Textbook

Electrochemical Methods—fundamentals and applications, 2nd edition (2001).

by A. J. Bard and L. R. Faulkner, John Wiley.

References—For the details about laboratory procedures:

1. Electrochemistry for Chemists, 2nd edition by D.T Sawyer and J.L. Roberts
(1995).
2. Experimental Electrochemistry for Chemists by D.T. Sawyer and J.L. Roberts
(1974)
3. Laboratory Techniques Electroanalytical Chemistry by P.T. Kissinger and W.R.
Heineman (1982).

For a List of Symbols: Pure Appl. chem., 37, 503 (1974).

For classification: Pure Appl. Chem., 45, 83 (1976).

What is the physical meaning by potential?

Volt is the common unit of joule/coul, energy per charge, related to energy.

What is the physical meaning by current?

Ampere is the common unit of coul./sec, charge per second, related to reaction rate.

Coulomb is the unit of charge. Each electron has charge of 1.6x10-19 coul.
1 mole electrons has charge of 96500 coul, which is defined as 1 Faraday (1 F).
1 F = 96500 coul./mole of electrons or 96500/1 equivalent.

1 
 
Chapter 1 Introduction

Applications of electrochemical measurements:

1. Obtaining thermodynamic/kinetics data;
2. Generating and studying unstable intermediates: radical ions…;
3. Analyzing trace species: metal ion, organics…;
4. Investigating electrochemical properties: batteries, fuel cells, synthesis….

Electrochemical cell:
Electrolyte － liquid solutions, fused salts, solids
Electrode － metals, semiconductors, liquids

Effect of Potential drop on the electrode:

Sharp transition of electric potential between two phases

high electric field at the phase interface
great effect on kinetic behavior of charge carriers

C + O2  CO2 ΔG = -394 KJ/mole

H2 + 0.5O2  H2O ΔG = -237 kJ/moles E° = 1.23 V
H2O(l)  H2O(g) ΔHvap = 127 kJ/moles
Energy change happens in the thickness of about 0.1 nm.
Potential drops in the range of 1 volt/0.1 nm = 100 MV/cm

Experimental electrochemistry is the issue of measurement/ control of cell potential

Convention for cell expression Fig 1.1.1:
Zn  Ag 

Zn/Zn2+, Cl-/AgCl/Ag
Zn2+
Cl‐  AgCl

    H2 
Pt  Ag
+ -
Pt/H2/H , Cl /AgCl/Ag
H+
Cl‐ AgCl

2 
 
Half reaction is concerned with interfacial potential difference.

Half potentials are always standardized to a reference potential

(Cell potentials are the potential difference between working and counter electrodes.)

Common reference electrodes:

1. SHE － normal hydrogen electrode (in an acid solution with activity of H+ = 1 mol dm−3).
2. NHE － standard hydrogen electrode (in 1N acid solution).
3. RHE － reversible hydrogen electrode (directly used in electrolyte).
4. SCE － saturated calomel electrode (Hg/Hg2Cl2/KCL(sat'd in water)).
5. Ag/AgCl.

What is the effect of potential on electrode?

1. more negative potentials higher energy of the electrons at electrode

∆G nEF W q ∙ E
Fig 1.1.2(a) reduction current: Electrons transfer from electrode to electrolyte.

2. more positive potentials lower energy of the electrons at electrode

Fig 1.1.2(b) oxidation current: Electrons transfer from electrolyte to electrode.

Eeq is the potential with zero-current which means at equilibrium.

Eo is the equilibrium potential at standard condition.

A voltmeter can determine open circuit potentials (zero-current potential or rest

potential).

Fig 1.1.1 two half cells at equilibrium Pt/H2/H+, Cl-/AgCl/Ag

Fig 1.1.3 only one half cell at equilibrium Pt/H+, Br-/AgBr/Ag

In the cell: Pt/H+, Br-/AgBr/Ag

AgBr + e- Ag + Br- Eo = 0.07V vs. NHE
2H+ + 2e- H2 Eo = 0V vs. NHE -0.07V vs Ag/AgBr
Eo = 1.09V vs. NHE 1.02V vs Ag/AgBr

3 
 
Background limits:
Electrochemical window－the potential range without current from interferences,
which are usually solvent and electrode.
Open circuit potential－not easily obtained from thermodynamic calculation, and
may be affected by impurity, Fig1.1.4.

Fig 1.1.4 Pt/H+, Br-(1M)/AgBr/Ag

Fig 1.1.5 Hg/H+, Br-(1M)/AgBr/Ag (overpotential for 2H+ + 2e- H2)

Fig 1.1.6 Hg/H+, Br-(1M), Cd2+(10-3M)/AgBr/Ag

CdBr42- +2e- Cd(Hg) + 4Br- at negative potential
Hg 

Cd2+ +2e- Cd(Hg) Eo = -0.35V (vs. NHE)

Fig 1.1.7
(a) 0.01M Fe3+, 0.01M Sn4+, 0.01M Ni2+ in 1M HCl for Pt electrode (rapid kinetics)
potential ≧ 0.77V (no current or fully oxidized)
potential ＜ 0.77V Fe3+ + e- Fe2+
with Sn4+, H+, Ni2+
potential ＜ 0.15V Fe3+ + e- Fe2+
Sn4+ + 2e- Sn2+
with H+, Ni2+
potential ＜ 0.0V Fe3+ + e- Fe2+
Sn4+ + 2e- Sn2+
2H+ + 2e- H2
2+
with Ni
－ 

Sn2+ 
Reduction
2+
Fe Ni
H2 
+  －
0.77      0.15      0        ‐0.25 
+ 

4 
 
(b) 0.01M Sn2+, 0.01M Fe2+ in 1M Hl for Au electrode (rapid kinetics)
－

+  －

1.50    1.23    0.77    0.54    0.15   

Oxidation
 
Au3+  O2 Fe2+  I2  Sn2+ 
+

c) 0.01M Cr3+, 0.01M Zn2+ in 1M HCl for Hg electrode (slow kinetics)

－ 
Zn2+
2+
Cr H2 
+  －
0      ‐0.41      ‐0.76 

+ 

5 
 
§ 1-2 Nonfaradaic Current

Proposed Model for Double layer as shown in Figure 1.2.3 and 1.2.4

1. Faradaic process is the process related to the charge transfer from or to the electoactive
species. The current is the reaction rate and follows Faraday's law
2. Nonfaradaic process is a process related to the adsorption & desorption of ions. The
current is the accumulation rate of charges on the electrode.

Current flows when potential, electrode area, or solution composition changes

Ideal polarized electrode no charge transferred happen and behave like capacitors.
(ideal polarization in a potential range, e.g., Hg)
Real electrode (non ideal polarized electrode) due to H2O electrolysis or impurity.

Capacitance on an electrode
q 
C
μ ‐‐‐‐
10μF ++++ 

E 
Cd qM , qd (coulomb) － charge
σM, σi, σd (coulomb/cm2) － charge density
double layer

For a common capacitor C f potential

For a double layer C f potential

σi : excess charge density in IHP

σd : excess charge density in diffusion layer
σS : excess charge in the solution
σM : excess charge on the metal surface

σ σ σ σ

6 
 
1 joule = 1N ∙ m = 107 dyne ∙cm = 107 erg
  σ Cd
dyne/cm  μC/cm2  μF/cm2

integrate differentiate

E‐Ez  E‐Ez  E‐Ez 

Figure 13.2.2  Figure 13.2.3 Figure 13.2.1 

σ 
C σ
 ∬ Cd dE [dyne/cm=10-7 Joul/cm2]

Very low concentration of electroactive species significant nonfaradaic current

Cd              Rs            CSCE  Cd              Rs             

≈
(generally CSCE >> Cd)

‐‐‐‐ I
++++ 

0        τ                t 
1. When the circuit is open, the electrodes are not charged.
2. Whenever the circuit is closed, a constant potential (E) is applied, and the
electrodes are charged because electrons move to negative electrode and away
from positive electrode. During this process, we can measure a current, called
charging current or non-faradaic current as I = dq/dt. This current approaches
zero when the charges on the electrode reach saturation, namely the equilibrium
state. The charge (q) accumulating on the electrode follows the equation: Cd =
q/E. Before saturation, charge (q) and current (I) are functions of time (t).

7 
 
 Rs  Cd 
Considering Cd ≠ f(E) and Cd
Under the condition: I = 0 at t < 0
(a) Potential step (across the circuit)
E E E
q dq q
E IRs Rs E  I
C dt C

Initial condition (at t = 0): and the current is restricted to the resistant Rs.
Final condition (at t=∞): the charge reaches saturation and potential across the
capacitor is E

Solve for q E．Cd 1 exp

/
I e t =τ, I = 0.368 E/Rs
t =3τ, I = 0.050 E/Rs
For Rs =1 ohm and Cd = 20μF  τ= 20 μsec or 3τ= 60 μsec.

I
E E/Rs

0.368E/Rs
IFaradaic 
t 
0        τ                t 

(b) Current step (through the circuit)

E E E
E IRs IRs
t
E I Rs
C

I E
I
slope  
C
0                          t 
0                    t 

8 
 
(c) Potential sweep (across the circuit)
E Ei νt
E Ei νt Rs
Solve for q = f(t), then
I νCd νCd exp

At t=τ, I νCd 0.368 νCd

At t=∞, I νCd or I C ν
E I constant potential 
Ei/Rs  sweeping potential 
Ei
0.3678 νCd  
Rs
Ei 
νCd 
0                  t  0    t=τ                  t 
What will happen if EI = 0?

small RsCd 由 I =νCd at t =∞ 得  Cd  Cd

const. EI/Rs at t = 0
variable E

E 
Triangular wave

E  I
E   Ei larger  νCd 
Rs smaller  νCd 
slope  ν  ν
Ei 
νCd 
0            λ                t  0                λ                2λ          t 
νCd 
I
Ei larger  νCd 
Rs smaller  νCd 

νCd 
0                    Eλ                E 
νCd 
9 
 
§ 1.3 Faradaic current

1. constant variables: concentration, temperature

Experimental variables 2. controlled (or excited) variables: i or E
3. response variables: E or i

for thermodynamics
kinetics data
analytical

Ideal polarized electrode (e.g., Hg): Charge accumulation forming double layer.
Ideal non-polarizable electrode (e.g., Pt): 1. Always keeping at a specific potential.
2. also called depolarized electrode
3. no charge accumu. before electro. rxn
4. No double layer significantly.

Polarization curves I 

E 

overpotential η E E
Fig. 1.3.6 Combination of the steps in an electrochemical process
[ηΩ －ohmic overpotential = iRs, not considered as an overpotential in the textbook]

η －mass transfer overpotential, due to concentration polarization.

η －charge transfer overpotential, due to activation polarization.

η －overpotential associated with a proceeding reaction, due to reaction

polarization
η R η R η R

The overpotentials are located in series in an electrochemical system.

10 
 
 The cell potential is determined by Ecell = Eleft – Eright.

－    Power    ＋  1. OCP: 0.64V SCE

2. E . 0.6V SCE net current
2+ －
A Cd + 2Hg + 2Cl Cd + Hg2Cl2
3. E . 0.64V SCE no current
2+ －
Cd + 2Hg + 2Cl Cd + Hg2Cl2
Appl. E 
4. E . 0.74V SCE net current
2+ －
Cd + 2Hg + 2Cl Cd + Hg2Cl2
－  + 
Cu/Cd/Cd(NO3)2(1M)//KCl(sat)/HgCl2/Hg/Cu－

Cd2+ + 2e Eo = -0.40 V (NHE)

－
Cd
Eo = 0.24 V (NHE)
－ －
Hg2Cl2 + 2e 2Hg + 2Cl

Cd2+ + 2Hg + 2Cl Cd + Hg2Cl2 ΔEo = -0.64V (NHE)

－

Anodic reaction:  η＋, i－ 
E . E iRs E η iRs Cathodic reaction:η－, i＋ 

With two ideal nonpolarizable electrode, η 0 E . E iRs

i 
slope: Rs 

.
.

Working electrode is usually measured with respective to an ideal-nonpolarizable

electrode whose potential are not affected by current.

Counter electrode (or auxiliary electrode) is an

two-electrode cell: ideal-nonpolarized electrode (e.g. reference electrode),
e.g., potentiometric sensor whose iRs small (<1~2mV)

No product from counter electrode affects working

three-electrode cell:
e.g., amprometric sensor
for high iRs
electrode.
Negligible current through reference electrode (with a
high impedance in the instrument).
11 
Fig. 1.3.12 position of reference electrode

ρx
R  
d  A
electrode area 
x>2d 

ρ x
R  
4πr x r
                                    x → ∞ Ru    
                                    x → r Ru    

2ro 

High electrolyte resistance Low electrolyte resistance

Ref. electrode  Ref. electrode 
ϕ ϕ
iRu  iRu

ϕ ϕ

Ru  Ru

∂ϕ
i k  
∂r
∂ϕ
I Ai Ak const. 
∂r
∂ϕ
k4πr const. 
∂r

12 
 
§ 1.4 Mass-transfer-controlled reaction

(ηct ≈ 0  fast charge transfer, surface concentration available for Nernst equ.)
(ηrxn ≈ 0  homogeneous reactions is at equilibrium)
O ne → R 
RT O
Nernst Equation: E E ln
nF R

Thermodynamic Always for reversible i

mass-transfer reaction υ υ
relationship Nernstian nFA
controlled

Mass transfer of ions:

1. Migration－due to electrical potential gradient,

2. Diffusion－due to chemical potential gradient or concentration gradient,

density gradient (natural convection)

3. Convection－due to
pressure gradient (force convection)

Flux of ion i:
∂C ZF ∂ϕ
J x D DC Cν x
∂x RT ∂x

§ 1.4.2 Semiempirical Treatment of Steady-state Mass Trsnsfer

(With an excess of supporting electrolyte, migration is not important.)
O ne ⇆ R  x 
RT O activity 
E E ln   Co* 
nF R
RT C concentration  Co(x=0)
E E ln
nF C

At equilibrium, 
Co = Co* and CR = CR* Diffusion 
layer
RT C ∗   RT O ∗
E E ln   E ln  
nF C ∗ nF R ∗

13 
 
At steady state (i.e. constant current)

RT C
E E ln   (C x 0 and C x 0 :  functions of applied E) 
nF C

bulk solution 
surface concentration (mole/cm3) 
for O : m C∗ C

mass transfer coefficient (cm/sec)

for R : m C C∗

Limiting current il = nFAmoCo* where Co(x=0) =0

Co(x=0) 
C∗
ℓ
C x 0   or  ∗ 1  
ℓ

iℓ   i

(a) C ∗ 0 (no R presents) O ne ⇆ R 

i
m C
nFA
RT m RT iℓ
E E ln ln 1  
nF m nF i
iℓ
ln 1
i
E /  
(+) 
i  slope=  

由  ℓ
f E   求 n  iℓ

2 iℓ   E /   E(－)
cathodic  iℓ
i
2
iℓ
E /   E (－) log 1
anodic  i

slope=  
.

E   E(－)
/
iℓ
14  i
2
 
(b) C ∗ 0, C ∗ 0 (O, R present initially)

exp. 1: C 0 ⇒ iℓ, nFAm C∗ for O ne ⟶ R 

exp. 2: C 0 ⇒ iℓ, nFAm C∗ for R ⟶ O ne  

iℓ, i iℓ, iℓ,

i ⇔E E
RT m RT iℓ, i log
i iℓ, 2 /
E E ln ln  
nF m nF i iℓ,
slope=  
.
E /  

i  E   E (－)
/

iℓ,
iℓ  
E /  

iℓ, iℓ, E (－)

RT iℓ,
2 E   E E ln  
/
nF iℓ,
iℓ,
∗
       E / ln ∗  
∗
(C) R insoluble, 1        E ＋ ln ∗  
RT RT i
E E lnC∗ ln 1  
nF nF iℓ e 1 x ⋯   
 
E   η or η ≈ 1 + x (if x is small) 

i
small η . iℓ  
η . 

RT
η . i
nFiℓ
or
RT E (－) 
R E E lnC ∗
| ℓ| nF

What will the equation become if cathodic current is assigned negative?

15 
 
§ 1.4.3 Semiempirical Treatment of the Transient Response (non-steady state)
O ne ⇄ R 
In the steady state system, the diffusion layer thickness, and then the current, is
constant for a constant electrode potential. Before the steady state, the diffusion
layer thickness (t) increases with time. So, current i(t) changes with time during
this transition time. δ δ δ δ  
C∗  
C∗ C  
  t 
Resistance due to 
δ t 2 D t  C
double layer effect 
/ and instrument 
/
C∗ C i resistant in 20 sec 
similar to Cottrell Eq. 

with convection 
D ⇒x 2 D t i  t=0 
t ∞
D : 10 cm ⁄sec
0                        t 

/
t

16 
 
§ 1.5 Semiempirical Treatment of Nernstian Rxns with Coupled Chem. Rxn
For thermodynamic data of CE system
A ⇄ O qY  C ⋅C
K  
O ne ⇄ R  C

(a) Fast coupled chemical reaction (i.e. reversible reaction)

(Always in thermodynamic equilibrium)

C   If
C   A  C∗   in excess of C ∗
complex 
C     C∗   small C ∗
ion 
O      no C ∗
     
R  R  C∗  
Diffusion   
layer 
initially  C 0 
C C ∗   ∵ C ∗ ≫ C ∗   Y is not a reactant 
K<<1  ∵ complex ion  
RT RT m RT RT iℓ i
E E lnK ln qlnC ∗ ln  
nF nF m nF nF i
E /  

E /   shift
different  C ∗  
i  RT lnC ∗  
lnK
nF
slope= q 
E /   shift 

E(－) 
E /   shift lnK qlnC ∗  

17 
 
(b) Slow coupled chemical reaction
for kinetic data of EC system
O  O  O ne ⇆ R 
  k 
 
R T First order reaction (irreversible)
 
 
R  Initially C 0
 
    μ: reaction layer－thickness for R T
T 
 
μ  RT m RT iℓ
E E ln ln 1  
nF m nF i

E ln ∙ 1

E /

RT
E / E / ln 1  
nF m
RT i μk 0  μk 0 
E / shift ln 1  
nF m
ω 
Rotating disk electrode (RDE)
/ / /
m 0.62D ω υ E E   E(－)
/ /

For RDE and μk ≫ m   (R reacts to T completely) 

RT
E / shift ln  
nF m

RT RT
E / shift ln lnω 
nF 0.62D2/3
R υ
1/6 2nF
E / shift 

i  RT
smaller ω  larger ω  ln /
 
nF 0.62D υ /

RT
slope  
2nF

lnω 
E / E / E /   E(－) 
18 
 
Chapter 2 Potentials and Thermodynamics of Cells

§ 2.1 Basic Electrochemical Thermodynamics

Key: Thermodynamics discuss the relationship between potential and concentration

(or activity) at equilibrium. The reaction rate (or current) to reach a new
equilibrium not concerned in thermodynamics.

Reversibility: an aspect, not well-defined.

1. Chemical reversibility: Reversing the cell current merely reverses the cell reaction.
(yes) Pt/H2/H+, Cl-/AgCl/Ag 2Ag + 2H+ + 2Cl- ⇌ H2 + 2AgCl
(no) Zn/H+, SO42-/Pt Zn + 2H+  H2 + Zn2+
2H2O  2H2 + O2
2. Thermodynamic Reversibility
An infinitesimal reversal in a driving force (i.e. potential) causes the process to
reverse its direction--around the equilibrium
① Only small change in E is required to change reaction direction.
② Eeq is constant and independent of direction of transformation.

3. Practical Reversibility
Electrochemical system is always under current flow.
It depends on the expectations and detection ability of an observer:
1. measurement time,
2. driving force (which determines the response time),
3. the time to reach equilibrium (or transition time),
4. accuracy.

Nernst equation reversible electrode reaction

Zn/Zn2+(a=1), Cl-(a=1)/AgCl/Ag
Definition for cell potential:
Left half cell Anode: Zn  Zn2+ + 2e-
- Zn + 2AgCl  →  2Ag + Zn + 2Cl  
2+ ‐
-
Right half cell Cathode: AgCl + e  Ag + Cl
Cell reaction emf (electromotive force):
Erxn= Eright electrode - Eleft eletrode = +0.985 V (difference of the two equilibrium potential)

The “emf” means the driving force for the reaction.

The values in the emf table are given based on the normal hydrogen electrode
(NHE) as the “left electrode”.
19 
 
Free Energy: Thermodynamics data from 
electrochemical experiments? 
∆G nFE  ∆G nFE  
At unit activity ∆G nFE  
∆ ∂E
∆S  ∆S nF  
∂T
∆H ∆G T∆S ∂E
 ∆H nF T E  
∂T
∆G ∆G RTlnΠ
 
At equilibrium ∆G 0 ⇒ RTlnK ∆G  RTlnK nFE  
or E lnK  
Half cell reaction:

1. Absolute phase potential: work to bring a unit positive charge from the point at
infinity to the interior of the phase. difficult to measure

2. Difference of absolute phase potential: Practical to use

+
Standard hydrogen electrode: Pt/H2(a=1)/H (a=1) potential is 0 at all temperature

The emfs are calculated from electrostatic and thermodynamic information.

equilibrium constant
G Table of complexation constant
E Emf
(Appendix C)
solubility product
electrochemical information (to evaluate a spontaneous process)
Nernst Equation:
Pt / H2 / H+ // R / O
H  O⇄ R nH free energy

∆G ∆G RTlnΠ
∆G ∆G RTln G
∆G nFE , G nFE
RT R H
E E ln
nF O H
+
(H2) = (H ) = 1
RT R
E E ln
nF O
Erxn is replaced by E in the following sections.
20 
 
Formal Potential :
E E ln
RT O
E E ln
nF R
RT γ
E E ln
nF γ
E is affected by ionic strength. Table C.2 on p. 810

The reasons to use formal potential Eo instead of standard equilibrium potentials Eo’:
(a) Activities are difficult to determine.
(b) Eo , i.e. E , is difficult to measure.
(c) Other species, e.g. ligands, might present.

Reference Electrode (Figure E. 1):

See “Reference Electrodes” by D.J.G. Ives & G.J. Janz, Academic Press, (1961).

1. Ag/AgCl/KCl(sat.): smaller temperature coefficient and more compact than SCE.

2. Hg/Hg2SO4/K2SO4(sat.): no Cl- involved.
Hg/HgO/NaOH: for alkaline solution, and no Cl- involved.
3. Ag/Ag+ (0.01M in CH3CN): for non-aqueous solution.

, ,
potential ϕ x, y, z ∙ whereξis electric field.
1. work required to bring a unit positive charge (without phase interactions) from an
infinite distance to point (x,y,z)
2. no current in conducting phase  no potential difference in the interior of the
phase

Mobility: (supplementary handout)

electric force = friction drag Friction drag follows stokes law.

|Z |eξ 6πηrv whereξ: electric field, η: viscosity, vi = velocity, r = ion radius
| |
mobility u table 2.3.2

21 
 
relative mobility i = Fui (i is a function of concentration of ion i)
K F ∑|Z | u C
| |
transport no. transference t ∑

transport no. of speices i (ti): the ratio of current by species i over the total current.
for binary system t table 2.3.1

Liquid Junction: the junction between two different phases (supplementary handout)

Junction device: the permeable devices which separate two different phases.
Junction potential: the potential difference between two different phases.

Two binary electrolyte can be: RT

1. different concentrations of the same type of electrolyte, E t t
F
ln
2. different types of electrolytes

To minimize junction potential:

1. using salt bridge containing ions of nearly equal mobility, Table 2.3.3.
2. using ion selective electrode for reference electrode.

Reference electrodes: p. 811 Table C.3 and supplementary handout

① NHE
2H+ + 2e- ⇌ H2 E 0.059 log 0.059pH
② Ag/AgCl
smaller temperature coefficient than SCE
- -
e + AgCl ⇌ Ag + Cl E / 0.2224 0.0591log

③ Calomel
Hg2Cl2 + 2e- ⇌ 2Hg + 2Cl- E 0.2677 0.0591log
④ Hg/HgSO4
.
Hg2Cl2 + 2e- ⇌ 2Hg + 2SO4-2 E 0.615 log
⑤ Hg/HgO/Ba(OH)2(sat) E 0.1462V NHE 25 C
Hg/HgO/Ca(OH)2(sat) E 0.1923V NHE 25 C
Hg/HgO/NaOH(0.1M) E 0.926V NHE 25 C
⑥ Ag/Ag + (0.01M in CH3CN) for organic electrolytes

22 
 
Ion-Selective Electrodes:

Glass electrodes: measurement of activities of proton (pH meter) and alkaline ions.

Hg/Hg2Cl2/KCl(sat)/test soln./glass membrane/HCl(0.1M)/AgCl/Ag

SCE Glass electrode

small Ej 
SCE Ag

AgCl 

thin glass membrane (50m) 
0.1M HCl 
Test soln.

RT .
E C
ZF
Constant C is determined with a standard solution and its measured potential.

Hydrated zone  Hydrated zone 

m’  Dry glass  m’’ 

  H+  + + +
H  K  or Na
+  not H   β 
α  Na+    diffusion 
Na+    filling soln. 
test soln.  potential   
50m
membrane
potentiometric selectivity coefficient

E const. ln k ,
．

potentiometric selectivity coefficient: , k ,

 
:
For pH meter, k ,
⋅ ≪  . ln

ion-selective glass: different compositions of glass ⟹ different k values.

 different selectivities on H+, Na+, K+, Rb+, Cs+, Li+, Ca+2, NH4+.

23 
 
Chapter 3 Kinetics of Electrode Reactions (considering fast diffusion)
In chapters 1&2, the electrode potential is an
Elementary reaction kf  equilibrium potential based on Ci(x=0) because the
A  B reaction is so fast that the system reaches
kb 
equilibrium as soon as the condition is changes.
At equilibrium, υ 0 The reaction rate is determined by diffusion. Ci(x=0)
υ C   is not necessary the same with Ci*. Nernst
C equation is applicable between E and Ci(x=0).
K  
C In chapter 3, the reaction is not fast and diffusion is
very fast. The electrode potential is not an
equilibrium potential based on Ci(x=0). Nernst
Arrhenius equation for rate constant equation is not applicable between E and Ci(x=0). 

Empirical expression: Ae
probability of reactant with energy overcome energy
barrier, i.e. activation energy
frequency factor

internal energy = enthalpy - flow work Activated complex 

∆E ∆H ∆ PV ∆H potential 
H = G + TS ≈ G energy  E
E

∆ ‡ ∆ ‡ ∆ ‡
Ae A′e
∆ ‡
A′e ∆G ‡ : standard free energy

standard 
‡
∆E ‡ ∆H‡ ∆ PV  
free  ∆G  
∆G‡   ‡ T∆S ‡
∆H ∆ PV T∆S ‡  
energy 
∆G ‡ ∆ PV T∆S ‡  
∆G  

Boltzmamn constant 1.3806×10-23k-1

determines the shape of energy surface

∆ ‡
κ e
Planck constant 6.62 10 erg ⋅ sec
transmission coeff. 0~1

24 
 
§ 3.2 Essentials of Electrode Reaction
In the case of low current and efficient stirring
i by Tafel (1905)
log Tafel equation

§ 3.3 Butter-Volmer Model of Electrode kinetics

 
O e  ⇆ R one-step reaction on electrode
 
reaction rate , － ,  
∗
at equilibrium E E ln ∗

Figs. 3.3.1&3.3.2 potential the energy level of electrons on electrode

EO’ 
E
∆G‡   1 α F E E
 
F E E
∆G‡  
∆G‡   ∆G‡   ‡ ‡ ′
∆ ∆ 1 α F E E  

‡ ‡
∆ ∆ αF E E
′
 
‡ ‡
∆ ∆
exp exp  
‡ ‡
∆ ∆
exp exp

at E E ∆
‡
∆
‡
o
∗ ⟹ ⟹ exp exp
且 ∗  

| |⋅| | FA , ,
FA o , ,  
E 
E  
transfer coefficient α
θ ϕ 
 
θ ϕ ⟹ α 0.5
0 < α < 1.0 Fig 3.3.4
25 
 
§ 3.4 Implications of the Butler-Volmer Model for the One-step process
§3.4.1 Equilibrium condition

At equilibrium, E = Eeq, CO(0,t) = CO* , CR(0,t) = CR*, and equation  = 0

o o
FA , FA ,
∗
,
∗  
,
∗
E E ln ∗

o o ∗ ∗
exchange current FA , FA  
∗ ∗
C  FA C

§ 3.4.2 Current-overpotential Equation

At any state and set f = F/RT

equation  , ,
 
equation  ∗ ∗ ∗ ∗

C∗ C , C , C∗
e e
C∗ C∗ C∗ C∗
Combined with equation 
C , C ,
e ∗ e
C∗ C
, ,
∗ ∗ where η = E - Eeq

§ 3.4.3 Approximation form (quasi-reversible process)

, ,
∗ ∗

i = cathodic current – anodic current Conditions for fast mass transport:

1. kinetic-controlled system
, ,
In the case of fast mass transfer, 2. well stirred 0.9 ∗ , ∗ 1.1
C , C∗ and C , C∗ 3. small i, i < 10% of ilim 

] Butler-Volmer equation
small io ⟹ small ⟹ give high overpotential
large io ⟹ large ⟹ give low overpotential
26 
 
(a) Small η, |η| 20
fη
R charge transfer resistance
large ⟹ small R

(b) Tafel region, |η| 100

Cathodic reaction (i > 0), η < -100 mV η ln ln

or ln ln η

Anodic reaction (i < 0), η > 100 mV η ln ln

or ln ln η
Tafel equation: η = a + b lni usually for galvanic processes
lni = a + bη usually for electrolytic processes
Tafel plot: the plot of the logarithm of current vs. overpotential (or potential)
Tafel slope: the slope from Tafel plot, galvanic process or ⟹α
electrolytic process or ⟹α
intercept: io can be obtained from the intercept of the and i-axis.

(c) Mixed region, without approximation

1
log log Good for linear region, Tafel region and the
. region between these two regions.

27 
 
§ 3.4.4 Exchange current Plots
∗ ∗
∗ ∗
FA FA C
log log FA 1 log ∗ log ∗
Obtain α from the slope of curve of log io vs. CO* or log io vs. CR*.

§ 3.4.5 Very Facile Kinetics and Reversible Behavior

For Facile kinetics (which means reversible system)

① large ⟹ →0⟹η→0
i may not be very small but still small compared with
,
E E ln (No kinetic term presents. See § 1.4.2)
,

② practically
C∗ C , and C ∗ C ,  mass transport  current

At equilibrium
∗ ∗
, RT
E E ln ∗
∗
,
nF

§ 3.4.5 Effect of Mass Transfer (see fig. 3.56 and handout)

, ,
∗ ∗

ℓ, 0 
1 1 0 
ℓ, ℓ, ℓ,

| |≪1
η R R , R ,
ℓ, ℓ,
≪ ℓ R ≫R , R , activation controlled
≫ ℓ R ≪R , R , concentration controlled

≪ 1 1
ℓ,
RT RT ,
ln ln
αF , αF

28 
 
§ 3.5 Multistep Mechanisms
§ 3.3 & 3.4 discuss single-step and single-electron reactions. The elementary
reaction is single-electron reaction. The rate determining step in most
electrochemical reaction is a single-electron reaction.

O ne ⇆ R O n′ e ⇆ O′
O e ⇆ R
R n e ⇆ R

nFA C , C , eq. B
∆G nE F
∆G E F
∆G n E F
∆G nE F nE F E F n E F

where E
nE E n E
E
n
At equilibrium
∗

∗
⟹ ∗
∗ ∗
∗ ⟹e ∗ ⟹E E ln ∗

At any potential E
,

, ,
E E ln
, ,
,
,

nFA C , nFA C ,  

nFA k C , k C ,

29 
 
(a)
O Y ⇆ O K From eq. B
O e ⇆R , , , calculated from
equilibrium constant K K
R ⇆ R Z K

(b) From eq. B

O e ⟶R , , ,
R n e ⟶ R (totally irreversible)
nFA ,
O ne ⇆ R n 1 n

(c) Chemically Reversible Process Near Equilibrium

, ,
∗ ∗ ln  

∗ ∗ slope 1
nFA  

= lnC ∗

ln  
For small current or efficient mass transfer,

] slope  

]
lnC ∗
small | | ⟹ , R

large | | cathodic    ln ln  
anodic        ln| | ln 1  

lini 
Fe ⟶ Fe 2e  
H ⟶ 2H 2e  
2H 2e ⟶ H   Fe 2e ⟶ Fe

0                                ‐0.44                    E () 

Eeq                    Emix            Eeq 

30 
 
Chapter 4 Mass Transfer by Migration and Diffusion

Flux of species j J D C DC ϕ CV
Flux of species j in one-dimension system
J D DC CV x where

In an unstirred or stagnant solution, without density gradient ⟹ V 0

no convection
J D C DC ϕ

diffusion migration
Current carried by species j in one-dimensional system
Z FAJ Z FAD A DC Z FD
 
RT

, , C |Z |FA
Total current i =  j ij

§ 4.2 Migration
In the bulk solution ∑ |Z | C FA
A 1 Δx
Δ R
Δ A
| | | |
t ∑ | ∑ |
| |
transference number

§ 4.3 Mixed Migration and Diffusion

Figure 4.3.1
charge transferred and measured
at the surface for electroactive species may be in opposite directions
| | , , ,

in the bulk in diffusion layer

31 
 
only one electroactive species on a working electrode
∑ ,

on the surface in the bulk solution

no. of electroactive species due to migration onto the electrode

+: for reduction, : for oxidation
n: no. of electron for each reacting species, Zj: charge of electroactive species j

1∓

Fig. 4.2.4
The effect of supporting electrolyte:
1. decreasing cell resistance,
2. simplifying the mathematical treatment to diffusion controlled,
3. decreasing the importance of migration of electroactive species,
4. helping electroactive species reach electrode by diffusion.

§ 4.4 Diffusion
O ne ⇌ R
∂Co x,t
Fick's 1st law J , Do ∂x
flux: [mole/cm2/sec]
,
Fick's 2nd law D C
Mathematic model can be established by solving Fick's law (differential equation)
with initial condition/boundary conditions
C x, t
Then the current i can be expressed by taking the derivation on x at x=0 (on the
electrode surface),
∂C ,
J , D |
nFA ∂x
For q electroactive species, the total current will be:
∂C ,
n D |
FA ∂x

32 
 
To solve the differential equation, we may use following condition
Initial condition:
C , C∗ for all x C∗  
C , 0

Semi-infinite B. C.:
lim → C , C∗ for all t
lim C , 0 C∗  
→
t 
Electrode surface B.C.:
1. For a fast kinetic, Nernst equation can be applied and electrode potential can be
either constant or any function of time. – controlled potential technique.
,
f E
,
2. A i-t relationship also can be used as a boundary condition. – controlled current
technique.
,
D | t

Material balance:
J , J ,

For steady state:

,
1. Diffusion controlled process: D C 0  C =0
2. Ohmic controlled process: j k ϕ⟹ ϕ=0

The results are similar to the differential equation for heat transfer T 0.

33