EMA4303/5305

Electrochemical Engineering
Lecture 03
Electrochemical Kinetics
Prof. Zhe Cheng, Dr. Junheng Xing
Mechanical & Materials Engineering
Florida International University
 Electrochemical Kinetics

❑Definition
“…a field of electrochemistry studying the rate of electrochemical processes.”
(Wikipedia)

“The main goal of the electrochemical kinetics is to find a relationship between the
electrode overpotential and current density …” (S. N. Lvov)

Rate - represented by current (density) for electrochemical reactions

❑Contents
▪ Cell potential, voltage loss, and overpotential (η)
▪ Charge transfer overpotential & Butler-Volmer equation
• Tafel relationship
• Linear approximation
▪ Mass transfer limitation

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 2

 Cell Potential for Galvanic & Electrolytic Cells

Galvanic cell (GC) Electrolytic cell (EC)

e- - + e-
e- e-

Zn Rext Cu Zn Cu

M M
e e
H2O e- Cl- Cl- H2O e- - Cl- Cl-
m Cl- e - Cl Cl m - e-
- Cl- Cl-
Cl b b
Zn2+ Zn2+
r Cu2+ Cu2+ r Cu2+ Cu2+
Zn 2+ Zn2+
a Cl- a
Cl- Zn → Zn2+ + 2e- Cl- n Cl- Cu2+ + 2e- → Cu Zn + 2e → Zn Cl- n
2+ - Cl- Cu → Cu2+ + 2e-
e e

𝑬𝒆𝒒 = 𝑰 (𝑹𝒆𝒙𝒕 + 𝑹𝒊𝒏𝒕 )

𝑬𝒄𝒆𝒍𝒍 = 𝑬𝑨𝒑𝒑 = 𝑬𝒆𝒒 + |𝑰| ∙ 𝑹𝒊𝒏𝒕
𝑬𝒄𝒆𝒍𝒍 = 𝑰𝑹𝒆𝒙𝒕 = 𝑬𝒆𝒒 − 𝑰𝑹𝒊𝒏𝒕

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 3

 Cell (External) Potential vs.
Current Relationship
Actual cell (external) potential Ecell is related to equilibrium cell potential Eeq and the
current passing through the cell
If cell internal resistance Rint a constant (an oversimplification) → linear relationship
Cell potential E vs. Current I

= 𝑬𝒆𝒒 + |𝑰| ∙ 𝑹𝒊𝒏𝒕

𝑬𝒄𝒆𝒍𝒍 = 𝑬𝒆𝒒 − 𝑰𝑹𝒊𝒏𝒕

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 Cell (External) Potential - Current Example (1)

j-V for a reversible solid oxide fuel cell (SOFC, a galvanic cell, j > 0)/solid
oxide electrolysis cell (SOEC, an electrolytic cell, j <0) in both modes

H2O/H2 = 0.9 : 1

Chauveau, J Power Sourcesv195 (2010) p. 744

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 Cell (External) Potential - Current Example (2)

j-V for a reversible solid oxide fuel cell (SOFC, a galvanic cell, j > 0)/solid
oxide electrolysis cell (SOEC, an electrolytic cell, j <0) in both modes

Current Applied Physics (2011), 11(1), p.S223

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 Voltage Loss from Equilibrium Cell Potential
in an Electrochemical Cell
❑Difference between cell equilibrium potential Eeq and actual cell
(external) potential Ecell is due to cell internal resistance 𝑅𝑖𝑛𝑡
If current takes absolute value:
Galvanic cell (GC)
Δ𝑬𝑮𝑪 = 𝑬𝒆𝒒 − 𝑬𝒄𝒆𝒍𝒍 = 𝑰𝑹𝒊𝒏𝒕 = 𝜼𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆𝒔 + 𝑰𝑹Ω
𝑰𝑹Ω voltage loss due to ohmic resistance (mostly in electrolyte)
𝜼𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆𝒔 voltage loss or overpotential due to electrode processes
Ecell < Eeq → less energy is converted to outside electrical work (i.e., EcellQ) than
predicted under equilibrium condition, i.e., EeqQ
Electrolytic cell (EC)
Δ𝑬𝑬𝑪 = 𝑬𝑨𝒑𝒑 − 𝑬𝒆𝒒 = 𝑰𝑹𝒊𝒏𝒕 = 𝜼𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆𝒔 + 𝑰𝑹Ω
Ecell > Eeq → electrical energy provided EAppQ is higher than what is actually stored
as chemical energy, EeqQ
▪ 𝜼𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆𝒔 from both anode & cathode 𝜼𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆𝒔 = |𝜼𝒂𝒏 | + |𝜼𝒄𝒂𝒕 |
▪ 𝑹𝒊𝒏𝒕 often not constant and 𝜼𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆𝒔 often non-linear with I
▪ Overpotential for an individual electrode (reaction) cannot be separated without
using a third electrode or reference electrode
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 Overpotential η

❑Definition
Difference between actual potential (e.g., measured) E and the equilibrium potential
𝑬𝒆𝒒 for an electrode (or redox or half cell) reaction:
𝜼 = 𝑬 𝑶𝒙/𝑹𝒆𝒅 − 𝑬𝒆𝒒 𝑶𝒙/𝑹𝒆𝒅
▪ For situation when i ≠ 0 or electrode (half cell) reaction is NOT at equilibrium
▪ Changes with current density & direction
❑ Significance
V
+
𝑬 𝑶𝒙/𝑹𝒆𝒅 > 𝑬𝒆𝒒 𝑶𝒙/𝑹𝒆𝒅 , 𝜼 > 𝟎
Anodic polarization (or bias) Red → Ox + ne-

𝑬𝒆𝒒 𝑶𝒙/𝑹𝒆𝒅 Ox + ne- ↔ Red

𝑬 𝑶𝒙/𝑹𝒆𝒅 < 𝑬𝒆𝒒 𝑶𝒙/𝑹𝒆𝒅 , 𝜼 < 𝟎

Cathodic polarization (or bias) Ox + ne- → Red
-
❑ Often takes absolute value with note about nature (anodic or cathodic)
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 Contributions to Overpotential for
a Single Electrode (Reaction)
❑Charge transfer overpotential 𝜼𝒄𝒕
Voltage loss associated with charge (or electron) transfer for an electrode (half-cell)
reaction, usually across the electrode/electrolyte interface
❑Mass transfer overpotential 𝜼𝒎𝒕
Voltage loss related to delivering of
reactants to or removing of products
from the electrode/electrolyte
interface, significant at high current
(density)
❑Others
▪ Adsorption/desorption
▪ Chemical reactions (away from
electrode interface)
❑ Total overpotential for a single
electrode (either anode or cathode)
reaction is sum of contributions Possible processes in an electrochemical electrode
from charge transfer, mass (or half cell) reaction
transfer, and, maybe, other effects:
𝜼 = 𝜼𝒄𝒕 + 𝜼𝒎𝒕 + 𝜂𝑜𝑡ℎ𝑒𝑟𝑠 S. Lvov, CRC Press (2015). ISBN: 978-1-4665-8285-9
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 Polarization Curve for Electrode Reaction
& an Example
▪ Plot of current density j vs electrode overpotential 𝜂 is called polarization curve
▪ Often nonlinear

η>0
E(Cu2+/Cu+) more positive than Eeq(Cu2+/Cu+)
Anodic polarization → oxidation
Cu+ (aq) → Cu2+ (aq) + e-

η<0
E(Cu2+/Cu+) more negative than Eeq(Cu2+/Cu+)
Cathodic polarization → reduction
Cu2+ (aq) + e- → Cu+ (aq)

Polarization curve of for Cu2+(aq, 0.1 mol/kg) / Cu+(aq, 0.1 mol/kg) electrode (redox or half cell) reaction at 25oC
1 atm with HCl (aq) supporting electrolyte of 8 mol/kg
S. Lvov, CRC Press (2015). ISBN: 978-1-4665-8285-9
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 Butler-Volmer Equation without
Mass Transport Limitation
For a one-step electrode (half cell) reaction without mass transport limitation
𝑂𝑥 + 𝑛𝑒 − ↔ 𝑅𝑒𝑑
Butler-Volmer equation describes net current density j as a function of total
overpotential for that electrode (half cell) reaction 𝜂 = 𝐸 𝑂𝑥/𝑅𝑒𝑑 − 𝐸𝑒𝑞 𝑂𝑥/𝑅𝑒𝑑
𝟏 − 𝜷 𝒏𝑭𝜼 𝜷𝒏𝑭𝜼
𝒋 = 𝒋𝐚 + 𝒋𝐜 = 𝒋𝐨 𝐞𝐱𝐩 − 𝐞𝐱𝐩 −
𝑹𝑻 𝑹𝑻
ja Anodic (oxidation) current density, in A/cm2
jc Cathodic (reduction) current density, in A/cm2
𝑗𝐨 Exchange current density, in A/cm2
β Symmetry factor, unitless
R Gas constant 8.314 J/(mol·K)
T Absolute temperature, K
Notes:
❑ Assuming uniform concentration for all active species:
• Extensively stirring and/or keep current relatively low
❑ Sign convention
• For 𝜂 & j: Anodic (oxidation) as positive (+); Cathodic (reduction) as negative (-)
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 Butler-Volmer Equation - Anodic Bias

For a one-step electrode (half cell) reaction:

𝑂𝑥 + 𝑛𝑒 − ↔ 𝑅𝑒𝑑
Butler-Volmer equation describes net current density j as a function of total
overpotential for that electrode (half cell) reaction 𝜂 = 𝐸 𝑂𝑥/𝑅𝑒𝑑 − 𝐸𝑒𝑞 𝑂𝑥/𝑅𝑒𝑑
1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂
𝑗 = 𝑗a + 𝑗c = 𝑗o exp − exp −
𝑅𝑇 𝑅𝑇
Anodic polarization or bias:
𝜂 = 𝐸 𝑂𝑥/𝑅𝑒𝑑 − 𝐸𝑒𝑞 𝑂𝑥/𝑅𝑒𝑑 > 0

Ratio of anodic (oxidation) to cathodic (reduction) current absolute value:

1 − 𝛽 𝑛𝐹𝜂
𝑗a exp 1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂 𝑛𝐹𝜂
𝑅𝑇
= = exp + = exp
|𝑗c | 𝛽𝑛𝐹𝜂 𝑅𝑇 𝑅𝑇 𝑅𝑇
exp − 𝑅𝑇
>1
Net current density 𝑗 > 0
Electrode (half cell) reaction proceeds along anodic/oxidation direction
𝑅𝑒𝑑 → 𝑂𝑥 + 𝑛𝑒 −
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 Butler-Volmer Equation - Cathodic Bias

For a one-step electrode (half cell) reaction:

𝑂𝑥 + 𝑛𝑒 − ↔ 𝑅𝑒𝑑
Butler-Volmer equation describes net current density j as a function of total
overpotential for that electrode (half cell) reaction 𝜂 = 𝐸 𝑂𝑥/𝑅𝑒𝑑 − 𝐸𝑒𝑞 𝑂𝑥/𝑅𝑒𝑑
1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂
𝑗 = 𝑗a + 𝑗c = 𝑗o exp − exp −
𝑅𝑇 𝑅𝑇
Cathodic polarization or bias:
𝜂 = 𝐸 𝑂𝑥/𝑅𝑒𝑑 − 𝐸𝑒𝑞 𝑂𝑥/𝑅𝑒𝑑 < 0

Ratio of anodic (oxidation) to cathodic (reduction) current absolute value:

1 − 𝛽 𝑛𝐹𝜂
𝑗a exp 1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂 𝑛𝐹𝜂
𝑅𝑇
= = exp + = exp
|𝑗c | 𝛽𝑛𝐹𝜂 𝑅𝑇 𝑅𝑇 𝑅𝑇
exp − 𝑅𝑇
<1
Net current density 𝑗 < 0
Electrode (half cell) reaction proceeds along cathodic/reduction direction
𝑂𝑥 + 𝑛𝑒 − → 𝑅𝑒𝑑
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 Butler-Volmer Equation at Equilibrium

For a one-step electrode (half cell) reaction:

𝑂𝑥 + 𝑛𝑒 − ↔ 𝑅𝑒𝑑
Butler-Volmer equation describes change of net current density j, as a function of
overpotential, 𝜂 = 𝐸 𝑂𝑥/𝑅𝑒𝑑 − 𝐸𝑒𝑞 𝑂𝑥/𝑅𝑒𝑑
1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂
𝑗 = 𝑗a + 𝑗c = 𝑗o exp − exp −
𝑅𝑇 𝑅𝑇
At equilibrium,
𝜂 = 𝐸 𝑂𝑥/𝑅𝑒𝑑 − 𝐸𝑒𝑞 𝑂𝑥/𝑅𝑒𝑑 = 0
1 − 𝛽 𝑛𝐹𝜂
Anodic (oxidation) current density 𝑗𝑎 = 𝑗o 𝑒𝑥𝑝 = 𝑗o > 0
𝑅𝑇
𝛽𝑛𝐹𝜂
Cathodic (reduction) current density 𝑗𝑐 = −𝑗o 𝑒𝑥𝑝 − = −𝑗o < 0
𝑅𝑇
Net current density 𝑗 = 𝑗a + 𝑗c = 0
→ No net reaction i.e., reaction at equilibrium
→ No change in (local) concentration of different (active) species

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 From Butler Volmer Equation to
Polarization Curve
1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂
𝑗 = 𝑗𝑎 + 𝑗𝑐 = 𝑗o exp − exp −
𝑅𝑇 𝑅𝑇
0.20 j (A/cm2)
▪ At equilibrium j0 = 0.05 A/cm2
𝜂 = 0, 𝑗 = 0 anodic (oxidation) ja
β = 0.5 0.15
𝑗𝑎 = 𝑗0 T = 298.15 K
𝑗𝑐 = −𝑗0 n=1 0.10
overall j = ja + jc
𝑗 = 𝑗a + 𝑗c = 0
0.05
η (V)
▪ 𝜂 > 0, 𝑗 > 0 0.00
Anodic/oxidation -0.08 -0.06 -0.04 -0.02 0 0.02 0.04 0.06 0.08
-0.05

▪ 𝜂 < 0, 𝑗 < 0 -0.10

Cathodic/reduction
-0.15
cathodic (reduction) jc
-0.20
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 Exchange Current Density j0
1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂
𝑗 = 𝑗a + 𝑗c = 𝑗o exp − exp −
𝑅𝑇 𝑅𝑇

β = 0.5
0.15 j (A/cm2)
Larger j0 →
T = 298.15 K j0 = 0.5 A/cm2
at the same 𝜂, n=1 0.10
much higher j j0 = 0.05 A/cm2

→ intrinsically faster 0.05

reaction (both ways) j0 = 0.005 A/cm2

η (V)
0.00
-0.08 -0.06 -0.04 -0.02 0 0.02 0.04 0.06 0.08

-0.05

-0.10

-0.15
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 Symmetry Factor β
1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂
𝑗 = 𝑗a + 𝑗c = 𝑗o exp − exp −
𝑅𝑇 𝑅𝑇
β is an indicator of 0.20 j (A/cm2)
symmetry of the j0 = 0.05 A/cm2
polarization curve, T = 298.15 K 0.15
ranges from 0 to 1 β = 0.2
n=1 β = 0.5
0.10
▪ β = 0.5
Symmetrical 0.05
β = 0.8

η (V)
▪ β < 0.5 0.00
anodic (oxidation) -0.08 -0.06 -0.04 -0.02 0 0.02 0.04 0.06 0.08
direction “easier” -0.05

▪ β > 0.5 -0.10

cathodic (reduction)
direction “easier” -0.15

-0.20

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 17

 Experimental Data on β and 𝑗o and Notes

▪ Exchange current density

& symmetry factor data S. Lvov, CRC Press (2015). ISBN: 978-1-4665-8285-9
limited due to experimental
difficulties & insufficient
studies

▪ Different electrode/half cell

reactions have different j0
− Fe3+/Fe2+
− K3Fe(CN)6/K4Fe(CN)6
− H+, O2/H2O

▪ The same electrode/half

cell reaction may have
different j0 values,
depending on catalyst or
(inert) electrode material
− H+/H2 on Hg
− H+/H2 on Pt
EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 18
 Butler-Volmer Equation Near Equilibrium
1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂
For B-V equation: 𝑗 = 𝑗o exp − exp −
𝑅𝑇 𝑅𝑇
At very small overpotential (|𝜂| < 10 mV), exponents in the B-V equation are small:
e.g., β = 0.5, n = 1, T = 298.15 K
1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂 0.5 × 1 × 96485𝐶/𝑚𝑜𝑙 × 0.01𝑉
= = = 0.195
𝑅𝑇 𝑅𝑇 8.314𝐽
∙ 298.15𝐾
𝑚𝑜𝑙 ∙ 𝐾
Consider 𝑒 𝑥 ≈ 1 + 𝑥 when 𝑥 → 0 𝑒 0.195 = 1.215 ≈ 1 + 0.195
1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂 1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂 𝑛𝐹𝜂
We have 𝑗 ≈ 𝑗o 1 + − 1− = 𝑗o + = 𝑗o ∙
𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇
𝒏𝑭
𝒋 = 𝒋𝒐
∙𝜼
𝑹𝑻
Current density linearly proportional to overpotential under very small bias (< 10 mV)
𝜂 𝑅𝑇 a way of determining 𝑗o - under
Define charge transfer resistance 𝑅𝑐𝑡 = =
𝑗 𝑛𝐹𝑗o very small bias

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 Tafel Equation (1)
1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂
For B-V equation: 𝑗 = 𝑗o exp − exp −
𝑅𝑇 𝑅𝑇
When 𝜂 ≫ 0, large anodic polarization (still no mass transport limitation):
1 − 𝛽 𝑛𝐹𝜂 1 − 𝛽 𝑛𝐹𝜂 1 − 𝛽 𝑛𝐹𝜂
𝑗 ≈ 𝑗o exp ln 𝑗 = ln 𝑗o + = − ln 𝑗o + ln 𝑗
𝑅𝑇 𝑅𝑇 𝑅𝑇
𝑅𝑇 𝑅𝑇
𝜂=− ln𝑗o + 𝑙𝑛𝑗
1 − 𝛽 𝑛𝐹 1 − 𝛽 𝑛𝐹

When 𝜂 ≪ 0, large cathodic polarization (still no mass transport limitation):

𝛽𝑛𝐹𝜂 𝛽𝑛𝐹𝜂 𝛽𝑛𝐹𝜂
|𝑗| ≈ 𝑗o exp − ln |𝑗| = ln 𝑗o − − = − ln 𝑗o + ln |𝑗|
𝑅𝑇 𝑅𝑇 𝑅𝑇
𝑅𝑇 𝑅𝑇
−𝜂 = − ln𝑗o + 𝑙𝑛|𝑗|
𝛽𝑛𝐹 𝛽𝑛𝐹

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 20

 Tafel Equation (2)

B-V equation: 1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂

𝑗 = 𝑗o exp − exp −
𝑅𝑇 𝑅𝑇

𝜂≫0 𝜂≪0
𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇
𝜂=− ln𝑗o + 𝑙𝑛𝑗 −𝜂 = − ln𝑗o + 𝑙𝑛|𝑗|
1 − 𝛽 𝑛𝐹 1 − 𝛽 𝑛𝐹 𝛽𝑛𝐹 𝛽𝑛𝐹

Tafel equation – general form Anodic overpotential (bias)

𝑅𝑇 𝑅𝑇
|𝜼| = 𝒂 + 𝒃 ∙ 𝐥𝐧 𝒋 = 𝒂 + 𝒃′ ∙ 𝐥𝐨𝐠 𝟏𝟎 |𝒋| 𝑎=− ln𝑗o 𝑏=
1 − 𝛽 𝑛𝐹 1 − 𝛽 𝑛𝐹
Cathodic overpotential (bias)
𝑅𝑇 𝑅𝑇
𝑎=− ln𝑗o 𝑏=
𝛽𝑛𝐹 𝛽𝑛𝐹
▪ Fitting of experimental 𝜂 - j data yields Tafel intercept a and slope 𝑏 (or b’ = 2.303b),
which allows estimation of 𝑗o and 𝛽
▪ Applicable when η > ~100 mV
▪ NOT applicable near equilibrium or |j| → 0
EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 21
 Deviation of Tafel from Butler-Volmer
Assuming NO mass transport limitation 0.30
η (V)
j0 = 0.05 A/cm2
β = 0.5 0.25
T = 298.15 K
n=1
0.20
η = 100 mV, 𝑅𝑇
𝑆𝑙𝑜𝑝𝑒 𝑏 =
jB-V = 0.343 A/cm2 1 − 𝛽 𝑛𝐹
jTafel = 0.350 A/cm2 0.15
𝑅𝑇
𝜂 𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 𝑎 = − ln𝑗o
~2% error 1 − 𝛽 𝑛𝐹
1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂
𝑗 = 𝑗𝑜 𝑒𝑥𝑝 − 𝑒𝑥𝑝 −
𝑅𝑇 𝑅𝑇 0.10 Tafel
1 − 𝛽 𝑛𝐹𝜂
η = 60 mV, Butler-Volmer 𝑗 ≈ 𝑗𝑜 𝑒𝑥𝑝
𝑅𝑇
jB-V = 0.145 A/cm2 0.05 𝑅𝑇 𝑅𝑇
𝜂=− ln𝑗o + 𝑙𝑛𝑗
jTafel = 0.161 A/cm2 1 − 𝛽 𝑛𝐹 1 − 𝛽 𝑛𝐹

~11% error ln j
0.00
-6 -5 -4 ln𝑗o -3 -2 -1 0 1 2 3
EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 22
 Measurement of Overpotential for
an Electrode (half cell) Reaction
▪ Overpotential for an electrode (reaction) of
interest that is passing a current (working j Rext
electrode, WE) cannot be measured with V
respect to the other current-carrying electrode
reaction (counter electrode, CE) in an
electrochemical cell.
→A third electrode (reaction) must be - +
introduced as the reference electrode (RE)
▪ Measure potential difference for WE vs. RE
under equilibrium (j = 0) and with different CE
current density j,
WE
then the “overpotential” for WE ηRE ≈ 0
ηWE = [E (WE) – E (RE)] – [Eeq (WE) – Eeq(RE)] j
ηWE ≈ E (WE) – Eeq (WE) ηWE ηCE
could be obtained as a function of j
▪ To avoid overpotential contribution from RE, no
significant current must pass through RE, which
is achieved with a high impedance voltmeter

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 23

 Example of Data Fitting to B-V Equation (1)

Data below were taken for a NiOOH electrode reaction involving a single electron. Fit
the data to obtain kinetic parameters in the Butler-Volmer equation.
Enter the data into MS Excel

2
Overpotential (V) j (A/m )
-0.10 -4.20
-0.09 -3.36
-0.08 -2.40
-0.07 -2.30 Initial guessed values for j0 and β
-0.06 -1.80
-0.05 -1.25 Calculated from B-V equation
-0.04 -1.00
-0.03 -0.80 Error = j – Calculated from B-V
-0.02 -0.50
-0.01 -0.22
0.01 0.24
0.02 0.45
0.03 0.80
0.04 1.00
0.05 1.45
0.06 1.80
0.07 2.10
0.08 2.80
0.09 3.50
0.10 4.10 = SUMSQ(J10:J29)
EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 24
 Example of Data Fitting to B-V Equation (2)
Use Excel Solver to fit for j0 and β values

Objective:
sum of error squared (D30) to Min
By changing variables cell:
β (cell D6) and j0 (cell D7)
Constraints:
β (cell D6) <= 1

Click “Solve”

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 25

 Example of Data Fitting to B-V Equation (3)
Excel Solver provides fitted j0 and β that minimize sum of error squared (cell D30)

Fitted values for j0 and β values

An (optimized) solution found

(i.e., converge)

Sum of error squared greatly reduced (to minimum)

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 26

 Fitting to Tafel & Comparison w/ BV (1)
j (A/m2) Overpotential (V) lnj #1 Calculate lnj
Anode polarization data on for 60300 0.20910 11.01
chlorine gas production from 5 M 41300 0.19940 10.63
NaCl solution at 20oC is provided 22300 0.17030 10.01
(Kunh and Mortimer, J Electrochem 12400 0.15150 9.43
8080 0.13590 9.00
Soc v120, 231 (1973)). 6180 0.12080 8.73
By fitting data to Tafel equation, 4110 0.10360 8.32
determine exchange current 2070 0.07934 7.64
7.11
density j0 and symmetry factor β 1230 0.05512
817 0.04727 6.71
for the anode reaction. 621 0.04047 6.43
427 0.03433 6.06
2Cl- → Cl2 + 2e- 240 0.02547 5.48
173 0.02204 5.15
n=2 4.75
116 0.01658
58 0.01175 4.07
30 0.00489 3.40 #2 Linear fit for
#3 Calculate (1-β) and j0 from fitted Fitted slope b 0.0398 Overpotential (as
slope b and 𝜂 axis intercept 𝑎 : 𝑅𝑇 Fitted intercept a -0.2258
𝑆𝑙𝑜𝑝𝑒 𝑏 =
y) vs. lnj (as x) for
r2 0.9978
1 − 𝛽 𝑛𝐹 η >50 mV
1-β 0.317
𝑅𝑇 j0 (A/m2) 291
𝜂 𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 𝑎 = − ln𝑗o = −𝑏 ln 𝑗o
1 − 𝛽 𝑛𝐹 Fuller textbook: 𝛼𝑎 = 1 − 𝛽 𝑛 = 0.635
EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 27
 Fitting to Tafel & Comparison w/ BV (2)
Calculated from B-V equation based on initial
j (A/m2) Overpotential (V) lnj j from B-V error guessed values for (1-β) and j0 (e.g., 0.5 and 1,
60300 0.20910 11.01 3935.5 56365
41300 0.19940 10.63 2680.6 38619 respectively)
22300 0.17030 10.01 847.1 21453
12400 0.15150 9.43 402.4 11998
8080 0.13590 9.00 217.0 7863 Error between experimental j and calculated j
6180 0.12080 8.73 119.4 6061
4110 0.10360 8.32 60.4 4050 from B-V equation, i.e.,
2070 0.07934 7.64 23.1 2047 j – j from B-V
1230 0.05512 7.11 8.8 1221
817 0.04727 6.71 6.3 811
621 0.04047 6.43 4.8 616
427 0.03433 6.06 3.6 423
240 0.02547 5.48 2.4 238
173 0.02204 5.15 2.0 171 Anode polarization data on for chlorine gas
116 0.01658 4.75 1.4 115
58 0.01175 4.07 1.0 57 production from 5 M NaCl solution at 20oC.
30 0.00489 3.40 0.4 30 (Kunh and Mortimer, J Electrochem
Fitted slope b 0.0398
Fitted intercept a -0.2258 Soc v120, 231 (1973)).
r2 0.9978 Fitting all polarization data to B-V equation
1-β 0.317 0.500 <-- initial guessed 1-beta
j0 (A/m2) 291 1 <-- initial guessed j0
Sum of
error
squared 5.395E+09
= SUMSQ(J10:J29)

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 28

 Fitting to Tafel & Comparison w/ BV (3)
Excel Solver provide fitted 1‒β (E27) and j0 (E28) values, minimizing sum of error squared (F29)

Objective:
sum of error squared (cell
F29) to Min

By changing variables cells:

cell E27 for 1-β
cell E28 for j0
Constraints:
1-β (cell E27) <= 1

Click “Solve”

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 29

 Fitting to Tafel & Comparison w/ BV (4)
Excel Solver provides fitted 1‒β and j0 values that minimizes sum of error squared (cell F29)

An (optimized) solution found

(i.e., converge)

Fitted values for (1‒ β) (cell E27) and j0 (cell E28) values
Sum of error squared (cell 29) greatly reduced (to minimum)
Fitted values by Tafel (0.317, 291 A/m2) different from B-V (0.336, 225 A/m2), but close – on same order!
EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 30
 Fitting to Tafel & Comparison w/ BV (5)
Anode 100,000 j (A/m2)
polarization
data for Cl2
production from
NaCl solution at
20oC (Kuhn and 10,000
Mortimer, J
Electrochem
Soc v120, 231
(1973))
1,000 T = 293.15 K
n=2

Good fitting at high

100 Tafel
overpotential
(> ~0.05 V), but B-V
overestimation at
lower bias, more
Experiment η (V)
obvious for Tafel 10
than B-V
0 0.05 0.1 0.15 0.2 0.25
EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 31
 Voltage Loss in Electrochemical Cell

For an actual electrochemical cell, voltage loss from cell equilibrium

potential Eeq is coming from several contributions

Galvanic cell (GC)

Δ𝑬𝑮𝑪 = 𝑬𝒆𝒒 − 𝑬𝒄𝒆𝒍𝒍 = |𝑰|𝑹𝒊𝒏𝒕 = 𝜼𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆𝒔 + |𝑰|𝑹Ω = 𝜼𝒂𝒏 + 𝜼𝒄𝒂𝒕 + |𝑰|𝑹Ω

𝑬𝒄𝒆𝒍𝒍 𝑮𝑪 = 𝑬𝒆𝒒 − |𝑰|𝑹𝒊𝒏𝒕 = 𝑬𝒆𝒒 − 𝜼𝒂𝒏 + 𝜼𝒄𝒂𝒕 + |𝑰|𝑹Ω

Electrolytic cell (EC)

Δ𝑬𝑬𝑪 = 𝑬𝑨𝒑𝒑 − 𝑬𝒆𝒒 = |𝑰|𝑹𝒊𝒏𝒕 = 𝜼𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒅𝒆𝒔 + |𝑰|𝑹Ω = 𝜼𝒂𝒏 + 𝜼𝒄𝒂𝒕 + |𝑰|𝑹Ω

𝑬𝒄𝒆𝒍𝒍 𝑬𝑪 = 𝑬𝑨𝒑𝒑 = 𝑬𝒆𝒒 + |𝑰|𝑹𝒊𝒏𝒕 = 𝑬𝒆𝒒 + 𝜼𝒂𝒏 + 𝜼𝒄𝒂𝒕 + |𝑰|𝑹Ω

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 32

 Voltage Loss in Electrochemical Cell
Example (1)
Consider a system with an Zn anode and a NiOOH cathode in an alkaline solution.
Electrode reactions are: Symbol Value Meaning
Anodic (oxidation) half cell (unit)
Zn + 2OH- → Zn(OH)2 + 2e- Ra, Ni 100 Surface roughness factor for Ni electrode
Cathodic (reduction) half cell Ra, Zn 2 Surface roughness factor for Zn electrode
NiOOH + H2O + e- → 0.61 A/m2
j0, Ni Exchange current density for Ni electrode
Ni(OH)2 + OH-
j0, Zn 60 A/m2 Exchange current density for Zn electrode
kinetic parameters are given
Equilibrium cell potential for NiOOH/Ni(OH)2
a) Determine cell potential Eeq 1.74 V
relative to Zn(OH)2/Zn
at galvanic current
αa, Ni 0.5 Anodic transfer coefficient for Ni electrode
density of 1000 A/m2
b) Determine discharge αc, Ni 0.5 Cathodic transfer coefficient for Ni electrode

current density that αa, Zn 1.5 Anodic transfer coefficient for Zn electrode
corresponds to total cell αc, Zn 0.5 Cathodic transfer coefficient for Zn electrode
voltage of 1.3 V κ 60 S/m Electrolyte conductivity
𝛼𝑎 = 1 − 𝛽 𝑛
L 2 mm Electrolyte thickness
𝛼𝑐 = 𝛽𝑛
EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 33
 Voltage Loss in Electrochemical Cell
Example (2)
Part a) Want 𝑬𝒄𝒆𝒍𝒍 𝑮𝑪 = 𝑬𝒆𝒒 − 𝜼𝒂𝒏 + 𝜼𝒄𝒂𝒕 + |𝑰|𝑹Ω Knowing net j → back calculate η (for
Ni surface
both Zn anode and Ni cathode) based
Zn surface roughness on B-V equation
roughness factor 2 factor 100
i0 (Zn) A/m2 60 i0 (Ni) A/m2 0.61
alfa-a Zn 1.5 alfa-a Ni 0.5 Zn electrode anodic (oxidation)
alfa-c Zn 0.5 alfa-c Ni 0.5
Overpotential (V) j Zn by BV (A/m2) j Ni by BV (A/m2) current corresponding to positive
-0.300 -41194.4 -20940.3 overpotential
-0.299 -40400.5 -20536.7
-0.298 -39621.8 -20140.9 Interpolation for Zn anodic +1000 A/m2
-0.297 -38858.1 -19752.7 0.038 − 0.037
-0.296 -38109.2 -19372.0 𝜂𝑎,𝑍𝑛 = 0.037 + × 1000 − 982.4
-0.295 -37374.7 -18998.6 1046.1 − 982.4
-0.294 -36654.3 -18632.4
𝜂𝑎,𝑍𝑛 = 0.0373𝑉
0.036 922.2 92.6
0.037 982.4 95.6
0.038 1046.1 98.7 Ni electrode cathodic (reduction)
0.039 1113.6 101.8
current corresponding to negative
overpotential
-0.145 -2017.2 -1021.8
-0.144 -1978.3 -1001.9 Interpolation for Ni cathodic -1000 A/m2
-0.143 -1940.2 -982.5
𝜂𝑐,𝑁𝑖 = −0.1439𝑉

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 34

 Voltage Loss in Electrochemical Cell
Example (2: Alternative-1)
Set up problem in Excel: calculate current density (B67,E67) using overpotential (B65,E65) values

Initial guessed values for overpotential Calculated j values from B-V equation
for both Zn and Ni electrodes using the overpotential values
EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 35
 Voltage Loss in Electrochemical Cell
Example (2: Alternative-2)
Excel Goal Seek to provide fitted overpotential (B65, E65) for target current density (B67, E67)

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 36

 Voltage Loss in Electrochemical Cell
Example (2: Alternative-3)
Excel Goal Seek
provide fitted
overpotential (e.g.,
B65) value for target
current density (e.g.,
B67)

Set cell: j from BV (cell B67)

To value: 1000, i.e., target ja for Zn
By changing cell: Zn overpotential (B65)
EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 37
 Voltage Loss in Electrochemical Cell
Example (2: Alternative-4)

Goal seek found a fit

Goal seek found a fit
for Ni overpotential
for Zn overpotential
at -0.1439 V (E65)
at 0.0373 V (B65)
that meets the goal
that meets the goal
-1000 (cell E67)
1000 (cell B67)
EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 38
 Voltage Loss in Electrochemical Cell
Example (3)
Total cell voltage:
𝑬𝒄𝒆𝒍𝒍 𝑮𝑪 = 𝑬𝒆𝒒 − 𝜼𝒂𝒏 + 𝜼𝒄𝒂𝒕 + |𝑰|𝑹Ω
𝐿 1 𝐿 𝐿
|𝐼|𝑅𝛺 = |𝑗 ∙ 𝐴| ∙ 𝜌 ∙ = |𝑗 ∙ 𝐴| ∙ ∙ = |𝑗| ∙
𝐴 𝜅 𝐴 𝜅
𝐴 0.002𝑚
= 1000 2 ×
𝑚 60𝑆/𝑚
𝐴
= 0.0333
𝑆
𝐴
= 0.0333
1/Ω
= 0.0333𝑉

𝐸𝑐𝑒𝑙𝑙 𝐺𝐶 = 1.74𝑉 − |0.0373𝑉| + | − 0.1439𝑉| + 0.0333𝑉 = 1.526𝑉

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 39

 Voltage Loss in Electrochemical Cell
Example (4)
Total cell voltage: 𝑬𝒄𝒆𝒍𝒍 𝑮𝑪 = 𝑬𝒆𝒒 − 𝜼𝒂𝒏 + 𝜼𝒄𝒂𝒕 + |𝑰|𝑹Ω

Open Circuit Closed Circuit

E (I = 0) E (I > 0, Galvanic mode)
Anode Electrolyte Cathode Anode Electrolyte Cathode

𝜼𝒄𝒂𝒕

Ecell = Eeq
Ecell GC = Eeq ‒ ( 𝜼𝒂𝒏
Eeq + 𝜼𝒄𝒂𝒕 + |𝑰|𝑹Ω )

0 0 |𝜼𝒂𝒏 | x
x
|𝑰|𝑹Ω

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 40

 Voltage Loss in Electrochemical Cell
Example (5)
Part b) Want j so that 𝑬𝒄𝒆𝒍𝒍 𝑮𝑪 = 𝑬𝒆𝒒 − 𝜼𝒂𝒏 + 𝜼𝒄𝒂𝒕 + 𝑰 𝑹Ω = 𝟏. 𝟑𝟎𝑽
Or 𝜼𝒂𝒏 + 𝜼𝒄𝒂𝒕 + 𝑰 𝑹Ω = 𝑬𝒆𝒒 − 𝑬𝒄𝒆𝒍𝒍 𝑮𝑪 = 𝟏. 𝟕𝟒𝑽 − 𝟏. 𝟑𝟎𝑽 = 𝟎. 𝟑𝟒 𝑽

Difference in absolute values

Initial guessed overpotential for Zn Average absolute
between anodic/positive (on
anode (cell A81) and Ni cathode (cell current for |ja|
Zn) and cathodic/positive
D81) and |jc|, to
current (on Ni);
calculate |I|R
should be small (< 1 A/m2)
EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 41
 Voltage Loss in Electrochemical Cell
Example (6)
Excel Solver to provide fitted ηa(Zn) (cell A81) and ηc(Ni) (cell D81) values
• Objective EGC (cell B84) of 1.3 V
• By changing ηa(Zn) (cell A81) and ηc(Ni) (cell D81)
• Subject to the constraints:
• ηa(Zn) (cell A81) in range of 0 to 2
• ηc(Ni) (cell D81) in range of -2 to 0
• ja+jc (cell F83) <=1, meaning ja and jc close in absolute value, but with opposite sign

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 42

 Voltage Loss in Electrochemical Cell
Example (7)
Excel Solver found a solution:
• Objective EGC (cell B84) became 1.300 V
• ηa(Zn) (cell A81) = 0.0627 V (anodic overpotential)
• ηc(Ni) (cell D81) = -0.2226 V (cathodic overpotential)
• ja (Zn) = +4641.1 A/m2, jc(Ni) = -4640.1 A/m2, ja+jc (cell F83) = 1.0 A

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 43

 Concentration Overpotential

Once electrochemical reaction starts, active species concentration often NOT uniform

𝒄𝑪𝒖𝟐+ 𝒄𝑪𝒖𝟐+

x x

Nernst equation roughly estimates overpotential due to concentration gradient of

electrochemically active species between electrode/electrolyte interface and the bulk:
If concentration of an active species (e.g., Ox) in 𝑂𝑥 + 𝑛𝑒 − → 𝑅𝑒𝑑 at the surface
s o
is 𝑐𝑎𝑐𝑡𝑖𝑣𝑒 and in bulk is 𝑐𝑎𝑐𝑡𝑖𝑣𝑒 ,
𝑹𝑻 𝒄𝐬𝒂𝒄𝒕𝒊𝒗𝒆
Electrode concentration overpotential 𝜼 = 𝐥𝐧 𝐨
𝒏𝑭 𝒄𝒂𝒄𝒕𝒊𝒗𝒆
s o s o
▪ 𝜂 can be positive (𝑐𝑎𝑐𝑡𝑖𝑣𝑒 > 𝑐𝑎𝑐𝑡𝑖𝑣𝑒 ) or negative (𝑐𝑎𝑐𝑡𝑖𝑣𝑒 < 𝑐𝑎𝑐𝑡𝑖𝑣𝑒 )
s
▪ 𝑐𝑎𝑐𝑡𝑖𝑣𝑒 often unknown
EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 44
 Mass Transfer Overpential (1)

When a reaction is limited by mass transfer, e.g., bringing of an active species from the
bulk to the electrolyte/electrode interface, current density often satisfy:
𝒋 ≈ 𝒏𝑭𝒌(𝒄𝐨𝒂𝒄𝒕𝒊𝒗𝒆 − 𝒄𝐬𝒂𝒄𝒕𝒊𝒗𝒆 )
When 𝒄𝐬𝒂𝒄𝒕𝒊𝒗𝒆 = 𝟎, current density reaches the max or limiting value, 𝒋𝐥𝐢𝐦 :
𝒋𝒍𝒊𝒎 ≈ 𝒏𝑭𝒌𝒄𝐨𝒂𝒄𝒕𝒊𝒗𝒆
The ratio s
𝑗 𝑐𝑎𝑐𝑡𝑖𝑣𝑒
≈1− o
𝑗lim 𝑐𝑎𝑐𝑡𝑖𝑣𝑒

Therefore, s
𝑐𝑎𝑐𝑡𝑖𝑣𝑒 𝑗
o ≈1−
𝑐𝑎𝑐𝑡𝑖𝑣𝑒 𝑗lim

s o
▪ j = 0, 𝑐𝑎𝑐𝑡𝑖𝑣𝑒 = 𝑐𝑎𝑐𝑡𝑖𝑣𝑒 , uniform concentration
s
▪ j = jlim , 𝑐𝑎𝑐𝑡𝑖𝑣𝑒 = 0, largest concentration gradient
▪ Applicable when migration mass transport is dominated by diffusion
is negligible and NOT electromigration
EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 45
 Mass Transfer Overpential (2)

From previous 𝑠
𝑐𝑎𝑐𝑡𝑖𝑣𝑒 𝑗
o ≈ 1 −
𝑐𝑎𝑐𝑡𝑖𝑣𝑒 𝑗lim

In this case, concentration overpotential due to mass transfer (e.g., diffusion) can be
approximated by:
𝑹𝑻 𝒄𝒔𝒂𝒄𝒕𝒊𝒗𝒆
𝜼= 𝐥𝐧 𝒐
𝒏𝑭 𝒄𝒂𝒄𝒕𝒊𝒗𝒆

𝑹𝑻 𝒋
𝜼= 𝐥𝐧 𝟏 −
𝒏𝑭 𝒋𝒍𝒊𝒎

▪ Also called mass transfer (diffusion in this case) overpotential

▪ Can be estimated if j and jlim are measured

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 46

 Generalized Butler-Volmer Equation (1)

For a general one-step electrode (half cell) reaction:

𝑂𝑥 + 𝑛𝑒 − ↔ 𝑅𝑒𝑑
Generalized Butler-Volmer equation for net current density j as a function of
overpotential for that electrode or half cell reaction 𝜂 = 𝐸 𝑂𝑥/𝑅𝑒𝑑 − 𝐸𝑒𝑞 𝑂𝑥/𝑅𝑒𝑑
𝒄𝐬𝑹𝒆𝒅 𝟏 − 𝜷 𝒏𝑭𝜼 𝒄𝐬𝑶𝒙 𝜷𝒏𝑭𝜼
𝒋 = 𝒋𝐚 + 𝒋𝐜 = 𝒋𝐨 ∙ 𝐞𝐱𝐩 − 𝐨 ∙ 𝐞𝐱𝐩 −
𝒄𝐨𝑹𝒆𝒅 𝑹𝑻 𝒄𝑶𝒙 𝑹𝑻
ja Anodic current density, often in A/cm2
jc Cathodic current density, often in A/cm2
𝑗𝐨 Exchange current density, often in A/cm2
β Symmetry factor, unitless
s
𝑐𝑅𝑒𝑑 Electrode surface concentration for reduced species Red
o
𝑐𝑅𝑒𝑑 Bulk concentration for reduced species Red
s
𝑐𝑂𝑥 Electrode surface concentration for oxidized species Ox
o
𝑐𝑂𝑥 Bulk concentration for oxidized species Ox
R Gas constant 8.314 J/(mol·K)
T Absolute temperature, K

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 47

 Generalized Butler-Volmer Equation (2)

If mass transfer limited by diffusion only, for the generalized Butler-Volmer equation
s s
𝑐𝑅𝑒𝑑 1 − 𝛽 𝑛𝐹𝜂 𝑐𝑂𝑥 𝛽𝑛𝐹𝜂
𝑗 = 𝑗o o ∙ exp − o ∙ exp −
𝑐𝑅𝑒𝑑 𝑅𝑇 𝑐𝑂𝑥 𝑅𝑇
s o s o
(𝑐𝑅𝑒𝑑 /𝑐𝑅𝑒𝑑 ) and (𝑐𝑂𝑥 /𝑐𝑂𝑥 ) are for the anodic and the cathodic processes of the same
electrode (half cell) reaction.
s s
𝑐𝑅𝑒𝑑 𝑗 𝑐𝑂𝑥 𝑗 j positive if anodic,
o ≈ 1 − o ≈ 1 + j negative if cathodic
𝑐𝑅𝑒𝑑 𝑗lim,𝑎 𝑐𝑂𝑥 𝑗lim,𝑐
Therefore,
𝑗 1 − 𝛽 𝑛𝐹𝜂 𝑗 𝛽𝑛𝐹𝜂
𝑗 = 𝑗o 1− ∙ exp − 1+ ∙ exp −
𝑗lim,a 𝑅𝑇 𝑗lim,c 𝑅𝑇

Expand, we have

1 − 𝛽 𝑛𝐹𝜂 1 − 𝛽 𝑛𝐹𝜂 𝑗0 𝛽𝑛𝐹𝜂 𝛽𝑛𝐹𝜂 𝑗0

𝑗 = exp 𝑗o − exp 𝑗 − exp − 𝑗o − exp − 𝑗
𝑅𝑇 𝑅𝑇 𝑗lim,𝑎 𝑅𝑇 𝑅𝑇 𝑗lim,c

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 48

 Generalized Butler-Volmer Equation (3)

From previous
1 − 𝛽 𝑛𝐹𝜂 1 − 𝛽 𝑛𝐹𝜂 𝑗0 𝛽𝑛𝐹𝜂 𝛽𝑛𝐹𝜂 𝑗0
𝑗 = exp 𝑗o − exp 𝑗 − exp − 𝑗o − exp − 𝑗
𝑅𝑇 𝑅𝑇 𝑗lim,𝑎 𝑅𝑇 𝑅𝑇 𝑗lim,c

1 − 𝛽 𝑛𝐹𝜂 𝑗0 𝛽𝑛𝐹𝜂 𝑗0 1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂

𝑗 + exp 𝑗 + exp − 𝑗 = exp 𝑗o − exp − 𝑗o
𝑅𝑇 𝑗lim,𝑎 𝑅𝑇 𝑗lim,c 𝑅𝑇 𝑅𝑇

Therefore,
1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂
exp 𝑗 − exp −
𝑅𝑇 o 𝑅𝑇 𝑗o
𝑗=
1 − 𝛽 𝑛𝐹𝜂 𝑗0 𝛽𝑛𝐹𝜂 𝑗0
1 + exp + exp −
𝑅𝑇 𝑗lim,a 𝑅𝑇 𝑗lim,c

or
1 − 𝛽 𝑛𝐹𝜂 𝛽𝑛𝐹𝜂
exp − exp −
𝑅𝑇 𝑅𝑇
𝑗=
1 1 1 − 𝛽 𝑛𝐹𝜂 1 𝛽𝑛𝐹𝜂
𝑗o + 𝑗lim,a exp 𝑅𝑇 + 𝑗lim,𝑐 exp − 𝑅𝑇

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 49

 j vs. η Plots for Generalized B-V Equation
n = 1, 𝛽 = 0.5, |η| very large (> ~0.5 V) 10
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

η (V)
T = 298.15 K, j → limiting values
1
𝑗o = 0.001 A/cm2,
𝑗lim,a = 𝑗lim,c = 1 A/cm2 0.1

j (A/cm2)
0.01
1.20 j (A/cm2)
1.00 0.001
→ Tafel: η = a + b lg | j|
0.80
0.0001
|η| ~ 0.1-0.3 V
0.60

0.40 0.00001

0.20 0.003 j (A/cm2)

η (V)
0.00 0.002
-1.5 -1 -0.5 0 0.5 1 1.5
-0.20
0.001
-0.40

-0.60
|η| very small (< ~0.015 V) 0.000
η (V)
-0.04 -0.03 -0.02 -0.01 0 0.01 0.02 0.03 0.04
-0.80 → Linear or j = η / Rct -0.001

-1.00
-0.002
-1.20

-0.003

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 50

 Homework

❑Read textbook chapter 3 and give an honor statement confirm reading

❑Raise THREE (3) question that you don't understand for lecture videos
In case you have understood everything and don’t have that many questions, please
give corresponding number of multiple-choice problem (together with your answer)
that you feel can be used to check a student's understanding.

An example multiple-choice problem could be:

Which of the units below can be the unit for current density j?
a) A
b) A/cm2 (Answer)
c) V
d) C

❑Problems (OPTIONAL for EMA4303)

▪ Textbook 3.3, 3.4, 3.8, 3.9, 3.10, 3.13

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 51

 Exchange Current Density j0
(Fuller Eq. 3.19)
From (3.11), anodic & cathodic reaction rate are the same at equilibrium:

𝑗0 1 − 𝛽 𝑛𝐹𝑈 𝛽𝑛𝐹𝑈
≡ 𝑟𝑎 = 𝑘𝑎 𝑐𝑅𝑒𝑑 exp = 𝑘𝑐 𝑐𝑂𝑥 exp − = 𝑟𝑐
𝐹 𝑅𝑇 𝑅𝑇

Therefore,
𝑛𝐹𝑈 𝑘𝑐 𝑐𝑂𝑥
exp =
𝑅𝑇 𝑘𝑎 𝑐𝑅𝑒𝑑

𝑛𝐹𝑈 𝑘𝑐 𝑐𝑂𝑥
= ln
𝑅𝑇 𝑘𝑎 𝑐𝑅𝑒𝑑

𝑅𝑇 𝑘𝑐 𝑐𝑂𝑥
𝑈= ln
𝑛𝐹 𝑘𝑎 𝑐𝑅𝑒𝑑

which is (3.19)

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 52

 Exchange Current Density j0
(Fuller Eq. 3.20a)
From (3.11), when anodic & cathodic reaction rate are the same at equilibrium:
𝑗0 1 − 𝛽 𝑛𝐹𝑈 𝛽𝑛𝐹𝑈
≡ 𝑟𝑎 = 𝑘𝑎 𝑐𝑅𝑒𝑑 exp = 𝑘𝑐 𝑐𝑂𝑥 exp − = 𝑟𝑐
𝐹 𝑅𝑇 𝑅𝑇
From (3.19), or
𝑅𝑇 𝑘𝑐 𝑐𝑂𝑥 𝑛𝐹𝑈 𝑘𝑐 𝑐𝑂𝑥
𝑈= ln = ln
𝑛𝐹 𝑘𝑎 𝑐𝑅𝑒𝑑 𝑅𝑇 𝑘𝑎 𝑐𝑅𝑒𝑑
Therefore,
𝑗0 𝑛𝐹𝑈 𝑘𝑐 𝑐𝑂𝑥
≡ 𝑟𝑎 = 𝑘𝑎 𝑐𝑅𝑒𝑑 exp 1 − 𝛽 ∙ = 𝑘𝑎 𝑐𝑅𝑒𝑑 exp 1 − 𝛽 ∙ ln
𝐹 𝑅𝑇 𝑘𝑎 𝑐𝑅𝑒𝑑
1−𝛽 1−𝛽
𝑗0 𝑘𝑐 𝑐𝑂𝑥 𝑘𝑐 𝑐𝑂𝑥
= 𝑘𝑎 𝑐𝑅𝑒𝑑 exp ln = 𝑘𝑎 𝑐𝑅𝑒𝑑 ∙
𝐹 𝑘𝑎 𝑐𝑅𝑒𝑑 𝑘𝑎 𝑐𝑅𝑒𝑑

𝑗0
= 𝑘𝑎 𝑐𝑅𝑒𝑑 ∙ 𝑘𝑐 𝑐𝑂𝑥 1−𝛽 ∙ 𝑘𝑎 𝑐𝑅𝑒𝑑 𝛽−1
𝐹
𝑗0
= 𝑘𝑐 𝑐𝑂𝑥 1−𝛽 ∙ 𝑘𝑎 𝑐𝑅𝑒𝑑 𝛽
𝐹
which is essentially (3.20a)
EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 53
 Mass Transfer on Reaction Rate
(Fuller Eq 3.33-1)
Mass transfer rate from bulk to surface:
𝑁𝑅 = 𝑘𝑚 𝑐𝑅,𝑏 − 𝑐𝑅,𝑠

At steady state, mass transfer and electrochemical reaction (charge transfer) match at
the electrode/electrode interface, where Tafel equation is assumed
𝑐𝑅,𝑠 𝛼𝑎 𝐹
𝑗 = 𝑛𝐹𝑘𝑚 𝑐𝑅,𝑏 − 𝑐𝑅,𝑠 = 𝑗0,𝑟𝑒𝑓 ∙ ∙ 𝑒𝑥𝑝 𝜂
𝑐𝑅,𝑟𝑒𝑓 𝑅𝑇 𝑠
Assuming bulk concentration equals reference/standard concentration
𝑐𝑅,𝑟𝑒𝑓 = 𝑐𝑅,𝑏

To solve for 𝑐𝑅,𝑠

1 𝛼𝑎 𝐹
𝑛𝐹𝑘𝑚 𝑐𝑅,𝑏 − 𝑛𝐹𝑘𝑚 𝑐𝑅,𝑠 = 𝑗0, 𝑏 ∙ ∙ 𝑒𝑥𝑝 𝜂 𝑐
𝑐𝑅,𝑏 𝑅𝑇 𝑠 𝑅,𝑠

1 𝛼𝑎 𝐹
𝑛𝐹𝑘𝑚 𝑐𝑅,𝑏 = 𝑛𝐹𝑘𝑚 𝑐𝑅,𝑠 + 𝑗0, 𝑏 ∙ ∙ 𝑒𝑥𝑝 𝜂 𝑐
𝑐𝑅,𝑏 𝑅𝑇 𝑠 𝑅,𝑠

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 54

 Mass Transfer on Reaction Rate
(Fuller Eq 3.33-2)
From previous:
1 𝛼𝑎 𝐹
𝑛𝐹𝑘𝑚 𝑐𝑅,𝑏 = 𝑛𝐹𝑘𝑚 + 𝑗0, 𝑏 ∙ ∙ 𝑒𝑥𝑝 𝜂 𝑐𝑅,𝑠
𝑐𝑅,𝑏 𝑅𝑇 𝑠
Therefore,
𝑛𝐹𝑘𝑚 𝑐𝑅,𝑏
𝑐𝑅,𝑠 =
1 𝛼𝑎 𝐹
𝑛𝐹𝑘𝑚 + 𝑗0, 𝑏 ∙ 𝑐 ∙ 𝑒𝑥𝑝 𝑅𝑇 𝜂𝑠
𝑅,𝑏
Recall
𝑐𝑅,𝑠 𝛼𝑎 𝐹
𝑗 = 𝑗0, 𝑏 ∙ ∙ 𝑒𝑥𝑝 𝜂
𝑐𝑅,𝑏 𝑅𝑇 𝑠

We have
1 𝛼𝑎 𝐹 𝑛𝐹𝑘𝑚 𝑐𝑅,𝑏
𝑗 = 𝑗0, 𝑏 ∙ ∙ 𝑒𝑥𝑝 𝜂 ∙
𝑐𝑅,𝑏 𝑅𝑇 𝑠 𝑛𝐹𝑘 + 𝑗 ∙ 1 ∙ 𝑒𝑥𝑝 𝛼𝑎 𝐹 𝜂
𝑚 0, 𝑏 𝑐𝑅,𝑏 𝑅𝑇 𝑠

𝛼𝑎 𝐹 𝑛𝐹𝑘𝑚
𝑗 = 𝑗0, 𝑏 ∙ 𝑒𝑥𝑝 𝜂 ∙
𝑅𝑇 𝑠 𝑛𝐹𝑘 + 𝑗 ∙ 1 ∙ 𝑒𝑥𝑝 𝛼𝑎 𝐹 𝜂
𝑚 0, 𝑏 𝑐𝑅,𝑏 𝑅𝑇 𝑠
EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 55
 Mass Transfer on Reaction Rate
(Fuller Eq 3.33-3)
From previous,
𝛼𝑎 𝐹 1
𝑗 = 𝑗0, 𝑏 ∙ 𝑒𝑥𝑝 𝜂 ∙
𝑅𝑇 𝑠 1 + 𝑗 ∙ 1 𝛼 𝐹
∙ 𝑒𝑥𝑝 𝑎 𝜂𝑠
0, 𝑏 𝑛𝐹𝑘𝑚 𝑐𝑅,𝑏 𝑅𝑇
1
𝑗=
1 1
𝛼𝑎 𝐹 +
𝑛𝐹𝑘𝑚 𝑐𝑅,𝑏
𝑗0,𝑏 ∙ 𝑒𝑥𝑝 𝜂
𝑅𝑇 𝑠

which is (3.33)

Note when 𝑐𝑅,𝑠 = 0 , electrode anodic/oxidative current as limited by mass transfer

𝑗 = 𝑛𝐹𝑘𝑚 𝑐𝑅,𝑏 − 𝑐𝑅,𝑠
,
reaches max or limiting value:
𝑗𝑙𝑖𝑚 = 𝑛𝐹𝑘𝑚 𝑐𝑅,𝑏

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 56

 Mass Transfer on Reaction Rate
(Fuller Eq 3.33-4)
On the other hand, if 𝑐𝑅,𝑟𝑒𝑓 = 𝑐𝑅,𝑏 , for current density from Tafel relationship
𝑐𝑅,𝑠 𝛼𝑎 𝐹
𝑗 = 𝑗0,𝑏 ∙ ∙ 𝑒𝑥𝑝 𝜂
𝑐𝑅,𝑏 𝑅𝑇 𝑠
We have
1 𝑐𝑅,𝑠 1
= ∙
𝛼𝑎 𝐹 𝑐𝑅,𝑏 𝑗
𝑗0,𝑏 ∙ 𝑒𝑥𝑝 𝑅𝑇 𝜂𝑠

Therefore,
1 1
𝑗= =𝑐
1 1 𝑅,𝑠 1 1
𝛼𝑎 𝐹 + ∙ +
𝑛𝐹𝑘𝑚 𝑐𝑅,𝑏 𝑐𝑅,𝑏 𝑗 𝑗𝑙𝑖𝑚
𝑗0,𝑏 ∙ 𝑒𝑥𝑝 𝑅𝑇 𝜂𝑠

𝑐𝑅,𝑠 𝑗
+ =1
𝑐𝑅,𝑏 𝑗𝑙𝑖𝑚
𝑐𝑅,𝑠 𝑗
=1−
𝑐𝑅,𝑏 𝑗𝑙𝑖𝑚

EMA 5305 Electrochemical Engineering Zhe Cheng 3 Electrochemical Kinetics 57