EMA4303/5305

Electrochemical Engineering
Lecture 04
Electrochemical Techniques
Prof. Zhe Cheng, Dr. Junheng Xing
Mechanical & Materials Engineering
Florida International University
 Electroanalytical Techniques

❑ Definition
Techniques that study an analyte/half
cell reaction by measuring potential or
current in an electrochemical cell
containing the analyte
❑ Categories
▪ Potentiometry - measure potential
(difference between electrodes, often j = 0)
▪ Amperometry - measure current,
often at fixed potential
▪ Coulometry - measure (total) charge (by
current) to complete reaction/exhaust (one)
active species
▪ Voltammetry - measure current while
changing potential
• Linear sweep voltammetry (LSV)
• Cyclic voltammetry (CV)
▪ Electrochemical impedance
spectroscopy (EIS) - measure
impedance, at different frequency http://community.asdlib.org/imageandvideoexchangeforum/2013/07/3
1/family-tree-for-interfacial-electrochemical-techniques/
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 2
 Electrochemical Measurement Configuration

❑Three-electrode configuration
Potentiostat/Galvanostat
WE Electrode of interest
CE Electrode counter/opposite to WE A Power source
to support/pass current
RE Electrode to probe potential
(difference) for electrode/half cell V
reaction of interest, often fast
(reversible) and close to WE
Potentiostat/galvanostat – instrument RE
that controls potential or current and measure
the other (current or potential)
❑Example measurements
▪ Potentiometry WE
measure V between WE & RE at constant I ;
when j = 0, CE/RE often connected
▪ Amperometry CE
measure I while fixing voltage between WE & RE
▪ Voltammetry
measure I while varying V between WE & RE
▪ EIS - measure impedance, usually at different f
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 3
 Potentiometry at Zero Current
Cell potential E vs. Current I

= 𝑬𝒆𝒒 + |𝑰| ∙ 𝑹𝒊𝒏𝒕

𝑬𝒄𝒆𝒍𝒍 = 𝑬𝒆𝒒 − |𝑰|𝑹𝒊𝒏𝒕

Ohmic drop IR
❑I = 0 =0 Ecell (or Eapp) = Eeq
Electrode overpotential η
❑Determine (standard) electrode potential for an electrode/half cell
reaction of interest, open circuit voltage (OCV), or activity including pH
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 4
 Activity from Cell Open Circuit Potential

An electrochemical cell with one electrode (redox pair) of Fe3+/Fe2+ and

the other electrode is standard AgCl/Ag electrode. If the activity for Fe2+
is 0.020, what is the activity for Fe3+ if the measured cell voltage is
0.531 V?

Fe3+ + e- = Fe2+, Eeqo (Fe3+/Fe2+) = 0.771 V

AgCl + e- = Ag + Cl-, Eeqo (AgCl/Ag) = 0.222 V
Overall: Fe3+ + Ag + Cl- = Fe2+ + AgCl
Ecello = Ecato – Eano = 0.771 V – 0.222 V = 0.549 V
𝑅𝑇 𝑅𝑇 𝑎𝐹𝑒 2+
o o
Nernst equation: 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − ln 𝑄 = 𝐸𝑐𝑒𝑙𝑙 − ln
𝑛𝐹 𝑛𝐹 𝑎𝐹𝑒 3+ ∙ 𝑎𝐶𝑙−
𝑎𝐹𝑒 2+ 0.020 o
𝑛𝐹 𝐸𝑐𝑒𝑙𝑙 − 𝐸𝑐𝑒𝑙𝑙
Therefore, = = exp −
𝑎𝐹𝑒 3+ ∙ 𝑎𝐶𝑙− 𝑎𝐹𝑒 3+ ∙ 1 𝑅𝑇
0.020
So, 𝑎𝐹𝑒 3+ = = 0.010
1 × 96485𝑄/𝑚𝑜𝑙 × 0.531𝑉 − 0.549𝑉
exp −
8.314𝐽/(𝑚𝑜𝑙 ∙ 𝐾) × 298.15𝐾
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 5
 Galvanostatic/Constant Current Measurement

❑ Galvanic cell Example: Effect of H2S contaminant in H2 on

solid oxide fuel cell (SOFC) operation
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑒𝑞 − 𝐼𝑅 − |𝜂𝑎 | − |𝜂𝑐 |
❑ Electrolytic cell
𝐸𝑎𝑝𝑝 = 𝐸𝑒𝑞 + 𝐼𝑅 + 𝜂𝑎 + |𝜂𝑐 |
H2 + OOx = H2O(g) + VO•• + 2e-
Cell potential E vs. Current I

recovery

Sulfur poisoning

𝑬𝒂𝒑𝒑 = 𝑬𝒆𝒒 + |𝑰|𝑹𝒊𝒏𝒕 𝑬𝒄𝒆𝒍𝒍 = 𝑬𝒆𝒒 − |𝑰|𝑹𝒊𝒏𝒕

Singhal, S. C., et al. (1986), Anode Development for Solid Oxide Fuel Cells,
Report No. DOE/MC/22046-2371

❑ Probe a reaction process,

❑ Ecell changes due to H2S poisoning of
poisoning/recovery, or stability
anode reaction, and, as a result,
increase in 𝜂𝑎
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 6
 Step Change in Potential -
Amperometry with Diffusion Control
E
Ox + ne- = Red E1
▪ Initial uniform concentration
▪ Static solution w/o stirring
▪ Large step change in potential
so that cact = 0 at electrode surface E2
▪ Diffusion control 0 t
𝜕𝑐act 𝑥, 𝑡 𝜕 2 𝑐act 𝑥, 𝑡 j ∗
𝑛𝐹𝐷0.5 𝑐act
= 𝑠𝑙𝑜𝑝𝑒 =
𝜕𝑡 𝜕𝑥 2 𝜋 0.5
Boundary conditions
∗
Initial condition 𝑐act 𝑥, 0 = 𝑐act
Boundary conditions:
𝑐act 0, 𝑡 = 0 Cottrell equation 0 𝑡 −0.5
∗ for measuring 𝑐𝑎𝑐𝑡
lim 𝑐act 𝑥, 𝑡 = 𝑐act ∗ ∗
𝑥→∞ D or 𝑐act 𝑐act t ≤ 0 < t1 < t2 < t3
Solution: ∗ 1
𝜕𝑐act 𝑥, 𝑡 𝑛𝐹𝐷0.5 𝑐act t1
𝑗 𝑡 = 𝑛𝐹 ∙ 𝐷 = 0.5 𝑡 0.5
t2 t3
𝜕𝑥 𝑥=0
𝜋
∗
𝑥
𝑐act 𝑥, 𝑡 = 𝑐act 𝑒𝑟𝑓
2 𝐷𝑡 0 x
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 7
 Step Change in Potential -
General Cases for Amperometry
Ox + ne - = Red E
E0
Assume 1
▪ Initial uniform concentration 2
▪ Static solution 3
4
▪ Initial positive enough and no Red 5
▪ Different potential steps 1, 2, 3, 4, and 5 0 t
Results I
▪ Diffusion brings active species (e.g., Ox) to 4& 5
electrode/electrolyte interface and sustain 3
current I 2
▪ Different situations w/ different step size 1
1. Too small a step, no (reduction) current
2. Larger step, some current 0 τ t
3. Even larger step, higher current
j (τ)
4. Step so large that leads to mass transport 4 5
limitation and limiting current 3
5. Same as 4: limited by diffusion for mass 2
transfer (saturated) 1
+E 0 -
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 8
 Cyclic Voltammetry (CV)

❑ Process E
▪ WE potential (vs. RE) is
ramped up & down linearly
with time in cycles 0
t
▪ Current at the WE is plotted vs
WE potential to give the cyclic
I
voltammogram (CV curve)
Simplest Case:
Resistor 0
❑ Applications t
▪ Study electrochemical
properties of an analyte or an I
V
electrode/half cell reaction
A
R 0 E
❑ Simplest example - resistor

EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 9

 CV for a Capacitor

Voltage ramp rate, unit V/s E

𝑑𝑉
=𝑣
𝑑𝑡
For a double-layer capacitor
0 t
during charging or discharging:
𝑑𝑄 = 𝐼 ∙ 𝑑𝑡 = 𝐶𝐷𝐿 𝑑𝑉 I
Therefore, current
Capacitor 0
𝑑𝑄 𝑑𝑉 t
𝐼= = 𝐶𝐷𝐿 = 𝑣𝐶𝐷𝐿
𝑑𝑡 𝑑𝑡
For given v and CDL : V I
▪ Constant current (absolute value)
A
during charging/discharging
CDL 0 E
▪ Current changes sign (polarity)
upon reaching limiting voltage

EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 10

 Example CV for Reversible
Electrode Reaction (1)
𝑶𝒙 + 𝒏𝒆− ↔ 𝑹𝒆𝒅 1. Starting point: 𝐼 = 0, E more positive than 𝐸 o (e.g.,
Equilibrium electrode/half cell reaction 0.361V - 0.222 V = 0.139 V vs. Ag/AgCl)
potential: 2. 𝐼 < 0 (cathodic) from Ox to Red, e.g.:
𝑅𝑇 𝑎𝑅𝑒𝑑 Fe(CN)63- + e- → Fe(CN)64-
𝐸𝑒𝑞 = 𝐸 o − ln
𝑛𝐹 𝑎𝑂𝑥 under negative (cathodic) overpotential
Assume: (i) Ox has much higher initial |𝐼| ↑ (more negative) due to larger (more
concentration than Red; and negative) cathodic overpotential
(ii) no convection (e.g., stirring) Surface Ox (i.e., Fe(CN)63-) concentration ↓
3. Cathodic peak current (ipc) and peak potential
(Epc) reached due to balance of cathodic
3
overpotential and mass transport limitation (by
4 diffusion)
2 4. 𝐼 < 0 due to cathodic overpotential;
5
|𝐼| ↓ due to mass transport (diffusion) limitation -
12 1 6
Ox (e.g., Fe(CN)63-) concentration gradient
7
|dC/dx|↓ as diffusion layer extends deeper into
11
8 electrolyte
10 5. Cathodic (negative) potential limit reached
6. E increases (more positive), but still negative
9
enough to reduce Fe(CN)63-,
|𝐼| ↓ as cathodic overpotential decreases and
further drop in |dC/dx| for Ox (e.g., Fe(CN)63-)
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 11
 Example CV for Reversible
Electrode Reaction (2)
𝑶𝒙 + 𝒏𝒆− ↔ 𝑹𝒆𝒅 7. Net reduction of Ox (e.g., Fe(CN)63-) no longer
Equilibrium electrode/half cell reaction occurs due to high concentration of accumulated
potential: Red (e.g., Fe(CN)64-) that promotes oxidation
𝑅𝑇 𝑎𝑅𝑒𝑑 8. 𝐼 > 0 (anodic) from Red to Ox, e.g.:
𝐸𝑒𝑞 = 𝐸 o − ln Fe(CN)64- → Fe(CN)63- + e-
𝑛𝐹 𝑎𝑂𝑥 under positive (anodic) overpotential
Assume: (i) Ox has much higher initial |𝐼| ↑ (more positive) due to larger (more positive)
concentration than Red, and anodic overpotential
(ii) no convection (e.g., stirring) Surface Red (i.e., Fe(CN)64-) concentration ↓
9. Anodic peak current (ipa) and peak potential (Epa)
reached due to balance of anodic overpotential
3 and mass transport limitation (by diffusion)
10. 𝐼 > 0 due to anodic overpotential;
4
2 |𝐼| ↓ due to mass transport (diffusion) limitation –
5
Red concentration gradient |dC/dx|↓ as diffusion
12 1 6 layer extends deeper into electrolyte
7 11. Anodic (positive) potential limit reached
11 12. E decreases (more negative), but still positive
8 enough to oxidize Red (e.g., Fe(CN)64-)
10 |𝐼| ↓ as anodic overpotential decreases and
further drop in |dC/dx| for Red (e.g., Fe(CN)64-)
9 1. Net oxidation of Red (e.g., Fe(CN)64-) no longer
occurs due to high concentration of accumulated
Ox (e.g., Fe(CN)63-) that promotes reduction
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 12
 Kinetic Information from CV for
Reversible Electrode/Half Cell Reaction
If rapid charge transfer - current
(electrode reaction rate) controlled
by diffusion
𝐸𝑝𝑎 and 𝐸𝑝𝑐 are independent of scan rate
▪ Equilibrium electrode potential
𝐸𝑒𝑞 = (𝐸𝑝𝑎 +𝐸𝑝𝑐 )/2

▪ Peak current 𝑖𝑝𝑐 = 𝑖𝑝𝑎

For dilute aqueous solution at RT:

▪ Number of electrons transferred
∆𝐸𝑝 = 𝐸𝑝𝑎 − 𝐸𝑝𝑐 = 0.059 𝑉/𝑛
▪ Peak current dependence
𝑖𝑝 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ∙ 𝑛3/2 𝑐𝐷1/2 𝑣 1/2
Fuller and Harb (2018), p. 125
c concentration
Determine D or c
D Diffusion coefficient
v scan rate, in mV/s

EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 13

 Quasi-reversible or Irreversible Reaction

For quasi-reversible or irreversible reaction, kinetics is slow →

Current is controlled by both charge transfer and mass transport (i.e.,
diffusion)

▪ As reaction rate constants (exchange

current) decreases, CV peaks shift to
higher (absolute) overpotentials since
the equilibrium at the surface is no
longer establishing rapidly

▪ Peak separation varies with scan rate.

Similarly, peak current no longer varies
with square root of the scan rate.
Current peaks are reduced in size
and are widely separated.

▪ As scan rate increases, irreversible

behavior becomes more noticeable
Fuller and Harb (2018), p. 125

EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 14

 CV Example - Supercapacitor

CV curves of ideal double layer capacitor (left) and pseudocapacitor (right)

http://www.sensorprod.com/research-articles/white-papers/2008_fcd/index.php
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 15
 CV Example - Li-ion Battery

de-lithiation

lithiation

+ LiCoO2 Charge Li1-xCoO2 + xLi+ + xe-

− xLi+ + xe- + 6C Charge LixC6 CV for LiCoO2 with variable potential
scanning rate
Illustration of Li-ion cell
R. Hausbrand et al., Materials Science and Engineering B 192 (2015) 3–25
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 16
 From Resistance to Impedance

❑Resistance & Ohm’s Law

Resistance - ability of a circuit element to resist the flow of (DC) electrical current
Ohm’s law:
𝑉
𝑅≡
𝐼
Ideal resistor
▪ Follows Ohm’s law at all current/voltage level and for both DC and AC
▪ Independent of AC frequency
▪ AC current and AC voltage are in phase with each other

❑Impedance Z
Circuit elements may exhibit more complex behavior, e.g.,
Capacitor C Inductor (e.g., coil) L
DC voltage V, DC current = 0 DC voltage V, DC current → ∞
෨ AC current 𝐼ሚ
AC voltage 𝑉, ෨ AC current 𝐼ሚ
AC voltage 𝑉,
Impedance Z - a general parameter to measure the 𝑉෨
ability of a circuit element to resist (impede) the flow of 𝑍=
electrical current, in both DC and AC 𝐼ሚ
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 17
 AC Voltage & Current

AC voltage or current are often sinusoidal

Example: AC voltage & AC current
AC voltage can be
written as:
𝑉෨ = 𝑉0 cos 𝜔𝑡
𝑉෨ = 𝑉0 cos 𝜔𝑡
𝑉0 AC voltage
amplitude

Current
Voltaage

ω radial frequency,
in radians/s

f frequency, in Hz

𝜔 = 2𝜋𝑓

𝐼ሚ = 𝐼0 cos(𝜔𝑡 − )
Time
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 18
 Impedance as a Complex Number (1)

If small signal, e.g., for voltage, 𝑉෨ = 𝑉0 cos 𝜔𝑡 = 𝑉0 cos 2𝜋𝑓𝑡

→ Linear response - Response (e.g., 𝐼) ሚ has same frequency, but shifted in phase by  :
𝐼ሚ = 𝐼0 cos(𝜔𝑡 − )
𝑉෨ 𝑉0 cos(𝜔𝑡) 𝑉0 cos(𝜔𝑡)
Impedance: 𝑍= = = ∙
𝐼ሚ 𝐼0 cos(𝜔𝑡 − ) 𝐼0 cos(𝜔𝑡 − )

𝑉0
Magnitude of impedance 𝑍 = 𝑍0 = Phase shift 
𝐼0
Recall for complex number, Euler’s formula gives: exp 𝑗 = cos + 𝑗sin
Introduce the imaginary part, potential and current responses can be presented as:
𝑉෨ = 𝑉0 exp 𝑗𝜔𝑡 𝐼ሚ = 𝐼0 exp 𝑗(𝜔𝑡 − )
Impedance is then represented as a complex number:
𝑉෨ 𝑉0 exp 𝑗𝜔𝑡 𝑉0
𝑍= = = exp 𝑗 = 𝑍0 (cos + 𝑗sin)
ሚ𝐼 𝐼0 exp 𝑗(𝜔𝑡 − ) 𝐼0

EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 19

 Impedance as a Complex Number (2)

❑Real & imaginary parts for impedance (vector)

𝑉෨ Im
𝑍= 𝑍 = 𝑍0 exp 𝑗 = 𝑍0 (cos + 𝑗sin)
𝐼ሚ
X 𝑍
𝑍 = 𝑅 + 𝑗𝑋 = 𝑍 ′ + 𝑗𝑍′′ = 𝑅𝑒 + 𝑗𝐼𝑚 |𝑍|
𝑅 = 𝑍 ′ = 𝑅𝑒 = 𝑍0 cos  𝑍 = 𝑍0 = 𝑅2 + 𝑋 2

𝑋= 𝑍 ′′ = 𝐼𝑚 = 𝑍0 sin  𝑡𝑎𝑛 = 𝑋/𝑅 0 R Re

❑Impedance for common elements under AC with frequency of f

Im
▪ Resistor R 𝑍𝑅 = 𝑅 = 𝑅 + 𝑗 ∙ 0
𝜔𝐿𝑗
1 1 1 𝑅
▪ Capacitor C 𝑍𝐶 = = = 0+𝑗∙ − 0
𝑗𝜔𝐶 𝑗2𝜋𝑓𝐶 𝜔𝐶 Re

1
▪ Inductor L 𝑍𝐿 = 𝑗 ∙ 𝜔𝐿 = 𝑗2𝜋𝑓𝐿 = 0 + 𝑗 ∙ 𝜔𝐿 − 𝑗
𝜔𝐶
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 20
 Common Circuit Elements Impedance

Resistor: 𝑍𝑅 = 𝑅 = 𝑅 + 𝑗 ∙ 0 = 𝑅 exp 𝑗 ∙ 0

𝑍 independent of f and has only real component

 = 0, i.e., current always in phase with voltage

1 1 1 𝜋
Capacitor: 𝑍𝐶 = 0 + 𝑗 ∙ − = = exp 𝑗 −
𝜔𝐶 𝑗𝜔𝐶 2𝜋𝑓𝐶 2
𝑍 = 1Τ 2𝜋𝑓𝐶 decreases as f increases
Only imaginary component
𝐼ሚ phase shifted − 𝜋Τ2 or -90o, i.e., ahead-of or before 𝑉෨

𝜋
Inductor: 𝑍𝐿 = 0 + 𝑗 ∙ 𝜔𝐿 = 𝑗𝜔𝐿 = 2𝜋𝑓𝐿 exp 𝑗
2
𝑍 = 2𝜋𝑓𝐿 increases as f increases
Only an imaginary component
𝐼ሚ phase shifted 𝜋Τ2 or 90o, i.e., behind or after 𝑉෨

EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 21

 Combining Impedance

❑Series combination

𝑍𝑡𝑜𝑡𝑎𝑙 = 𝑍1 + 𝑍2

Z1 Z2 𝑍𝑡𝑜𝑡𝑎𝑙 = 𝑅1 + 𝑅2 + 𝑗 𝑋1 + 𝑋2

❑Parallel combination
1 1 1
Z1 = +
𝑍𝑡𝑜𝑡𝑎𝑙 𝑍1 𝑍2

𝑍1 ∙ 𝑍2
𝑍𝑡𝑜𝑡𝑎𝑙 =
𝑍1 + 𝑍2
Z2

EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 22

 Impedance Spectra for Common Elements (1)

Measure impedance at different frequency f , e.g., 10-3 to 107 Hz

Resistor Capacitor Resistor & capacitor in series

1 1 1
𝑍𝑅 = 𝑅 𝑍𝐶 = =0−𝑗 𝑍 = 𝑍𝑅 + 𝑍𝐶 = 𝑅 − 𝑗
𝑗𝜔𝐶 2𝜋𝑓𝐶 2𝜋𝑓𝐶
𝑅𝑒 = 𝑅
𝑅𝑒 = 0 𝑅𝑒 = 𝑅
𝐼𝑚 = 0 1 1
𝐼𝑚 = − 𝐼𝑚 = −
2𝜋𝑓𝐶 2𝜋𝑓𝐶

-Im -Im -Im

𝑓 decreases 𝑓 decreases
(from ∞) (from ∞)
0 0 Re 0 Re
Re

EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 23

 Impedance Spectra for Common Elements (2)

Resistor & capacitor in parallel

1
𝑅 ∙ 𝑗𝜔𝐶 𝑅 𝑅(1 − 𝑅𝑗𝜔𝐶) 𝑅 𝜔𝑅2 𝐶
𝑍= = = = 2 − 𝑗 1 + (𝜔𝑅𝐶)2
1 𝑅𝑗𝜔𝐶 + 1 (1 + 𝑅𝑗𝜔𝐶)(1 − 𝑅𝑗𝜔𝐶) 1 + (𝜔𝑅𝐶)
𝑅 + 𝑗𝜔𝐶
𝑅 𝜔𝑅2 𝐶
𝑅𝑒 = 𝐼𝑚 = −
1 + (𝜔𝑅𝐶)2 1 + (𝜔𝑅𝐶)2
2 2 2
𝑅 2𝑅 − 𝑅 1 + 𝜔𝑅𝐶 𝑅 − 𝑅 𝜔𝑅𝐶 𝑅 2
𝑅2 1 − 2 𝜔𝑅𝐶 2 + 𝜔𝑅𝐶 4
4𝑅2 𝜔𝑅𝐶 2
𝑅𝑒 − = = 𝑅𝑒 − + 𝐼𝑚 = +
2 2 1 + 𝜔𝑅𝐶 2 2 1 + 𝜔𝑅𝐶 2 2 4 1 + 𝜔𝑅𝐶 2 2 4 1 + 𝜔𝑅𝐶 2 2

2 2
𝑅 2
𝑅2 1 − 2 𝜔𝑅𝐶 2 + 𝜔𝑅𝐶 4
4 𝜔𝑅𝐶 2 𝑅2 1 + 2 𝜔𝑅𝐶 2 + 𝜔𝑅𝐶 4
𝑅
𝑅𝑒 − + 𝐼𝑚 = + = =
2 4 1 + 𝜔𝑅𝐶 2 2 1 + 𝜔𝑅𝐶 2 2 4 1 + 𝜔𝑅𝐶 2 2 2

-Im
2 2 A circle centered at (R/2, 0) & radius R/2
𝑅 𝑅
𝑅𝑒 − + 𝐼𝑚2 = ω → ∞, Re → 0, Im → 0
2 2 ω → 0, Re → R, Im → 0 ω→0
0
ω→∞ Re
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 24
 Impedance Spectrum for an Electrode
w/o Diffusion Limitation
Cd
Simplified Randles cell for an electrode R
▪ (Electrolyte) ohmic resistance 𝑅Ω
▪ Double layer capacitor 𝐶𝑑
▪ Charge transfer resistance 𝑅𝑐𝑡 Rct
1 2
𝑑|𝐼𝑚| 𝐶𝑑 𝑅𝑐𝑡 ∙ 1 + 𝜔2 𝐶𝑑2 𝑅𝑐𝑡
2 2
− 𝜔𝐶𝑑 𝑅𝑐𝑡 ∙ 2𝜔𝐶𝑑2 𝑅𝑐𝑡
2
𝑍 = 𝑅Ω + =
1 𝑑𝜔 1 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡
2 2
𝑗𝜔𝐶𝑑 + 𝑅
𝑐𝑡
2
2
𝑑|𝐼𝑚| 𝐶𝑑 𝑅𝑐𝑡 + 𝜔2 𝐶𝑑3 𝑅𝑐𝑡
4
− 2𝜔2 𝐶𝑑3 𝑅𝑐𝑡
4 2
𝐶𝑑 𝑅𝑐𝑡 − 𝜔2 𝐶𝑑3 𝑅𝑐𝑡
4
𝑅𝑐𝑡 𝜔𝐶d 𝑅𝑐𝑡 𝑑𝜔
=
1 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡
2 2 = 2 2 =0
1 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡
𝑍 = 𝑅Ω + 2 −𝑗1
1 + 𝜔 2 𝐶d2 𝑅ct + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡
2
2
𝐶𝑑 𝑅𝑐𝑡 = 𝜔2 𝐶𝑑3 𝑅𝑐𝑡
4
𝑅𝑐𝑡
𝑅𝑒 = 𝑅Ω +
1 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡
2
2
𝜔𝐶𝑑 𝑅𝑐𝑡 1
𝐼𝑚 = − 𝜔=
1 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡
2 -Im 𝑅𝑐𝑡 𝐶𝑑
2 2
𝑅𝑐𝑡 2
𝑅𝑐𝑡
𝑅𝑒 − 𝑅Ω − + 𝐼𝑚 = ω→∞ ω→0
2 2
▪ 𝑅Ω & 𝑅𝑐𝑡 obtained from Im – Re (Nyquist) plot 0 𝑅Ω 𝑅Ω + 𝑅𝑐𝑡 Re
▪ 𝐶𝑑 calculated from top of the semi-cycle
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 25
 Additional Electrical Circuit Elements -
Constant Phase Element (CPE)
▪ Actual electrode processes often do not behave like ideal capacitor or
resistor in combination.
▪ Introduce CPE with constant phase shift between 𝑉෨ & 𝐼ሚ to simulate the
process
1 𝑌0 equivalent to capacitance C or
𝑍𝐶𝑃𝐸 = conductance
𝑌0 (𝑗𝜔)𝛼 𝛼 Exponent from 0 to 1

1 −𝛼 1 𝜋 −𝛼 1 𝛼𝜋
𝑍𝐶𝑃𝐸 = 𝑗 = exp 𝑗 = exp −𝑗
𝑌0 𝜔 𝛼 𝑌0 𝜔 𝛼 2 𝑌0 𝜔 𝛼 2
1
Magnitude |𝑍𝐶𝑃𝐸 | =
𝑌0 𝜔 𝛼
𝛼𝜋 -Im 𝑓 decreases
Phase shift 𝐶𝑃𝐸 = −
2 (from ∞)
|𝑍𝐶𝑃𝐸 | ↓ with increasing 𝜔 or f
𝛼 = 0, 𝐶𝑃𝐸 = 0 = 0° , ideal resistor  = 𝛼𝜋/2
0
𝛼 = 1, 𝐶𝑃𝐸 = − 𝜋Τ2 = 90° , ideal capacitor Re
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 26
 Additional Electrical Circuit Elements -
Warburg Element (W)
A special type of CPE (𝛼 = 0.5) representing impedance 𝑍 = 1
W
due to mass transfer limitation by diffusion. 𝑌0 𝑗𝜔
1 𝜋 −0.5 1 𝜋
𝑍W =
𝑌0 𝜔
∙ exp 𝑗
2
=
𝑌0 𝜔
∙ exp −𝑗
4 -Im 𝑓 decreases (from ∞)
1 1 1
𝑍W = ∙ −𝑗 = 𝜎𝜔−0.5 1 − 𝑗
𝑌0 𝜔 2 2  = 𝜋/4
▪ |ZW| depends on f 0
Re
▪ High f, ZW negligible since diffusing reactants don't have to move far
▪ Low f, reactants have to diffuse farther, increasing |ZW|
▪ A diagonal line with slope = 1 (phase shift of 45°) on Im-Re plot
Summary
R L C Q W
Element
(resistor) (inductor) (capacitor) (CPE) (Warburg)

1 1 1
Impedance 𝑍=𝑅 𝑍 = 𝑗𝜔𝐿 𝑍= 𝑍= 𝑍=
𝑗𝜔𝐶 𝑌0 (𝑗𝜔)𝛼 𝑌0 𝑗𝜔
* 𝑌0 is equivalent to capacitance C or conductance; 𝛼 is an exponent from 0 to 1.
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 27
 Impedance Spectrum for Electrode with
Warburg Element (i.e., Involving Diffusion) (1)
Electrode reaction controlled by both
Cd
charge transfer & diffusion
R
1
𝑍 = 𝑅Ω + ZW
1
𝑗𝜔𝐶𝑑 + Rct
𝑅𝑐𝑡 + 𝜎𝜔 −0.5 (1 − 𝑗)

𝑅𝑐𝑡 + 𝜎𝜔−0.5
𝑅𝑒 = 𝑅Ω +
(𝐶𝑑 𝜎𝜔 0.5 + 1)2 +𝜔 2 𝐶𝑑2 (𝑅𝑐𝑡 + 𝜎𝜔 −0.5 )2

𝜔𝐶𝑑 (𝑅𝑐𝑡 + 𝜎𝜔−0.5 )2 +𝜎𝜔−0.5 (𝐶𝑑 𝜎𝜔0.5 + 1)

𝐼𝑚 = −
(𝐶𝑑 𝜎𝜔 0.5 + 1)2 +𝜔 2 𝐶𝑑2 (𝑅𝑐𝑡 + 𝜎𝜔 −0.5 )2

When 𝝎 → 𝟎 (approaching DC):

𝑅𝑒 ≈ 𝑅Ω + 𝑅𝑐𝑡 + 𝜎𝜔−0.5
𝐼𝑚 ≈ 𝜎𝜔−0.5 + 2𝜎 2 𝐶𝑑
Cancel 𝜔, we have:
𝐼𝑚 = 𝑅𝑒 − 𝑅Ω − 𝑅𝑐𝑡 + 2𝜎 2 𝐶𝑑
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 28
 Impedance Spectrum for Electrode with
Warburg Element (i.e., Involving Diffusion) (2)
When 𝝎 very large, 𝜔−0.5 neglected,
1 1
𝑍 = 𝑅Ω + ≈ 𝑅Ω +
1 1
𝑗𝜔𝐶𝑑 + 𝑗𝜔𝐶𝑑 + 𝑅
𝑅𝑐𝑡 + 𝜎𝜔 −0.5 (1 − 𝑗) 𝑐𝑡

→ the same as charge-transfer controlled electrode process w/o diffusion limitation

Combine two scenarios:

High 𝜔 → charge transfer
limitation
Low 𝜔 → mass transfer
(diffusion) limitation
𝑅Ω , 𝑅𝑐𝑡 , 𝐶𝑑 , 𝜎 all can be
obtained from Im vs. Re
(Nyquist) plot
j0 obtained from 𝑅𝑐𝑡 by
𝑅𝑇
𝑗0 =
𝑛𝐹𝑅𝑐𝑡

EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 29

 Homework

❑Read textbook chapter 6 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

EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 30

 EIS Example (1) - Supercapacitor

EIS of the PANI/Px-MWCNT based supercapacitors

D. Potphode, et al., Electrochemica Acta, 2015, 155, 402-410
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 31
 EIS Example (2) - Li-ion Battery

Internal dynamic phenomena and the

corresponding Nyquist plot of Li-ion battery
D. Zhou, et al., Energies, 2016, 9, 123
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 32
 EIS Example (3) - Biosensor

Nyquist plots of electrodes incubated with

Label-free biosensor for 17β-estradiol
different concentration of 17β-estradiol

Which one has the highest concentration?

Z. Lin, et al., Analyst, 2012, 137, 819

EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 33
 EIS Modeling

❑EIS modeling
▪ Electrochemical cells can be modeled as a network of passive electrical circuit
elements. The network is so called “equivalent circuit”.
▪ The EIS response of an equivalent circuit can be calculated and compared to the
actual EIS response of the electrochemical cell.

❑Modeling process
▪ Get the experimental data
▪ Develop a possible equivalent circuit
▪ Adjust the parameters (e.g., Cd, Rp,
Ru) until fitting well

❑Common software
▪ ZSimpWin
▪ Gamry Echem Analyst

EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 34

 Impedance Spectrum for Electrode with
Warburg Element (i.e., Involving Diffusion) (3)
Electrode reaction controlled by both charge transfer & diffusion
1 1 𝜋 −0.5 1 𝜋 1 1 1
𝑍W = = ∙ exp 𝑗 = ∙ exp −𝑗 = ∙ −𝑗 = 𝜎𝜔−0.5 1 − 𝑗
𝑌0 𝑗𝜔 𝑌0 𝜔 2 𝑌0 𝜔 4 𝑌0 𝜔 2 2
Cd
1 R
𝑍 = 𝑅Ω +
1
𝑗𝜔𝐶𝑑 +
𝑅𝑐𝑡 + 𝜎𝜔 −0.5 (1 − 𝑗) ZW
1 Rct
𝑍 = 𝑅Ω +
1
𝑗𝜔𝐶𝑑 +
𝑅𝑐𝑡 + 𝜎𝜔 −0.5 − 𝑗𝜎𝜔 −0.5

𝑅𝑐𝑡 + 𝜎𝜔−0.5 − 𝑗𝜎𝜔−0.5 𝑅𝑐𝑡 + 𝜎𝜔−0.5 − 𝑗𝜎𝜔−0.5

𝑍 = 𝑅Ω + = 𝑅Ω +
𝑗𝜔𝐶𝑑 ∙ 𝑅𝑐𝑡 + 𝜎𝜔 −0.5 − 𝑗𝜎𝜔 −0.5 + 1 1 + 𝜎𝜔 0.5 𝐶𝑑 + 𝑗 𝜔𝐶𝑑 𝑅𝑐𝑡 + 𝜎𝜔 0.5 𝐶𝑑

𝑅𝑐𝑡 + 𝜎𝜔−0.5 − 𝑗𝜎𝜔−0.5 ∙ 1 + 𝜎𝜔0.5 𝐶𝑑 − 𝑗 𝜔𝐶𝑑 𝑅𝑐𝑡 + 𝜎𝜔0.5 𝐶𝑑

𝑍 = 𝑅Ω +
1 + 𝜎𝜔 0.5 𝐶𝑑 2 + 𝜔𝐶𝑑 𝑅𝑐𝑡 + 𝜎𝜔 0.5 𝐶𝑑 2
2
𝑅𝑐𝑡 + 𝜎𝜔−0.5 + 𝑅𝑐𝑡 𝜎𝜔0.5 𝐶𝑑 + 𝜎 2 𝐶𝑑 − 𝜎𝜔0.5 𝐶𝑑 𝑅𝑐𝑡 − 𝜎 2 𝐶𝑑 − 𝑗 𝜎𝜔−0.5 + 𝜎 2 𝐶𝑑 + 𝜔𝐶𝑑 𝑅𝑐𝑡 + 𝜎𝜔0.5 𝐶𝑑 𝑅𝑐𝑡 + 𝜎𝜔0.5 𝐶𝑑 𝑅𝑐𝑡 + 𝜎 2 𝐶𝑑
𝑍 = 𝑅Ω +
𝐶𝑑 𝜎𝜔 0.5 + 1 2 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡 + 𝜎𝜔 −0.5 2

2
𝑅𝑐𝑡 + 𝜎𝜔−0.5 − 𝑗 𝜎𝜔−0.5 + 𝜎 2 𝐶𝑑 + 𝜔𝐶𝑑 𝑅𝑐𝑡 + 2𝜎𝜔0.5 𝐶𝑑 𝑅𝑐𝑡 + 𝜎 2 𝐶𝑑
𝑍 = 𝑅Ω +
𝐶𝑑 𝜎𝜔 0.5 + 1 2 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡 + 𝜎𝜔 −0.5 2

EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 35

 Impedance Spectrum for Electrode with
Warburg Element (i.e., Involving Diffusion) (4)
2
𝑅𝑐𝑡 + 𝜎𝜔−0.5 − 𝑗 𝜎𝜔−0.5 + 𝜎 2 𝐶𝑑 + 𝜔𝐶𝑑 𝑅𝑐𝑡 + 2𝜎𝜔0.5 𝐶𝑑 𝑅𝑐𝑡 + 𝜎 2 𝐶𝑑
𝑍 = 𝑅Ω +
𝐶𝑑 𝜎𝜔 0.5 + 1 2 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡 + 𝜎𝜔 −0.5 2

2
𝑅𝑐𝑡 + 𝜎𝜔−0.5 𝜎𝜔−0.5 + 𝜎 2 𝐶𝑑 + 𝜔𝐶𝑑 𝑅𝑐𝑡 + 2𝜎𝜔0.5 𝐶𝑑 𝑅𝑐𝑡 + 𝜎 2 𝐶𝑑
𝑍 = 𝑅Ω + −𝑗
𝐶𝑑 𝜎𝜔 0.5 + 1 2 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡 + 𝜎𝜔 −0.5 2 𝐶𝑑 𝜎𝜔 0.5 + 1 2 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡 + 𝜎𝜔 −0.5 2

𝑅𝑐𝑡 + 𝜎𝜔−0.5
𝑅𝑒 = 𝑅Ω +
(𝐶𝑑 𝜎𝜔 0.5 + 1)2 +𝜔 2 𝐶𝑑2 (𝑅𝑐𝑡 + 𝜎𝜔 −0.5 )2

2
𝜎𝜔−0.5 + 𝜎 2 𝐶𝑑 + 𝜔𝐶𝑑 𝑅𝑐𝑡 + 2𝜎𝜔0.5 𝐶𝑑 𝑅𝑐𝑡 + 𝜎 2 𝐶𝑑
𝐼𝑚 = −
𝐶𝑑 𝜎𝜔 0.5 + 1 2 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡 + 𝜎𝜔 −0.5 2

2
𝜎𝜔−0.5 1 + 𝜎𝜔0.5 𝐶𝑑 + 𝜔𝐶𝑑 𝑅𝑐𝑡 + 2𝜎𝜔−0.5 𝑅𝑐𝑡 + 𝜎 2 𝜔−1
𝐼𝑚 = −
𝐶𝑑 𝜎𝜔 0.5 + 1 2 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡 + 𝜎𝜔 −0.5 2

𝜎𝜔−0.5 1 + 𝜎𝜔0.5 𝐶𝑑 + 𝜔𝐶𝑑 𝑅𝑐𝑡 + 𝜎𝜔−0.5 2

𝐼𝑚 = −
𝐶𝑑 𝜎𝜔 0.5 + 1 2 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡 + 𝜎𝜔 −0.5 2

𝜔𝐶𝑑 (𝑅𝑐𝑡 + 𝜎𝜔−0.5 )2 +𝜎𝜔−0.5 (𝐶𝑑 𝜎𝜔0.5 + 1)

𝐼𝑚 = −
(𝐶𝑑 𝜎𝜔 0.5 + 1)2 +𝜔 2 𝐶𝑑2 (𝑅𝑐𝑡 + 𝜎𝜔 −0.5 )2

EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 36

 Combining Impedance (2)
𝑍1 ∙ 𝑍2 𝑅1 + 𝑗𝑋1 ∙ 𝑅2 + 𝑗𝑋2
❑Parallel combination 𝑍𝑡𝑜𝑡𝑎𝑙 =
𝑍1 + 𝑍2
=
𝑅1 + 𝑗𝑋1 + 𝑅2 + 𝑗𝑋2
Z1
𝑅1 + 𝑗𝑋1 ∙ 𝑅2 + 𝑗𝑋2 𝑅1 𝑅2 − 𝑋1 𝑋2 + 𝑗 𝑅1 𝑋2 + 𝑅2 𝑋1
𝑍𝑡𝑜𝑡𝑎𝑙 = =
𝑅1 + 𝑅2 + 𝑗 𝑋1 + 𝑋2 𝑅1 + 𝑅2 + 𝑗 𝑋1 + 𝑋2

𝑅1 𝑅2 − 𝑋1 𝑋2 + 𝑗 𝑅1 𝑋2 + 𝑅2 𝑋1 ∙ 𝑅1 + 𝑅2 − 𝑗 𝑋1 + 𝑋2
𝑍𝑡𝑜𝑡𝑎𝑙 =
Z2 𝑅1 + 𝑅2 2 + 𝑋1 + 𝑋2 2

𝑅1 + 𝑅2 𝑅1 𝑅2 − 𝑋1 𝑋2 + 𝑋1 + 𝑋2 𝑅1 𝑋2 + 𝑅2 𝑋1 + 𝑗 𝑅1 + 𝑅2 𝑅1 𝑋2 + 𝑅2 𝑋1 − 𝑋1 + 𝑋2 𝑅1 𝑅2 − 𝑋1 𝑋2
𝑍𝑡𝑜𝑡𝑎𝑙 =
𝑅1 + 𝑅2 2 + 𝑋1 + 𝑋2 2
𝑅12 𝑅2 + 𝑅1 𝑅22 − 𝑅1 𝑋1 𝑋2 − 𝑅2 𝑋1 𝑋2 + 𝑅1 𝑋1 𝑋2 + 𝑅1 𝑋22 + 𝑅2 𝑋12 + 𝑅2 𝑋1 𝑋2
𝑅𝑒 =
𝑅1 + 𝑅2 2 + 𝑋1 + 𝑋2 2

𝑅12 𝑋2 + 𝑅1 𝑅2 𝑋2 + 𝑅1 𝑅2 𝑋1 + 𝑅22 𝑋1 − 𝑅1 𝑅2 𝑋1 − 𝑅1 𝑅2 𝑋2 + 𝑋12 𝑋2 + 𝑋1 𝑋22

𝐼𝑚 =
𝑅1 + 𝑅2 2 + 𝑋1 + 𝑋2 2

𝑅12 𝑅2 + 𝑅1 𝑅22 + 𝑅1 𝑋22 + 𝑅2 𝑋12 𝑅12 𝑋2 + 𝑅22 𝑋1 + 𝑋12 𝑋2 + 𝑋1 𝑋22

𝑅𝑒 = 𝐼𝑚 =
𝑅1 + 𝑅2 2 + 𝑋1 + 𝑋2 2 𝑅1 + 𝑅2 2 + 𝑋1 + 𝑋2 2

𝑅1 𝑅2 𝑅1 + 𝑅2 + 𝑅1 𝑋22 + 𝑅2 𝑋12 𝑅12 + 𝑋12 𝑋2 + 𝑅22 + 𝑋22 𝑋1

𝑅𝑒 = 𝐼𝑚 =
𝑅1 + 𝑅2 2 + 𝑋1 + 𝑋2 2 𝑅1 + 𝑅2 2 + 𝑋1 + 𝑋2 2

EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 37

 Impedance Spectrum for an Electrode
w/o Diffusion Limitation (2)
Cd -Im 1
R 𝜔=
𝑅𝑐𝑡 𝐶𝑑
ω→∞ ω→0
Rct
0 𝑅Ω 𝑅Ω + 𝑅𝑐𝑡 Re
2
1 𝑅𝑐𝑡 𝑅𝑐𝑡 𝜔𝐶d 𝑅𝑐𝑡
𝑍 = 𝑅Ω + = 𝑅Ω + = 𝑅Ω + 2 − 𝑗 1 + 𝜔 2 𝐶 2 𝑅2
𝑗𝜔𝐶𝑑 + 𝑅
1 1 + 𝑗𝜔𝐶𝑑 𝑅𝑐𝑡 1 + 𝜔 2 𝐶d2 𝑅ct 𝑑 𝑐𝑡
𝑐𝑡 2
𝑅𝑐𝑡 𝜔𝐶𝑑 𝑅𝑐𝑡
𝑅𝑒 = 𝑅Ω + 𝐼𝑚 = −
1 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡
2
1 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡
2

2 2 2 2 2
𝑅𝑐𝑡 𝑅𝑐𝑡 𝑅𝑐𝑡 𝑅𝑐𝑡 𝑅𝑐𝑡 𝑅𝑐𝑡
𝑅𝑒 − 𝑅Ω − = − = − +
2 1 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡
2 2 1 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡
2
1 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡
2 2
2 2 2 2 2 2
𝑅𝑐𝑡 𝑅𝑐𝑡 𝑅𝑐𝑡 𝑅𝑐𝑡 𝜔𝐶𝑑 𝑅𝑐𝑡
𝑅𝑒 − − 𝑅Ω + 𝐼𝑚2 = − + +
2 1 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡
2
1 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡
2 2 1 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡
2

2 2 2
𝑅𝑐𝑡 2
2
𝑅𝑐𝑡 2
− 𝑅𝑐𝑡 − 𝜔2 𝐶𝑑2 𝑅𝑐𝑡
4 2
+ 𝜔𝐶𝑑 𝑅𝑐𝑡 2 𝑅𝑐𝑡 𝑅𝑐𝑡
𝑅𝑒 − − 𝑅Ω + 𝐼𝑚 = + =
2 1 + 𝜔 2 𝐶𝑑2 𝑅𝑐𝑡
2 2 2 2
EMA 5305 Electrochemical Engineering Zhe Cheng 4 Electrochemical Techniques 38