Electrochemistry Basics

Kinetics
Outline

1. Electrical double layer

2. Electrode process
3. Electrochemical Kinetics

Most contents are from

Krystyna Jackowska, Paweł Krysiński

Applied Electrochemistry

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Electrical double layer
Simple Helmholtz model
Introduction
Think about what will happen if immerse a metal with negative charge rich
surface into solution, what will happen to the solution (ions)

Interactions
• Negative charge attract positive
charge ions (cations) due to
coulombic interactions

• Some solvent will be absorbed

on the surface

• Layer called Helmholtz layer

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Simple Helmholtz model
Potential profile

Key points
• Potential at metal determined by
electric potential

• Potential in the bulk electrolyte is zero

• In Helmholtz layer, linear distribution

• The model can be simplified as perfect

capacitor

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Gouy–Chapman model
Introduction
The Helmholtz model ignored the thermal motion of ions. A more practical
model needs to consider the diffusion
Two planes
• Inner Helmholtz plane (IHP),
cations (positive ions) will be
absorbed on inner layer

Negative Solution (A+B-) • outer Helmholtz plane (OHP),

Diffusion condsiered, potential
exponential decay, also termed
as Guoy-Chapman layer

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Gouy–Chapman model (Electrical double layer)
Potential profile

Negative Solution (A+B-)

• The IHP is linear as interaction is

strong, linear decay
• From the Helmholtz layer to the
bulk, diffuse, with exponential
potential decay.
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Electrical double layer
Simplified electrical equivalent circuit model

Equivalent Electrical Circuit

Mathematic description

Potential profile

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Electrode process
Electrode process
To generate electricity, the current is governed by the redox reactions.

𝐹𝑒 3+ + 𝑒 − = 𝐹𝑒 2+
Ox: oxidized
Red: reduced

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Electrode process
Main steps
Diffusion (Step 1 )

• Describes the diffusion of the

electroactive species, ) to/from
the Helmholtz plane (OHP) at the
electrode

• Governing equation: Nernst-

Planck equation for flux.
(introduce stationary case of
diffusion later)

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Electrode process
Main steps
Reorientation & organization (Step
2-4)

• The reorientation of ions 10-8 sec

• Reorganization of dipole solvents
10-11 sec
• Distance change of Fe4+/CN- ions
10-14 sec

Charge transfer (Step 5)

• Gain and loss of electron
• 10-16 sec

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Electrochemical Kinetics
Define the key concepts
❑Over-potential
In electrochemistry, overpotential is the potential difference (voltage)
between a half-reaction's thermodynamically-determined reduction
potential and the potential at which the redox event is experimentally
observed

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Electrochemistry kinetics
❑Definition (descriptive)
Electrochemical kinetics is the field of electrochemistry that studies the rate
of electrochemical processes.
The main goal of electrochemical kinetics is to find the relationship between
electrode over potential 𝜂 (EE-tah)and current density (j/i). (Cited from S. N.
Lvov)

Rate-Represented by the current density electrochemical reactions.

❑ Contents
▪ Cell potential, voltage loss, Over-potential (𝜼)
▪ Charge transfer resistance., Butter-Volmer equation.
▪ Tafel relationship Linear approximation
▪ Mass transfer resistance 15
Define the key concepts

❑Analysis Approach

• Find the slowest step

• Either diffusion or charge transfer

step

• If both matters, put them in series

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Case 1: diffusion limited
Diffusion: Fick’s 1st Law (Nernst-Planck equation at stationary
state)
𝑑𝐶𝑂𝑥
𝑗𝑂𝑋 = −𝐷 C: concentration, mol m-3
𝑑𝑥 x: distance, m
D: diffusivity, m2 s-1
J: flux, mol m-2 s-1

If J convert to current i density,

remember Faraday’ constant?
𝑑𝐶𝑂𝑥 i: current density, A/m-2
𝑖 = −𝑛𝐹𝐷
𝑑𝑥 F: Faraday's constant, C/mol

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Case 1: diffusion limited
Further simplify to linear concentration profile
𝑑𝐶𝑂𝑥
𝑗𝑂𝑋 = −𝐷
𝑑𝑥
C: concentration, mol m-3
x: distance, m
D: diffusivity, m2 s-1
J: flux, mol m-2 s-1
0
𝑑𝐶𝑂𝑥 [𝐶𝑜𝑥,𝑥=0 − 𝐶𝑜𝑥 ]
=
𝑑𝑥 𝛿
𝛿: diffusion layer thickness

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Case 1: diffusion limited
Equilibrium state
𝛿: diffusion layer thickness
𝑑𝐶𝑂𝑥 𝑑𝐶𝑂𝑥 0
[𝐶𝑜𝑥,𝑥=0 − 𝐶𝑜𝑥 ]
𝑗𝑂𝑋 = −𝐷 =
𝑑𝑥 𝑑𝑥 𝛿
𝑑𝐶𝑂𝑥
= 0, means the concentration gradient
𝑑𝑥
disappears, no reduction (oxidation) reaction
takes place at the electrode surface or, more
correctly, the rate of reduction equals the
rate of oxidation

For that species, the potential at electrode

equals to that in bulk, no voltage loss 19
Case 1: diffusion limited
Further simplify to linear concentration profile
𝑜 0 𝛿: diffusion layer thickness
𝑑𝐶𝑂𝑥 𝑑𝐶𝑂𝑥 [𝐶𝑜𝑥,𝑥=0 − 𝐶𝑜𝑥 ]
𝑗𝑂𝑋 = −𝐷 =
𝑑𝑥 𝑑𝑥 𝛿
Cox=0, x = 0 , meaning that the redox
reaction is so fast that it literally consumes
all of Ox form diffusing to the electrode
from the bulk, converting it into Red form.

The maximum value of ion flux.

𝑑𝐶𝑂𝑥 0
𝐶𝑜𝑥
𝑗𝑂𝑋 = −𝐷 =𝐷
𝑑𝑥 𝛿
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Case 1: diffusion limited
Further simplify to linear concentration profile
𝑜 0 𝛿: diffusion layer thickness
𝑑𝐶𝑂𝑥 𝑑𝐶𝑂𝑥 [𝐶𝑜𝑥,𝑥=0 − 𝐶𝑜𝑥 ]
𝑗𝑂𝑋 = −𝐷 =
𝑑𝑥 𝑑𝑥 𝛿
𝑑𝐶𝑂𝑥
= 0, means the concentration gradient
𝑑𝑥
disappears, no reduction (oxidation) reaction takes
place at the electrode surface or, more correctly, the
rate of reduction equals the rate of oxidation

Cox=0, x = 0 , meaning that the redox reaction is so

fast that it literally consumes all of Ox form diffusing
to the electrode from the bulk, converting it into Red
form.
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Case 1: diffusion limited
The concentration polarization 𝐹𝑒 3+ + 𝑒 − = 𝐹𝑒 2+

𝛿: diffusion layer thickness

At x=0, 𝑅𝑇
𝑜
𝐶𝐹𝑒3+
𝐸𝑥=0 =𝐸 − 𝐼𝑛[ ]
𝑛𝐹 𝐶𝐹𝑒4+,𝑥=0

At x=𝛿, 𝑅𝑇 𝐶𝐹𝑒3+
𝐸𝑥=𝛿 = 𝐸𝑜 − 𝐼𝑛[ 𝑜 ]
𝑛𝐹 𝐶𝐹𝑒4+,

Potential difference
from electrode to 𝑅𝑇 𝐶𝐹𝑒4+,𝑥=0
𝜂= 𝐼𝑛 0 <0
equilibrium 𝑛𝐹 𝐶𝐹𝑒4+
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Case 1: diffusion limited
The polarization at diffusion limited process
• charge transfer and step2-4 fast
• All the polarization attributed to diffusion

• There is a limit current density il

0
𝐶𝑜𝑥
𝑖𝐿 = 𝑛𝐹𝑗𝑂𝑋 = 𝑛𝐹𝐷
𝛿
𝑅𝑇 𝐶𝑥=0 𝑅𝑇 𝑖𝐿 − 𝑖
𝜂= 𝐼𝑛 0 = 𝐼𝑛[ ]<0
𝑛𝐹 𝐶 𝑛𝐹 𝑖𝐿

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Case 1: diffusion limited
The 𝛿 is not constant
0
𝐶𝑜𝑥
𝑖𝐿 = 𝑛𝐹𝑗𝑂𝑋 = 𝑛𝐹𝐷
𝛿

the thickness δ of the diffusion layer also

increases, expanding from the electrode
surface toward the bulk of the electrolyte,

slowing down the diffusion of the electroactive

species to the electrode surface. This, in turn
reduce the current

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Case 2: charge transfer limited
Main steps
Reorientation & organization (Step
2-4)

• The reorientation of ions 10-8 sec

• Reorganization of dipole solvents
10-11 sec
• Distance change of Fe4+/CN- ions
10-14 sec

Charge transfer (Step 5)

• Gain and loss of electron
• 10-16 sec

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Case 2: charge transfer limited
Charge transfer step (grand one) sometimes get slow
Find a governing equation to
describe

• Charge transfer resistance

But needs much more efforts, we

simply give you

Buffer-Volmer equation

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Buffer-Volmer for charge transfer (for knowledge only)

Find the relationship between and current, but we want to eliminate the geometric effect using
current density j
𝑗 = 𝑓(𝜂)

𝛼𝑎 + 𝑎𝑐 = 1

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Butler-Volmer for charge transfer (for knowledge only)
Linear response

At low overpotential region

𝛼𝑎 𝑧𝐹𝜂 𝛼𝑎 𝑧𝐹𝜂
exp ≈1+ ,
𝑅𝑇 𝑅𝑇
𝛼𝑎 𝑧𝐹𝜂 𝛼𝑐 𝑧𝐹𝜂
J = 𝑗𝑜 {1 + −1+ }=
𝑅𝑇 𝑅𝑇
(𝛼𝑎 +𝛼𝑐 )𝑧𝐹𝜂
𝑗𝑜
𝑅𝑇
linear to 𝜂 , current is linear to overpotential
at low overpotentials
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Butler-Volmer for charge transfer (for knowledge only)
Tafel response
At high overpotential region, Tafel equation
𝛼
➢ 𝜂>> 𝑎𝑍𝐹 , overpotential prefers anodic
𝑅𝑇
direction,
𝛼𝑐 𝑧𝐹𝜂
− is extremely small compared to the
𝑅𝑇
anode part, and can be neglected,

𝛼𝑎 𝑧𝐹𝜂
𝑗 = 𝑗𝑜 exp[ ]
, we can take In for both side
𝑅𝑇
𝛼𝑎 𝑧𝐹𝜂
In 𝑗 = In 𝑗0 + as the linear form,
𝑅𝑇

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Butler-Volmer for charge transfer (for knowledge only)
Tafel response
At high overpotential region, Tafel equation

𝑎𝑐 𝑍𝐹
➢𝜂 << ,
overpotential prefers cathodic
𝑅𝑇
direction,

𝛼𝑐 𝑧𝐹𝜂
In 𝑗 = In 𝑗0 + as the linear form
𝑅𝑇

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Tafel plots
When 𝜂 is significant

𝛼𝑎 𝑧𝐹𝜂
In 𝑗 = In 𝑗0 + Cathodic
𝑅𝑇
𝛼𝑐 𝑧𝐹𝜂
In 𝑗 = In 𝑗0 + Anodic
𝑅𝑇

• slope is related to the transfer

coefficient
• the y-intercept gives the
exchange current.

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General case: all steps account in series
Resistances of each step 𝜂 = 𝐼 𝑅𝑖𝑛𝑡 = 𝐼 ∗ (𝑅𝑜ℎ𝑚𝑖𝑐 + 𝑅𝑚𝑡 + 𝑅𝑐𝑡 )

𝑅𝑜ℎ𝑚𝑖𝑐 : from the external circuit

𝑅𝑚𝑡 : mass transport resistance
𝑅𝑐𝑡 : charge transfer resistance
𝑅𝑇 𝑖𝐿 − 𝑖
𝜂= 𝐼𝑛[ ]
𝑛𝐹 𝑖𝐿

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Exercise
Given the data below, estimate the diffusion layer thickness (in cm) for
oxygen diffusion.
0
𝐶𝑜𝑥 𝑛𝐹𝐷𝐶𝑏𝑢𝑙𝑘
𝑖𝐿 = 𝑛𝐹𝑗𝑂𝑋 = 𝑛𝐹𝐷 →𝛿=
𝛿 𝑖𝐿
𝑂2 + 4𝑒 − = 2𝑂2− , n = 4

4 ∗ 96500 ∗ 0.708 ∗ 10−4 𝐷

𝛿= 𝑐𝑚 = 0.094𝑐𝑚
0.35 ∗ 10−5

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Exercise
Hydrogen gassing can be a serious problem for lead-acid batteries.
Exchange current density for Reaction 1 is 100
A m−2 and that for Reaction 2 is 6.6 × 10−10 A
m−2. Calculate the current for each reaction and
the current efficiency if the Pb electrode has an
overpotential of 0.1 V relative to SHE at 25 °C.
Assume that the cathodic transfer coefficient for
𝛼𝑎 𝑧𝐹𝜂
In 𝑗 = In 𝑗0 + Anodic both reactions is 0.25
𝑅𝑇
0.25 ∗ 2 ∗ 96500 ∗ 0.1
In 𝑗 = In 100 +
8.314 ∗ 298.15

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Take-home
1. What happens to an electrode immersed in a solution?
Electrical double layer
2 What processes do the ions go through in the interface region
Electrode process
3. How fast the current can generate?
Electrochemical kinetics

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