ELECTRODE PROCESSES AND Advanced Physical Chemistry

(SCC4009)
Dr. Leung Chi Fai
REACTIONS Department of Science and
Environmental Studies
 ELECTROCHEMISTRY: GALVANIC VS ELECTROLYTIC CELLS

When an potential (Eapplied) is applied

across the electrodes, what will happen?
o If Ecell > Eapplied , current in the external
circuit flows in the same direction, but
reduced.
o If Ecell = Eapplied, current = 0 A
o If Ecell < Eapplied , current in the external
circuit flows in the reversed direction.
(Now, become an electrolytic cell)
ELECTROLYSIS AND ELECTROLYTIC CELLS
In galvanic cells (also called voltaic cells) and
batteries, spontaneous chemical reactions provide the
driving force, i.e. electromotive force (EMF), for
electrons, producing an electric current through an
outside circuit.
The reverse reaction is non-spontaneous (a process is e– e–
Z– Y+
known as electrolysis)and requires the provision of an
external driving force (an applied potential/voltage,
Z Y
Eoapplied).
The cell (electrolytic cells) does work on the chemical
system by driving an electric current through the
system.
Electrons are forced through the cell, causing a
chemical reaction on a pair of inert electrodes
ELECTROLYTIC CELLS
Electrons are supplied by an external source, entering through the cathode and coming
out through the anode
The direction of electron flow in electrolytic cells are reversed from that of spontaneous
electron flow in galvanic cells
The sign of the electrodes and cell potential are reversed (not the magnitude) as
opposite to Galvanic cells.
▪Cathode (negative): reduction
(=>Spontaneous)
▪Anode (positive): Oxidation
Reactants ⇌ Products + Electrical Energy
(<=Non-spontaneous)
 G = – nFE
o

If E is negative, oG is positive (non-spontaneous)

ELECTROLYSIS AND ELECTROLYTIC CELLS
As atoms and ions have to move physically in electrolysis, the reaction medium has to be a
fluid. Thus, the process is carried out in solutions or molten salts (liquid) and ions are
attracted to electrodes bearing opposite charges
Aqueous-state reaction: Molten-state reaction:
Water (acidified) can be decomposed. ▪Cathode (Reduction): providing electron(s)
 Cathode: 2H+ + 2e− → H2 Na+ + e− → Na
 Anode: 2H2O → 4H+ + 4e− + O2 ▪Anode (oxidation): removing electron(s)
 Overall: 2H2O → 2H2 + O2 2Cl− → Cl2 + 2e−
Pt|H2O, [H+] = 1M|O2||H2O, [OH−] =1M|H2|Pt ▪Overall: 2Cl− + 2Na+ → Cl2 + 2Na
 ELECTROLYTIC CELLS
Aqueous-state reaction:
Conditions Eocathode Eoanode Eocell
Water (acidified) can be decomposed.
Standard condition
0V 1.23 V – 1.23 V
 Cathode: 2H+ + 2e− → H2 ([OH-] and [H+] = 1 M,
P =1atm) (pH = 0)
 Anode: H2O → 4H+ + 4e− + O2
pH = 14 –0.82V 0.40V – 1.23 V
 Overall: 2H2O → 2H2 + O2

Pt|H2O, [H+] = 1M|O2||H2O, [OH−] =1M|H2|Pt

𝑛
0.0591 [𝑟𝑒𝑑𝑢𝑐𝑒𝑑 𝑠𝑝𝑒𝑐𝑖𝑒𝑠]
𝐸 = 𝐸𝑜 − log
𝑛𝐹 [𝑜𝑥𝑖𝑑𝑖𝑧𝑒𝑑 𝑠𝑝𝑒𝑐𝑖𝑒𝑠]𝑚

ΔG° = –nFE = 474.48 kJ

Pure water feature a low autoionization, Kw = 1.0 ×
10−14 at room temperature, and thus a poor conductivity
(0.055 µS·cm−1).
Usually, a large potential is applied to increase the
autoionization; slow rate limited conductivity.
 ELECTROLYTIC CELLS

Aqueous-state reaction Diaphragm prevent the Cl2 formed from coming

Molten-state reaction: into contact with the cathode and NaOH
Cathode (–):
Cathode (–):
Na+ + e– → Na (Eo = –2.71 V)
Na+ + e– → Na (Eo = –2.71 V)
2 H2O + 2 e– → H2 + 2 OH – (Eo = – 0.83 V) (OH- formed)
Anode (+):
Anode (+):
2 Cl- → Cl2 + 2e– (Eo = 1.36 V) reduction potential
2 Cl- → Cl2 + 2e– (Eo = 1.36 V)
Overall: 2 NaCl(l) → 2 Na(l) + Cl2(g)
Eocell= Eocathode– Eoanode = – 2.71 V – (1.36 V) = – 4.07V 2 H2O → O2 + 4 H+ + 4 e– (Eo = 1.23 V)

Applied potential of ≥4.07V is needed Overall: 2 NaCl(aq) + 2 H2O(l) → 2 Na+(aq) + 2 OH –(aq) + H2(g) + Cl2(g)
If 25% (w/w) NaCl (aq) solution used, E lower than Eo
Product: NaOH (aq), H2(g) and Cl2(g)
ELECTROPLATING
Electroplating: the process by which a layer of a
second metal is deposited on the metal electrode
that acts as the cathode during electrolysis
Cathode (fork):
Ag+(aq) + e− ⟶ Ag(s) E°cathode = 0.80V
Anode (silver bar):
Ag(s) ⟶ Ag+(aq) + e− E°anode = 0.80V

Eocell = 0.8 V – 0.8 V = 0.0V

Thus, a low applied potential (Eapplied) will be enough

to drive the process.
MASS TRANSPORT
Faradaic current: measure of the rate of electrochemical
reaction taking place at the electrode and is dependent on:
o Rate at which material gets from the bulk of solution to
the electrode, i.e. mass transport
o Rate at which electrons can transfer across the interface,
or charge transfer kinetics.
Basic mechanisms of mass transport:
o Diffusion: spontaneous movement of any material from
where it is to where it is not
o Migration: movement of charged particles in electric field
o Convection: movement of bulk solution carrying species
with it, e.g. eddy current
 MASS TRANSPORT
Diffusion: random movement of molecules from
a region of high concentration to regions of
lower concentration.
Diffusion rate depends upon the difference in
concentration between two points in solution, i.e.
the concentration gradient, and the diffusion
coefficient, D, which is characteristic of a
specific solution species at a certain
temperature. 𝑑𝐶
The movement of the species (i) through a cross- 𝐽𝑖 = −𝐷
𝑑𝑥
sectional area as a function of the concentration
gradient dC/dx) across the selected area (is
described by Fick’s first law.
MASS TRANSPORT
Migration: movement of charged particles in response to a
local electric field, i.e. coulombic forces.
The net flux (ij) of a charged species (j) contribute to the total
flux and is proportional to:
o Charge of the ion (z),
o Ion concentration, 𝑧𝑗2 𝐹 2 𝐴𝐷𝑗 𝐶𝑖 𝜙
𝑖𝑖 = ×
𝑅𝑇 𝑥
o Diffusion coefficient, and
o Magnitude of the electric field gradient (thus applied A = cross sectional area (cm2)
potential at the electrode) experienced. D = diffusion coefficient (cm2 s-1)
C = molar concentration (M)
Resulting in the charging of the interfaces between electrode 𝛿𝜙
= electric field gradient (V cm-1)
and solution and the formation of the double-layer. 𝛿𝑥
MASS TRANSPORT
Convection: the forced movement of solution species by
mechanical (stirring) or other means (evaporation of solution.
The rate of stirring is generally controlled and the convective
contribution (to total flux) of a species (x) is described by its
hydrodynamic velocity (νx)
o Important for movement of a species over a large distance
(<0.5 nm)
o Also caused by the evaporation from the surface of a static
(unstirred) solution (unimportant)
Total mass transport of material, or flux, to an electrode is
described (in one dimension) by the Nernst-Planck equation.
HETEROGENEOUS ELECTRON TRANSFER
▪ Tunnelling of e- from atoms on electrode surface
to a species in solution (reduction) or vice versa Solution
(oxidation). Electrode
▪ Rate of e- transfer depends on: LUMO
a) Structure of double layer (vacant)

b) Energetics and distance between the electrode Fermi fixed

and the species in solution. Level

⇌
HOMO
(occupied)
▪ Femi level (electrode) : highest energy occupied
levels state;
a) Varied with the polarization of electrode by
applied voltage (+ve or –ve; unit: V = JC-1)
b) Equilibrium: E (Femi level) vs E (frontier orbital)
 HETEROGENEOUS ELECTRON TRANSFER
▪ If E (FL) > E (FO), reduction occurs
▪ If E (FL) > E (FO), oxidation occurs Electrode Electrode
▪ Electron transfer: e–
–ve FL ↿ –ve
a) Occurs to and from solution species
continuously LUMO LUMO
↿
b) Manifested as net current density/flux

⇌
(J, unit: A cm-2); difference of current
+ve HOMO HOMO
for the anodic (from solution species to +ve
FL
e–
electrode) and cathodic (from
electrode to solution species) reactions
J = Ja – Jc Reduction: Oxidation:
c) Rate constant of e– transfer (ko) A + e– → A – A → A + + e–
ELECTRODE EQUILIBRIUM & FORMAL POTENTIALS
▪ Equilibrium electrode potential (E):
a) Potential at which the rate (forward ET) = rate (reverse ET)
b) Net current flux = 0
c) Not necessarily same as the standard electrode potential
▪ If applied potential  equilibrium electrode potential,
a) rate (forward ET)  rate (reverse ET) and
b) net current  0
▪ Current (i) depends exponentially on overpotential () and is
describe by the Tafel equation.
ELECTRODE EQUILIBRIUM & FORMAL POTENTIALS
▪ [FeIII(CN)6]3-(aq) + Ag(s) + Cl- (aq) ⇌ [FeII(CN)6]4– (aq) + AgCl(s)

Working electrode (WE): [FeIII(CN)6]3-(aq) + e– ⇌ [FeII(CN)6]4– (aq)

Reference electrode (RE): AgCl(s) + e– ⇌ Ag(s) + Cl– (aq)
𝑅𝑇 𝛼𝐹𝑒2+
▪ 𝐸= °
𝐸(𝐹𝑒 3+ /𝐹𝑒 2+ ) − ln (a = activity = aCa)
𝑛𝐹 𝛼𝐹𝑒3+

▪ At varied E, a different [Fe2+]/[Fe3+] is required to be at equilibrium

and a generating a current for the conversion between oxidation states.
𝛼𝐹𝑒2+ 𝛼𝐹𝑒2+
▪ E = E , when = 1 and ln =0
𝛼𝐹𝑒3+ 𝛼𝐹𝑒3+

▪ When Cred = Cox, will red = ox ? (red  ox)

 ELECTRODE EQUILIBRIUM & FORMAL POTENTIALS
▪ Formal potential (𝑬°𝒇 ):
𝑅𝑇 𝛼𝐹𝑒2+
a) the potential under a specified set of conditions °
𝐸 = 𝐸(𝐹𝑒 3+ /𝐹𝑒 2+ ) −
𝑛𝐹
ln
𝛼𝐹𝑒3+
(pH, ionic strength, and concentration of
solutions, e.g pH 7 in biology) 𝑅𝑇 𝛾𝑟𝑒𝑑 𝐶𝑟𝑒𝑑
𝐸= 𝐸° − ln
b) arises, as red  ox 𝑛𝐹 𝛾𝑜𝑥 𝐶𝑜𝑥

▪ Overpotential (): 𝑅𝑇 𝛾𝑟𝑒𝑑 𝐶𝑟𝑒𝑑

𝐸 = 𝐸° − ln + ln
a) The extra electrode polarization required be 𝑛𝐹 𝛾𝑜𝑥 𝐶𝑜𝑥
beyond the formal potential (𝑬°𝒇 ) to proceed
𝑅𝑇 𝛾𝑟𝑒𝑑 𝑅𝑇 𝐶𝑟𝑒𝑑
at significant reaction rate (current) 𝐸= 𝐸° −
𝑛𝐹
ln
𝛾𝑜𝑥
−
𝑛𝐹
ln
𝐶𝑜𝑥
b) The difference between the applied and the
equilibrium electrode potentials (E1/2), usually 𝐸 = 𝐸𝑓° −
𝑅𝑇
ln
𝐶𝑟𝑒𝑑
represented by the formal potential) 𝑛𝐹 𝐶𝑜𝑥

c)  = Eapplied – E1/2
ELECTRODE EQUILIBRIUM & FORMAL POTENTIALS
▪ Potential at electrode surface (elec)
IHP OHP
▪ Potential at the electrolyte (sol)
––
▪ Galvani potential difference  = elec – sol –– +

–– +
▪ The driving force available to do work! elec ––
––
––
+
–– +
––
––
–– + + 
sol
––
––
–– +
Helmholtz or Stern
double layers (0.5nm thick)
CHEMICAL AND ELECTROCHEMICAL POTENTIAL
▪ Electrical work done (WE) in an electrochemical reaction:
WE= –nFE d
At constant temperature and pressure, e –
+ + e–

WE = GT,P and GT,P = –nFE F WE = F x d

GR = nR and R = GR/n
R = change of the chemical potential for the reaction

▪ The work of transport of a charged species includes the

electrical work (𝑧𝐹𝜙) associated with charge movement
between phases of different potential ()
▪ 𝜇ҧ = 𝜇 + 𝑧𝐹𝜙 and Δ𝜇ҧ1−2 = Δ𝜇1−2 + 𝑧𝐹Δ𝜙1−2
▪ 𝜇ҧ = electrochemical potetnail
 THERMODYNAMICS OF ELECTRODE REACTIONS
▪ H+(aq) + M(s) → M+(aq) + ½ H2(g)
▪ Driving force for reaction (Δ𝑟 𝐺 ° ):
Δ𝑟 𝐺 ° = 𝐺𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝐺𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
1
= 𝜇 + 𝜇𝑀 + − 𝜇𝐻 + + 𝜇𝑀
2 𝐻2
1
= 𝜇 − 𝜇𝐻 + − 𝜇𝑀 + 𝜇𝑀 +
2 𝐻2
▪ M(s)M+(aq)H+(aq), H2(g)Pt
✓ LHS reaction: M+(aq) + e– → M(s) ∆𝑟 𝐺𝐿
✓ RHS reaction: H+(aq) + e–→ ½H2(g) ∆𝑟 𝐺𝑅
✓ Overall reaction: H+(aq) + M(s) → M+(aq) + ½H2(g)
✓ Reaction driving force (std condition): ∆𝑟 𝐺 ° = ∆𝑟 𝐺𝑅 − ∆𝑟 𝐺𝐿
 THERMODYNAMICS OF ELECTRODE REACTIONS
▪ LHS electrode (M/M+): M+ + e– → M(s) ▪ RHS electrode (H+/H2): H+ + e– → ½H2
▪ ∆𝑟 𝐺𝐿° = 𝜇(products)
ҧ – 𝜇(reactants)
ҧ ▪ ∆𝑟 𝐺𝑅° = 𝜇(products)
ҧ – 𝜇(reactants)
ҧ
1
i.e. ∆𝐺𝐿° = 𝜇ҧ𝑀 − (𝜇ҧ𝑀+ + 𝜇ҧ 𝑒 − ) i.e. ∆𝐺𝑅° = 𝜇ҧ𝐻2 − (𝜇ҧ𝐻 + + 𝜇ҧ𝑒 − )
2
𝜇ҧ𝑀 = 𝜇𝑀 (for metal, neutral) 𝜇ҧ𝐻2 = 𝜇𝐻2 (for gas, neutral)
𝜇ҧ𝑀+ = 𝜇𝑀+ + 𝐹𝜙𝑠𝑜𝑙 𝜇ҧ𝐻 + = 𝜇𝐻 + + 𝐹𝜙𝑠𝑜𝑙
(z = +1 or –1 for singly charged species) (z = +1 or –1 for singly charged species)
𝜇ҧ𝑒 − = 𝜇𝑒 − − 𝐹𝜙𝑀 𝜇ҧ𝑒 − = 𝜇𝑒 − − 𝐹𝜙𝑒𝑙𝑒𝑐
𝜙𝑠𝑜𝑙 and 𝜙𝑀 = Galvani potentials of solvent
and electrode (metal)
1
Δ𝑟 𝐺𝑅° = 𝜇𝐻2 − [ 𝜇𝐻 + + 𝐹𝜙𝑠𝑜𝑙 + 𝜇𝑒 − − 𝐹𝜙𝑒𝑙𝑒𝑐 ]
Δ𝑟 𝐺𝐿° = 𝜇𝑀 − [ 𝜇𝑀+ + 𝐹𝜙𝑠𝑜𝑙 + 𝜇𝑒 − − 𝐹𝜙𝑀 ] 2
1
Δ𝑟 𝐺𝐿° = 𝜇𝑀 − 𝜇𝑀+ − 𝜇𝑒 − + 𝐹 𝜙𝑀 − 𝜙𝑠𝑜𝑙 Δ𝑟 𝐺𝑅° = 𝜇𝐻2 − 𝜇𝐻 + − 𝜇𝑒 − + 𝐹 𝜙𝑒𝑙𝑒𝑐 − 𝜙𝑠𝑜𝑙
2

(Galvani potential difference on LHS electrode) (Galvani potential difference on RHS electrode)
 THERMODYNAMICS OF ELECTRODE REACTIONS
H+(aq) + M(s) → M+(aq) + ½ H2(g)

1
▪ Δ𝑟 𝐺𝑅 = 𝜇𝐻2 − 𝜇𝐻 + − 𝜇𝑒 − + 𝐹Δ𝜙𝑅𝐻𝑆
2

▪ Δ𝑟 𝐺𝐿 = 𝜇𝑀 − 𝜇𝑀+ − 𝜇𝑒 − + 𝐹Δ𝜙𝐿𝐻𝑆
▪ Driving force for overall reaction: 𝜟𝒓 𝑮𝒄𝒆𝒍𝒍 = 𝜟𝒓 𝑮𝑹 − 𝜟𝒓 𝑮𝑳

1
= 𝜇𝐻2 − 𝜇𝐻 + − 𝜇𝑒 − + 𝐹Δ𝜙𝑅𝐻𝑆 − 𝜇𝑀 − 𝜇𝑀+ − 𝜇𝑒 − + 𝐹Δ𝜙𝐿𝐻𝑆
2
1
= 𝜇𝐻2 − 𝜇𝐻 + − 𝜇𝑒 − + 𝐹Δ𝜙𝑅𝐻𝑆 − 𝜇𝑀 + 𝜇𝑀+ + 𝜇𝑒 − − 𝐹Δ𝜙𝐿𝐻𝑆
2 If the system is in equilibrium, 𝛥𝑟 Gcell = 0 and
Δ 𝐺  = − 𝐹Δ𝜙
𝟏
= 𝝁 + 𝝁𝑴+ − 𝝁𝑯+ − 𝝁𝑴 + 𝐹Δ𝜙𝑅𝐻𝑆 − 𝐹Δ𝜙𝐿𝐻𝑆 r 𝑅𝐻𝑆 − 𝐹Δ𝜙 𝐿𝐻𝑆
𝟐 𝑯𝟐

𝜟𝒓 𝑮𝒄𝒆𝒍𝒍 = 𝜟𝒓 𝑮 + (𝑭𝜟𝝓𝑹𝑯𝑺 − 𝑭𝜟𝝓𝑳𝑯𝑺 )

Since Δ𝐸 = 𝐸𝑅 − 𝐸𝐿 = Δ𝜙𝑅𝐻𝑆 − Δ𝜙𝐿𝐻𝑆
Δ 𝐺  = −𝐹Δ𝐸 or
r

Δr 𝑮 = −𝑭𝑬 (when no. of e– >1)

KINETICS OF ELECTROCHEMICAL REACTIONS
▪ Change in the electrode potential drive the system to re-establish new
equilibrium
▪ The rate at which the equilibrium re-establish is manifested in the current
measured and I vs E relation could be determined (voltammetric technique)
▪ Current can be limited by the following steps involved in the electrode
reaction:
o Heterogeneous e– transfer kinetics
o Chemical reactions
o Reorganization (solvent, ion)
o Absorption/desorption of species at the electrode
o Mass transport…
 Jc

ELECTROCHEMICAL RATES Ox

▪ Current (I)  cross sectional area (A) of the electrode Red

Electrolyte
Electrode
▪ Current density (J, unit: A cm-2): comparison between systems of different
electrode area (A) J
net current
▪ Net current density (J = Ja – Jc): net oxidation (Ja)/reduction (Jc) at the
electrode, continuous exchange of e– between electrode and redox Red
active species in the solution.
▪ Rate (unit: Ms–1)  concentration species Ox
Ja
(oxidized/reduced)
𝑑𝑂
Rate (reduction) = = 𝑘𝑐 𝑂𝑥 𝑥=0
𝑑𝑡
𝑑𝑅
Rate (oxidation) = = 𝑘𝑎 𝑅𝑒𝑑 𝑥=0
𝑑𝑡

kc and ka = rate constant for e– transfer to and from the electrode

[Ox]x=0 and [Red]x=0 = concentration of oxidize and reduced species at the electrode
 TRANSITION STATE THEORY & THE RATE Ox + e– → Red
OF HETEROGENEOUS ELECTRON TRANSFER
▪ Current density (Jc and Ja):
𝑑[𝑂𝑥]
𝐽𝑐 = 𝜈𝐹 = 𝜈𝐹𝑘𝑐 𝑂𝑥 𝑥=0
𝑑𝑡
𝑑[𝑅𝑒𝑑]
𝐽𝑎 = 𝜈𝐹 = 𝜈𝐹𝑘𝑎 𝑅𝑒𝑑 𝑥=0
𝑑𝑡
( = number of e– involved)
▪ Thus,
𝑱 = 𝑱𝒂 − 𝑱𝒄 = 𝝂𝑭𝒌𝒂 𝑹𝒆𝒅 − 𝝂𝑭𝒌𝒄 𝑶𝒙 rG = −nFE

▪ Eyring-Polanyi Equation (modified):  = transmittion coefficient (1)

‡ kB = Boltzmann constant (unit: J K-1)
𝑘 = 𝐵𝑐 exp −𝛥𝐺 /𝑅𝑇 (where 𝐵𝑐 = 𝜅𝑘𝐵 𝑇/ℎ ) h = Planck constant (unit: J s)
Bc (unit: s-1 or cm s-1 for heterogeneous rxn)
 TRANSITION STATE THEORY & THE RATE OF
HETEROGENEOUS ELECTRON TRANSFER
▪ Rate constant for reduction (kc)and oxidation (ka):
𝑘𝑐 = 𝐵𝑐 exp −Δ𝑟𝑒𝑑 𝐺 ‡ /𝑅𝑇
𝑘𝑎 = 𝐵𝑎 exp −Δ𝑜𝑥 𝐺 ‡ /𝑅𝑇
▪ E1/2 of the Ox/Red species in solution is constant
▪ Potential of e- in the electrode is variable (polarization)
▪ Reduction (backward) spontaneous, as rG = –ve
▪ How will Oxidation (forward) be spontaneous, if rG = +ve
▪ Increasing electrode potential ? Moving LH potential well vertically (upward)
▪ When Δ𝐺𝑐‡ = Δ𝐺𝑎‡ = ∆‡ 𝐺 ° , 𝑘𝑐 = 𝑘𝑎 rxn at equilibrium
potential
▪ Change in the driving force (∆𝑟 𝐺) resulted from the change in electrode potential: energy
well
∆∆𝑟 𝐺 = 𝜈𝐹(𝐸𝑎𝑝𝑝𝑙𝑖𝑒𝑑 − 𝑬𝟏/𝟐 ) = 𝜈𝐹𝜂 ▪ 𝜶 = fractional change of overpotential
𝜟𝒓𝒆𝒅 𝑮‡ = △‡ 𝑮∘𝒄 + 𝜶𝝂𝑭𝜼 ▪ asymmetry factor/transfer coefficient
𝜟𝒐𝒙 𝑮‡ = △‡ 𝑮∘𝒂 − (𝟏 − 𝜶)𝝂𝑭𝜼 ▪ typically 0.5 for reversible redox process
THE STANDARD/EXCHANGE RATE CONSTANT
AND THE BUTLER-VOLMER EQUATION
▪ If  = 1
𝑘𝑐 = 𝐵𝑐 exp −Δ𝑟𝑒𝑑 𝐺 ‡ /𝑅𝑇 and Δ𝑟𝑒𝑑 𝐺 ‡ = △‡ 𝐺𝑐∘ + 𝛼𝜈𝐹𝜂
△‡ 𝐺𝑐∘ + 𝛼𝐹𝜂
𝑘𝑐 = 𝐵𝑐 exp −
𝑅𝑇
𝑘𝑎 = 𝐵𝑎 exp −Δ𝑜𝑥 𝐺 ‡ /𝑅𝑇 and Δ𝑜𝑥 𝐺 ‡ = △‡ 𝐺𝑎∘ − (1 − 𝛼)𝜈𝐹𝜂
△‡ 𝐺𝑎∘ − (1 − 𝛼)𝐹𝜂
𝑘𝑎 = 𝐵𝑎 exp −
𝑅𝑇

△‡ 𝐺𝑎∘ − (1 − 𝛼)𝐹𝜂 △‡ 𝑮∘𝒂 (𝟏 − 𝜶)𝑭𝜼

𝑱𝒂 = 𝐹𝐵𝑎 𝑅𝑒𝑑 𝐵𝑎 exp − = 𝑭𝑩𝒂 𝑹𝒆𝒅 𝐞𝐱𝐩 − 𝒆𝒙𝒑
𝑅𝑇 𝑹𝑻 𝑹𝑻
△‡ 𝐺𝑐∘ + 𝛼𝐹𝜂 △‡ 𝑮∘𝒄 𝜶𝑭𝜼
𝑱𝒄 = 𝐹𝐵𝑐 𝑂𝑥 𝐵𝑐 exp − = 𝑭𝑩𝒄 𝑶𝒙 𝒆𝒙𝒑 − 𝒆𝒙𝒑 −
𝑅𝑇 𝑹𝑻 𝑹𝑻
THE STANDARD/EXCHANGE RATE CONSTANT
AND THE BUTLER-VOLMER EQUATION
Question(1): Calculate the change in, i.e. the ratio of, the cathodic current density at an electrode
when the potential difference changes from ′ and  by 1.0 V, when T = 298K and = ½; assuming
the concentration of the oxidized species [Ox] remain unchanged.
△‡ 𝐺𝑐∘ 𝛼𝐹𝜂
Hint: Use to expression, 𝐽𝑐 = 𝐹𝐵𝑐 𝑂𝑥 𝑒𝑥𝑝 − 𝑒𝑥𝑝 − to find the ratio of cathodic current
𝑅𝑇 𝑅𝑇
densities jc′ and jc.

𝐹
𝐽𝑐′ −𝛼 𝜂1 −𝜂
= 𝑒 𝑅𝑇
𝐽𝑐
1
𝛼𝐹 ×96485 Cmol−1 ×1.0V
− 𝜂1 − 𝜂 = 2
= −19.47
𝑅𝑇 8.3145 JK−1 mol−1 ×298 K
𝛼𝐹
𝐽𝑐′ − 𝜂1 −𝜂
= 𝑒 𝑅𝑇 = 𝑒 −19.47 = 𝟑. 𝟓 × 𝟏𝟎−𝟗
𝐽𝑐
 THE STANDARD/EXCHANGE RATE CONSTANT
AND THE BUTLER-VOLMER EQUATION
If  = 0 (zero overpotential, i.e. Eapplied = E1/2) and 𝑱 = 𝑱𝒂 − 𝑱𝒄
J = 0 and Ja = Jc = Jo (i.e. exchange current density)

△‡ 𝐺𝑎∘ △‡ 𝐺𝑐∘
𝐽𝑜 = 𝜈𝐹𝐵𝑎 𝑅𝑒𝑑 𝐵𝑎 exp − = 𝜈𝐹𝐵𝑐 𝑂𝑥 𝐵𝑐 exp −
𝑅𝑇 𝑅𝑇
(1 − 𝛼)𝐹𝜂
𝐽𝑎 = 𝐽𝑜 exp
𝑅𝑇
𝛼𝐹𝜂
𝐽𝑐 = 𝐽𝑜 exp −
𝑅𝑇

(𝟏 − 𝜶)𝑭𝜼 𝜶𝑭𝜼 Butler-Volmer

𝑱 = 𝑱𝒐 𝒆𝒙𝒑 − 𝑱𝒐 𝒆𝒙𝒑 − Equation
𝑹𝑻 𝑹𝑻
TAFEL PLOT
(1 − 𝛼)𝐹𝜂 𝛼𝐹𝜂
𝐽 = 𝐽𝑜 exp − 𝐽𝑜 exp −
𝑅𝑇 𝑅𝑇
At low overpotential:
𝑭𝜼
When  is small (<0.01V), 𝑱 ≈ 𝑱𝟎
𝑹𝑻
At large overpotential:
When  is large (0.12V),
(𝟏−𝜶)𝑭𝜼 𝟏−𝜶 𝑭𝜼
𝑱 = 𝑱𝒐 𝐞𝐱𝐩( ) and 𝐥𝐧 𝑱 = 𝐥𝐧 𝑱𝒐 +
𝑹𝑻 𝑹𝑻
When  is large (–0.12V),
𝜶𝑭𝜼 𝜶𝑭𝜼
𝑱 = 𝑱𝒐 𝐞𝐱𝐩(− ) and 𝐥𝐧 𝑱 = 𝐥𝐧 𝑱𝟎 −
𝑹𝑻 𝑹𝑻
TAFEL PLOT
Question (2): The exchange current density of a Pt(s)|H2(g) |H+(aq) electrode at 298
K is 0.79 mA cm−2. Calculate the current through the electrode, which has an area of
5.0 cm-2, when the overpotential (η) is +5.0 mV.

𝐹𝜂
The current density through the electrode obtained by using 𝐽 ≈ 𝐽0 :
𝑅𝑇
𝐹𝜂 96485 Cmol−1 ×5×10−3 V
𝐽≈ 𝐽0 = 0.79 mA cm−2 × = 0.154 mA cm−2
𝑅𝑇 8.1345 JK−1 mol−1 ×298 K

The current through an electrode of total area 5.0 cm2 is therefore:

0.154 mA cm-2  5.0 cm2 = 0.77 mA
TAFEL PLOT
Question (3): The data below refer to the anodic current through a platinum electrode of area 2.0 cm2 in contact with
an Fe3+,Fe2+ aqueous solution at 298 K. Calculate the exchange current density and the transfer coefficient for the
electrode process. (Hint: The anodic process is the oxidation Fe2+(aq)→Fe3+(aq) + e−. To analyse the data, we make a
Tafel plot (lnj vs η) using the anodic form. The intercept at η = 0 is ln j0 and the slope is (1 −α)F/RT.)
η/mV 50 100 150 200 250
I/mA 8.8 25.0 58.0 131 298

(mV) I (mA) I (A) J (A cm-2)  (V) ln J

50 8.8 0.0088 0.0044 0.05 -5.42615
100 25 0.025 0.0125 0.1 -4.38203 lnJ vs 
150 58 0.058 0.029 0.15 -3.54046 0
0 0.05 0.1 0.15 0.2 0.25 0.3
200 131 0.131 0.0655 0.2 -2.72571 -0.5
250 298 0.298 0.149 0.25 -1.90381 -1
-1.5
y = 16.499x - 6.0253
𝟏−𝜶 𝑭𝜼 -2 R² = 1
At high η, 𝐥𝐧 𝑱 = 𝐥𝐧 𝑱𝒐 + -2.5
𝑹𝑻
-3
-3.5

ln𝐽𝑜 = -6.0253 and 𝐽𝑜 = 2.4 mA cm-2 -4

-4.5
-5

1−𝛼 𝐹 1 − 𝛼 × 964857 C mol−1

= 16.499 V-1 =
𝑅𝑇 8.1345 J mol−1 𝐾 −1 × 298 K
 = 0.58
 LIMITING CURRENT DENSITY
VOLTAMMETRIC TECHNIQUE
▪ The rate processes and a redox couple of the type Mz+/M;
Reduction: Mz+ + ze− → M.
▪ No flow of current can exceed the limiting current density
(Jlim )

▪ Jlim  z, D (diffusion coefficient) and c (bulk concentration)

▪ Jlim  1/ ( = thickness of the diffusion layer
 LIMITING CURRENT DENSITY Typical LSV

VOLTAMMETRIC TECHNIQUE
▪ Study of I as a function of Eapplied
▪ Monitor the change in I , while varying Eapplied
Typical CV
▪ Examples:
o Linear Sweep Voltammetry (LSV):
Eapplied varies linearly with time.
o Cyclic Voltammetry (CV):
Eapplied is varied in a sawtooth manner on the
working electrode and I is monitored. (a) The change of potential with time
▪ Voltammogram: current-potential curve (b) The resulting current/potential curve in a cyclic
voltammetry (CV) experiment.
▪ Obtained using a three-electrode configuration:
oWorking electrode
oReference electrode
oCounter or auxiliary electrode
VOLTAMMETRIC METHODS
For an overall electrode reaction: Anodic scan:
O + ne– ⇌ R (1)
As E is varied, the potential energy of e– varies with
respect to that of the solution species.
Cathodic scan: PE increases (>LUMO) and reduction
occurs. Cathodic scan:
the potential sweeps
Anodic scan: PE lowers (<HOMO) and oxidation occurs in the negative direction

In reversible electrode process, where rate of e– transfer is

>> rate of mass transfer (controlled by diffusion rate),
electrochemical potential can be represented as:
0.05916 [𝐶 ]
𝐸 = 𝐸𝑜 − 𝑙𝑜𝑔 𝑅 𝑖 (forward rxn)
𝑛 [𝐶𝑂 ]𝑖

0.05916 [𝐶 ]
𝐸 = 𝐸𝑜 − 𝑙𝑜𝑔 𝑂 𝑖 (reversed rxn)
𝑛 [𝐶𝑅 ]𝑖
Calculated concentration of oxidant (O) and
Where i denote concentrations at the surface of interface reductant (R) profiles at electrode surface by
(electrode-solution) Nernst equation (solid line: O, broken line: R). T
= 298.15 K. C* = total concentration of the
reaction species in eq. (1)
VOLTAMMETRIC METHODS
Direction of potential
sweep reversed

Cyclic voltammetry:
Es
A potential sweep method providing a considerable
understanding of reactions near the electrode surface and
E0
the reactivity of electrochemically or chemically active
species
The input signal is a linear potential scan with triangular Es’
waveform, sweeping the potential back and forth between
two values (called switching potential)
▪The initial, Ei (open circuit/resting/equilibrium) potential
is set usually at value where no apparent external current
flows.
▪ The potential is then scanned at a constant rate (; units =
V s−1) at the beginning time, i.e. measurement time (t) = 0,
▪The followed by the reverse of the sweep direction at a
reversal (switching) potential (Esand Es’).
VOITAMMETRIC METHODS
If there would be not diffusion limit, the measured current (i)
would have a sigmoidal profile.
Under a diffusion-controlled (limited) condition, the active
species on the electrode surface will be consumed in (eq.1)
and depleted eventually.
As Eapplied increased, [CO] (all R converted to O) will become 0
and current will exhibit a maximum and decrease thereafter.
At the switching potential, the direction of scan is reversed.
In a one-step reaction, the peak current is:
𝑖𝑝 = (2.69 × 105 )𝑛3/2 𝐴𝐶𝐷1/2 𝜐1/2
n = no. of e–

A = electrode area (cm2)

C = concentration (mol cm-3)

D = diffusion coefficient (cm2 s-1)

 = potential scan rate (V s-1)

 VOLTAMMETRIC METHODS
Revesibility of ET process can be evaluated
experimentally,
Reversible process:
▪Position of Ep is independent of the scan rate ()
▪ip varies proportionally to 1/2 and ipa/ipc  1
▪no. of e– transferred (n) in an electrode
0.057
𝐸𝑝𝑎 − 𝐸𝑝𝑐 = and
𝑛
E = Epa – Epc = 0.057 V (for an one-electron rxn)

Quasi-reversible process:
0.057
▪ipa/ipc  1 and E >
𝑛
Irreversible process:
▪Disappearance of the reversed peak.