝑅 𝑅𝑅𝑅𝑅

Too many unknown parameters are remaining (𝐴𝐴𝑎𝑎 , 𝐴𝐴𝑐𝑐 , ∆𝐺𝐺𝑎𝑎≠°, ∆𝐺𝐺𝑐𝑐≠°)! These expressions can be
simplified by considering the special case where the electrode interface is at equilibrium with
equal quantity of O and R in solution (𝐶𝐶𝑂𝑂 = 𝐶𝐶𝑅𝑅 ). According to Nernst law, then E = E°.

Since the interface is at equilibrium, 𝑣𝑣𝑐𝑐 = 𝑘𝑘𝑐𝑐 𝐶𝐶𝑂𝑂 = 𝑣𝑣𝑎𝑎 = 𝑘𝑘𝑎𝑎 𝐶𝐶𝑅𝑅 and as 𝐶𝐶𝑂𝑂 = 𝐶𝐶𝑅𝑅 , 𝑘𝑘𝑐𝑐 = 𝑘𝑘𝑎𝑎 = k°

∆𝐺𝐺𝑎𝑎≠ ° ∆𝐺𝐺𝑐𝑐≠ °
Then 𝐴𝐴𝑎𝑎 . exp (− ) = k° and 𝐴𝐴𝑐𝑐 . exp (− ) = k°
𝑅𝑅𝑅𝑅 𝑅𝑅𝑅𝑅
k° is called the standard rate constant of
the electrochemical reaction
 Anodic and Cathodic Rate Constants

1−𝛼𝛼 𝐹𝐹(𝐸𝐸−𝐸𝐸°)
Finally 𝑘𝑘𝑎𝑎 = k°. exp
𝑅𝑅𝑅𝑅

𝛼𝛼𝐹𝐹(𝐸𝐸−𝐸𝐸°)
And 𝑘𝑘𝑐𝑐 = k°. exp −
𝑅𝑅𝑅𝑅

k 𝑎𝑎 ↗ when E ↗

k 𝑐𝑐 ↗ when E ↘

k𝑎 = k𝑐𝑐 = k° when E = E°

Only two kinetic parameters (k° and

α) are necessary to express the
anodic and cathodic rate constants
 About the Standard Rate Constant k°

The values of standard rate constants of electrochemical reactions span a range of

about 17 orders of magnitude! They depend on the nature of the species, on the
nature of the medium (solvant, viscosity) and importantly on the nature and surface
condition of the electrode.

Redox couple Conditions k° (cm.s-1)

I2/I- Pt/HClO4 aq 60
Anthracene/Anthracene- Pt/NEt4BF4 (CH3CN) 5
Fe(CN)63-/Fe(CN)64- Pt/K2SO4 aq 10-2
H+/H2 Platinized Pt/H2SO4 10-3
H+/H2 Polished Pt/H2SO4 2.5×10-6
H+/H2 Fe/H2SO4 10-8
H+/H2 Hg/H2SO4 3×10-15
O2/H2O Pt/H2SO4 10-12
 Butler-Volmer Equations
The Butler Volmer equation describes how the electrical current
through an electrode depends on the potential applied to the electrode:

𝑖𝑖 = 𝐹𝐹𝐹𝐹(𝑘𝑘𝑎𝑎 𝐶𝐶𝑅𝑅𝑒𝑒𝑒𝑒 − 𝑘𝑘𝑐𝑐 𝐶𝐶𝑂𝑂𝑒𝑒𝑒𝑒 )

1 − 𝛼𝛼 𝐹𝐹(𝐸𝐸 − 𝐸𝐸𝐸) 𝑒𝑒𝑒𝑒

𝛼𝛼𝐹𝐹(𝐸𝐸 − 𝐸𝐸𝐸)
𝑖𝑖 = 𝐹𝐹𝐹𝐹k° 𝐶𝐶𝑅𝑅𝑒𝑒𝑒𝑒 exp − 𝐶𝐶𝑂𝑂 exp −
𝑅𝑅𝑅𝑅 𝑅𝑅𝑅𝑅

anodic branch cathodic branch

This is the first expression of the Butler-Volmer equation.

 Butler-Volmer Equations
Another equivalent expression can be derived in which the current
depends on the difference E – Eeq instead of E – E°

𝐶𝐶𝑅𝑅𝑒𝑒𝑒𝑒 1 − 𝛼𝛼 𝐹𝐹(𝐸𝐸 − 𝐸𝐸𝑒𝑒𝑒𝑒 ) 𝐶𝐶𝑂𝑂𝑒𝑒𝑒𝑒 𝛼𝛼𝐹𝐹(𝐸𝐸 − 𝐸𝐸𝑒𝑒𝑒𝑒 )

𝑖𝑖 = 𝑖𝑖° bulk exp − bulk exp −
𝐶𝐶𝑅𝑅 𝑅𝑅𝑅𝑅 𝐶𝐶𝑂𝑂 𝑅𝑅𝑅𝑅

1−𝛼𝛼 𝛼𝛼
where 𝑖𝑖° = FSk° 𝐶𝐶𝑂𝑂𝑏𝑏𝑏𝑏𝑒𝑒𝑏𝑏 𝐶𝐶𝑅𝑅𝑏𝑏𝑏𝑏𝑒𝑒𝑏𝑏 is the so-called exchange current.
NB: 𝑖𝑖° is not a new kinetic parameter because it is related to k°!

𝐶𝐶𝑂𝑂𝑏𝑏𝑏𝑏𝑒𝑒𝑏𝑏 and 𝐶𝐶𝑅𝑅𝑏𝑏𝑏𝑏𝑒𝑒𝑏𝑏 are the concentrations of the oxydant and reductant far from the
electrode.

E – Eeq is called the overpotential (η)

 Equilibrium Conditions
When the electrode is at equilibrium (E = Eeq), there is no net current flowing through and no
gradient of concentration :
𝐶𝐶𝑅𝑅𝑒𝑒𝑒𝑒 = 𝐶𝐶𝑅𝑅𝑏𝑏𝑏𝑏𝑒𝑒𝑏𝑏
𝐶𝐶𝑂𝑂𝑒𝑒𝑒𝑒 = 𝐶𝐶𝑂𝑂𝑏𝑏𝑏𝑏𝑒𝑒𝑏𝑏

1−𝛼𝛼 𝐹𝐹(𝐸𝐸𝑒𝑒𝑒𝑒−𝐸𝐸𝐸) 𝛼𝛼𝐹𝐹(𝐸𝐸𝑒𝑒𝑒𝑒−𝐸𝐸𝐸)

Then 𝑖𝑖 = 0 = 𝐹𝐹𝐹𝐹k° 𝐶𝐶𝑅𝑅𝑏𝑏𝑏𝑏𝑒𝑒𝑏𝑏 exp − 𝐶𝐶𝑂𝑂𝑏𝑏𝑏𝑏𝑒𝑒𝑏𝑏 exp −
𝑅𝑅𝑅𝑅 𝑅𝑅𝑅𝑅

1−𝛼𝛼 𝐹𝐹(𝐸𝐸𝑒𝑒𝑒𝑒−𝐸𝐸𝐸) 𝛼𝛼𝐹𝐹(𝐸𝐸𝑒𝑒𝑒𝑒−𝐸𝐸𝐸)

⇒ 𝐶𝐶𝑅𝑅𝑏𝑏𝑏𝑏𝑒𝑒𝑏𝑏 exp = 𝐶𝐶𝑂𝑂𝑏𝑏𝑏𝑏𝑒𝑒𝑏𝑏 exp −
𝑅𝑅𝑅𝑅 𝑅𝑅𝑅𝑅

𝐹𝐹(𝐸𝐸𝑒𝑒𝑒𝑒−𝐸𝐸𝐸)
⇒ 𝐶𝐶𝑅𝑅𝑏𝑏𝑏𝑏𝑒𝑒𝑏𝑏 exp = 𝐶𝐶𝑂𝑂𝑏𝑏𝑏𝑏𝑒𝑒𝑏𝑏
𝑅𝑅𝑅𝑅

𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏
𝑅𝑅𝑅𝑅 𝐶𝐶𝑂𝑂
⇒ 𝐸𝐸𝐸𝐸𝐸𝐸 = 𝐸𝐸𝐸 + ln We find the Nernst equation, which was expected!
𝐹𝐹 𝐶𝐶𝑅𝑅𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏

But electrochemical equilibriums are dynamic!

i = 𝑖𝑖𝑎𝑎 + 𝑖𝑖𝑐𝑐 = 0 , however 𝑖𝑖𝑎𝑎 = −𝑖𝑖𝑐𝑐 = 𝑖𝑖° ≠ 0
 Reversible Electrochemical Systems
When the electron transfer kinetics is very fast, the exchange current i° is very high

𝑒𝑒𝑏𝑏
𝑖𝑖 𝐶𝐶𝑅𝑅𝑒𝑒𝑏𝑏 1−𝛼𝛼 𝐹𝐹(𝐸𝐸−𝐸𝐸𝑒𝑒𝐸𝐸) 𝐶𝐶𝑂𝑂 𝛼𝛼𝐹𝐹(𝐸𝐸−𝐸𝐸𝑒𝑒𝐸𝐸)
Then = exp − exp − ≈0
𝑖𝑖0 𝐶𝐶𝑅𝑅𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑅𝑅𝑅𝑅 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏
𝐶𝐶𝑂𝑂 𝑅𝑅𝑅𝑅

𝑒𝑒𝑏𝑏
𝐶𝐶𝑅𝑅𝑒𝑒𝑏𝑏 1−𝛼𝛼 𝐹𝐹(𝐸𝐸−𝐸𝐸𝑒𝑒𝐸𝐸) 𝐶𝐶𝑂𝑂 𝛼𝛼𝐹𝐹(𝐸𝐸−𝐸𝐸𝑒𝑒𝐸𝐸)
⇒ exp = exp −
𝐶𝐶𝑅𝑅𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑅𝑅𝑅𝑅 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏
𝐶𝐶𝑂𝑂 𝑅𝑅𝑅𝑅

𝑒𝑒𝑏𝑏 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏
𝐶𝐶𝑂𝑂 𝐶𝐶𝑂𝑂 𝐹𝐹(𝐸𝐸−𝐸𝐸𝑒𝑒𝐸𝐸)
⇒ = exp
𝐶𝐶𝑅𝑅𝑒𝑒𝑏𝑏 𝐶𝐶𝑅𝑅𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑅𝑅𝑅𝑅

𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑒𝑒𝑏𝑏
𝐶𝐶𝑂𝑂 𝐹𝐹(𝐸𝐸𝑒𝑒𝐸𝐸−𝐸𝐸𝐸) 𝐶𝐶𝑂𝑂 𝐹𝐹(𝐸𝐸−𝐸𝐸𝐸)
As 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 = exp , then 𝑒𝑒𝑏𝑏 = exp
𝐶𝐶𝑅𝑅 𝑅𝑅𝑅𝑅 𝐶𝐶𝑅𝑅 𝑅𝑅𝑅𝑅

𝑒𝑒𝑏𝑏
𝑅𝑅𝑅𝑅 𝐶𝐶𝑂𝑂
⇒ 𝐸𝐸 = 𝐸𝐸𝐸 + ln
𝐹𝐹 𝐶𝐶𝑅𝑅𝑒𝑒𝑏𝑏 Whenever a potential is applied at the electrode, electron
transfer occurs with such a high rate that the equilibrium
conditions are allways established at the electrode!
 Chapter 3: Charge Transfer Kinetics

The purpose of this chapter is to establish the expression of the rate law of the charge
transfer which occurs in electrochemical reactions.
What does the rate of charge transfer depend on?
Which kinetic parameters should be involved and what is their significance?

3.1 Introduction
3.2 Reminders of Homogeneous Kinetics
3.3 Definition and Measurement of Rates
in Electrochemistry
3.4 Butler-Volmer Equations
3.5 Marcus Theory of Electron Transfer
 Outer Sphere Electron Transfer
The term “outer sphere” electron transfer refers to the transfer of an
electron between two species without the creation or breaking of
covalent bonds.
Ex : Ru(NH3)63+ + e- = Ru(NH3)62+

The reductant and oxidant differ by the bond lengths (for instance the
distance between the metal and the ligands), as well as the position and
orientation of the surrounding solvent molecules.
 Outer Sphere Electron Transfer
The electron transfer, however, follows the Franck-Condon principle: the
nuclear positions do not change on the time-scale of electronic
transitions.
The oxidant O and reductant R thus share a common nuclear
configuration at the moment of transfer.
At the microscopic level, the electron transfer between the oxidant and
reductant can be divided in three steps:
1) Thermally-induced reorganisation of the solvent molecules and
ligands in order to obtain a geometry favorable for electron transfer
(the precursor complex)
2) Electron transfer from the electrode by quantum tunneling
3) Destruction of the precursor complex and relaxation to obtain the
stable geometry of the product.
 The Simple Mathematical Treatment of Marcus
G° 𝐺𝐺 ° 𝑞𝑞 = 1 𝑘𝑘(𝑞𝑞 − 𝑞𝑞 )2 + 𝐺𝐺 ° 𝑞𝑞 𝐺𝐺𝑂𝑂 ° 𝑞𝑞 =
1
𝑘𝑘(𝑞𝑞 − 𝑞𝑞𝑂𝑂 )2 + 𝐺𝐺𝑂𝑂 ° 𝑞𝑞𝑂𝑂
𝑅𝑅 𝑅𝑅 𝑅𝑅 𝑅𝑅
2 2

1
λ = 𝑘𝑘(𝑞𝑞𝑅𝑅 − 𝑞𝑞𝑂𝑂 )2
2 R
O + e-
G

GR°(qR)
∆Gc ∆G°
GO°(qO)

qO q qR Reaction coordinate (q)

We need to determine the reaction coordinate of the precursor complex

(q≠) and express the Gibbs free energy of activation ∆Gc≠
 The Simple Mathematical Treatment of Marcus
1
𝐺𝐺𝑂𝑂 ° 𝑞𝑞 = 𝑘𝑘(𝑞𝑞 − 𝑞𝑞𝑂𝑂 )2 + 𝐺𝐺𝑂𝑂 ° 𝑞𝑞𝑂𝑂
2
1
𝐺𝐺𝑅𝑅 ° 𝑞𝑞 = 𝑘𝑘(𝑞𝑞 − 𝑞𝑞𝑅𝑅 )2 + 𝐺𝐺𝑅𝑅 ° 𝑞𝑞𝑅𝑅
2
At 𝑞𝑞≠ , the Gibbs free energy curve of the oxidant O and reductant R
intersept, so 𝐺𝐺 °(𝑞𝑞≠ )= 𝐺𝐺 ° 𝑞𝑞≠
𝑂𝑂 𝑅𝑅

≠
⇒ 𝑞𝑞 =
𝑞𝑞𝑂𝑂 +𝑞𝑞𝑅𝑅
+
∆𝐺𝐺𝐺
2 𝑘𝑘(𝑞𝑞𝑅𝑅 − 𝑞𝑞𝑂𝑂)

2
𝑘𝑘(𝑞𝑞𝑅𝑅 − 𝑞𝑞𝑂𝑂) 2
⇒ ∆𝐺𝐺𝑐𝑐≠ = 𝐺𝐺𝑂𝑂 ° 𝑞𝑞≠ − 𝐺𝐺𝑂𝑂 ° 𝑞𝑞𝑂𝑂 =
2∆𝐺𝐺𝐺
1+
8 𝑘𝑘(𝑞𝑞𝑅𝑅 − 𝑞𝑞𝑂𝑂) 2

2
𝑘𝑘(𝑞𝑞𝑅𝑅 − 𝑞𝑞𝑂𝑂) 2 2∆𝐺𝐺𝐺
= 1+
8 𝑘𝑘(𝑞𝑞𝑅𝑅 − 𝑞𝑞𝑂𝑂) 2
 Influence of the Reorganization Energy
1
The parameter λ = 𝑘𝑘(𝑞𝑞𝑅𝑅 − 𝑞𝑞𝑂𝑂 )2 represents the energy necessary to
2
transform the nuclear configurations in the oxidant O to those of the
reductant R. It is called the reorganization energy.
It contains an inner contribution (changes in the bond lengths and angles
of the reactant) and outer contribution (changes in the polarization of
solvent molecules)
λ = λ𝑖𝑖 + λ𝑂𝑂

The Gibbs free energy of activation and thus the rate constant k strongly
depends on the reorganization energy:
≠ λ ∆𝐺𝐺𝐺 2
∆𝐺𝐺𝑐𝑐 = 1+
4 λ

The lower the reorganisation energy between the oxidant and reductant,
the faster the electron transfer reaction.
 Influence of the Driving Force ∆𝐺𝐺𝐺
Marcus Normal Region Marcus Inverted Region
G° G°

O + e-
∆G2c

∆G1c
R
O + e- ∆G1°
∆G2c ∆G2° R
∆G1c
∆G1° ∆G2°

qO qR q qO qR q

∆𝐺𝐺𝑐𝑐≠ ↘ when ∆𝐺𝐺𝐺↘ G°

∆𝐺𝐺𝑐𝑐≠ ↗ when ∆𝐺𝐺𝐺↘
O + e- λ

∆G° R

qO qR q

when ∆𝐺𝐺°= −λ there is

no activation barrier!
 Predictions from Marcus Theory
For an electrode reaction occurring at applied potential E,
∆𝐺𝐺° = F(E − E°)
The rate constant of the cathodic process can then be expressed:
∆𝐺𝐺𝑐𝑐≠ λ F(E−E°) 2
𝑘𝑘𝑐𝑐 = 𝐴𝐴𝑐𝑐 . exp − = 𝐴𝐴𝑐𝑐 . exp − 1+
𝑅𝑅𝑅𝑅 4𝑅𝑅𝑅𝑅 λ

NB: in the most common cases λ ≫ F(E − E°)

λ 2F(E−E°)
=> 𝑘𝑘𝑐𝑐 ≈ 𝐴𝐴𝑐𝑐 . exp − 1+
4𝑅𝑅𝑅𝑅 λ

λ 1 F(E−E°)
≈ 𝐴𝐴𝑐𝑐 . exp − exp −
4𝑅𝑅𝑅𝑅 2 2𝑅𝑅𝑅𝑅
λ
This is the Butler-Volmer equation with k° = 𝐴𝐴𝑐𝑐 . exp − and α = ½
4𝑅𝑅𝑅𝑅

k° ↘ when λ ↗ : a high reorganization makes a redox system slow!

 Exercise

Exercise 3.1
At 37°C the rate constant for a particular electron transfer reaction is twice the one at 0°C.
The driving force of the reaction is -11.3 kJ.mol-1 and assumed to be independent on the
temperature in the range studied here.

a) What is the reorganisation energy for this reaction?

b) What is the reorganisation energy when the rate constant is maximal?