Dynamic Electrochemistry

1. Rate of charge transfer

e e

Oxidation
M M+ M+ M

Anode Cathode

- weight deposited/ dissolved depends on quantity of

electricity
- weight loss at anode
- weight gain at cathode
- 1 e has charge of 1.6 x 10-19 C
1 mole of e = 96 500 C
∴ Faraday constant = 96 500 C / equivalent
N (equivalent) = Q/F

- Rate of a heterogeneous electrolytic reaction can be

expressed as the number of equivalents of reaction
that take place per unit time, dN/dt

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 N = Q/F
t
Q = I t or ∫ O I dt
∴ N = It/F
dN = I dt / F
or dN/dt = I / F
Rate of reaction is terms of equivalents.
or I = F dN/dt
- Current flowing is directly proportional to the rate.
- Rate can be controlled by controlling current.
- In order to remove the influence of the size of electrode,
use current density, j = I / A
j = (F / A) x (dN / dt) → coulomb flux
j/F = (1 / A) x (dN / dt) → electron flux

For single e transfer

Chemical flux = electron flux
-
Moles of chemical transferred area-1 time-1
= moles of electron flowing area-1 time-1

K [c] = j / F
K in s-1 and [c] in moles / area deposited / dissolved
Or K in dm s-1 and [c] in moles dm-3

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 ∴ j = F k [c], dependence of current density
(rate) on concentration

Rate of charge transfer under zero j

- process at electrodes are dynamics
→ must consider chemical flux in both direction
toward and away from electrode

→ net current density at electrode under zero

jnet = j anode – j cathode
= F Ka [red] – F Kc [ox]

Rate of oxidation of M

- At equilibrium, jnet = 0, electrons are continually

transferred both directions but no net transfer.
For an ion (or metal) to participate in charge transfer at an
electrode, it must:
→ migrate towards electrode and discard salvation
sphere as it accepts e, or
→ be detached from metal and migrate as an ion into bulk
solution

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 both require ‘activation’, so use activation and let rate to governed
by ∆G +
+

+
∆Gc +
+
∆Ga+

For anodic current (dissolution)

-∆Ga++ /RT
Ka = Ba e

For cathodic current (discharge)

-∆Gc++ /RT
Kc = Bc e

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Rate of charge transfer under the influence of an
electric field

Without φ (M,S) with φ (M,S)

φ (M,S)

+ φ (M)
∆Gc+

∆Ga+
+

φ (S)

OHP IHP
(Outer Helmholt plate)

∆Ga - w
φ (M) – potential of

∆Gc + w α metal
φ (S) – potential of
solution

• Reduction – need work, ∆G big

• Oxidation – ions go downhill, ∆G small

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• α= the symmetry factor or transfer coefficient to
locate the transition state
= distance across double layer to transition state
distance across entire double layer
- to separate the potential contributions to ∆Gc+ +
and ∆Ga++
- experimentally, α = ½

• Electrical work is required to move ion

Electrical work per charge = ze ∆φ
per mole = zF ∆φ
for z = 1,
⇒ Electrical work per mole = F ∆φ
At α,
⇒ Electrical work per mole = αF ∆φ

• So, activation Gibbs Function

∆Gc+ + = ∆Gc + αF ∆φ (for reduction)
∆Ga+ + = ∆Ga - (1-α) F ∆φ (for oxidation)

• Since j=Fk[]
k = B exp (-∆GE/RT)

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• For cathodic current, ∆GE = ∆GcE + αF ∆φ
• For anodic current, ∆GE = ∆GaE - (1 - α) F ∆φ

• Net current density becomes

jnet = ja - jc
jnet = {FBa [red] exp (-∆GaE/RT)} exp [(1 - α) F ∆φ /RT]
- {FBc [ox] exp (-∆GcE/RT)} exp [( - α) F ∆φ /RT]

cathodic ion density

• Since net current density, jnet = 0 at equilibrium

ja,e = jc,e = je (or jo) when ∆φ = ∆φe

and not at equilibrium, ∆φ - ∆φe = η

η = overpotential or overvoltage

• ja = {FBa [red] exp (-∆GaE/RT)} exp [(1 - α) F ∆φ /RT]

x exp [(1 – α) ηF/RT]
= ja,e exp [(1 – α) ηF/RT]
= je exp [(1 – α) ηF/RT]

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• jc = {FBc [ox] exp (-∆GcE/RT)} exp [(- α) F ∆φ /RT]
x exp (– α ηF/RT)
= jc,e exp (– α ηF/RT)
= je exp (– α ηF/RT)

• j = ja – j c
j = je {exp [(1 – α) ηF/RT] - exp (– α ηF/RT)}
Butler-Volmer Equation

• Two special cases:

(a) at low overpontentials – linear region
(b) at high overpontentials – exponential region

η
0

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• low overpotential approximation, η is small, 50 mV
j = je ηF/RT or I = A je ηF/RT
− interface behaves like an ohmic conductors,
I = E/R
- if η is positive, jnet is positive, have net aniodic
current, cations flow away from electrode

- if η is negative, jnet is negative, have net

cathodic current, cations flow toward the
electrode

high overpotential approximation, η > 50 mV

(a) η large and +ve
j = je {exp [(1 – α) ηF/RT] - exp (– α ηF/RT)}
= je {exp [(1 – α) ηF/RT]
⇒ In j = ln je + (1 – α) ηF/RT

(b) η large and –ve

j = -je {exp ( – α ηF/RT)}
⇒ In (-j) = ln je – α ηF/RT

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 Tafel plot: ln j vs η
- intercept → je; slope → α
ln j

(1 - α)F
RT

Question 9.1
For metal M (molar mass =53) in a solution of its ions, the
half reaction is
M3+ (aq) + 3e → M(s)
The equilibrium potential for the half reaction and the
measured potential of this metal electrode in the solution is
0.18 V and 0.43 V. The equilibrium current density is 2x
10-3 Am-2 and α = 0.5.

a) Determine whether the metal is dissolving from or

being deposited on the electrode

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b) Calculate the magnitude of the current density.
c) Determine the rate of the charge of electrode mass (in
g m-2 min-1).

Question 9.2
If jo = 2.5 x 10-5 Am-2 and α = 0.5 for the Cu2+ + 2e → Cu
system. Calculate the overpotential required to deposit
Cu(s) from a 1 M Cu2+ solution at j = 5 x 10-3 Am-2.

Additional Note
Three main stages involved during the discharging of ions
at an electrode:
i. transport of ions to the electrode surface
ii. discharge of the ions to form atoms
iii. conversion of the atom to the normal stable form

for stage
(i): concentration overpotential arises
(ii) & (iii) : activation overpotential arises

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