Chapter 1

Introduction and Overview of

Electrode Process
Speaker: Ta-Jen Li ( )
Electro-Optical Materials Laboratory
Department of Chemical Engineering
National Taiwan University
2011 / 07 / 11

Outline
1.1 Introduction to electrochemical cells and reactions
1.2 Nonfaradaic processes and the nature of the electrodesolution interface
1.3 Faradaic processes and factors affecting rates of electrode
reactions
1.4 Introduction to mass-transfer controlled reactions
2

Introduction
Electrochemistry is the branch of chemistry concerned with the interrelation of
electrical and chemical effects.
The field of electrochemistry encompasses a huge array of different phenomena
(e.g., electrophoresis and corrosion), devices (electrochromic displays, electro
analytical sensors, batteries, and fuel cells), and technologies (the electroplating
of metals and the large-scale production of aluminum and chlorine).
The main emphasis in this text book is on the application of electrochemical
methods to the study of chemical systems.
In chapter 1, the terms and concepts employed in describing electrode reactions
are introduced. In addition, the approximate treatments of several different
types
of electrode reactions to illustrate their main features.

Basic conceptions of
electrochemical cells
Typical electrode materials include solid metals (Pt, Au), liquid metals (Hg),
carbon (graphite), and semiconductors (indium-tin oxide ITO).
In the electrolyte phase, charge is carried by the movement of ions.
The most frequently used electrolytes are liquid solutions containing ionic
species, such as, H+, Na+, Cl-, in either water or a non-aqueous solvent.
It is natural to think about events at a single interface, but we will find that
one
cant deal experimentally with such an isolated boundary. Instead, one must
study the properties of collections of interfaces called electrochemical cells.
(Single interfacial potential difference can not be measured)
A difference in electric potential can be measured between the electrodes in an
electrochemical cell. This is done with a high impedance voltmeter typically.
4

Typical electrochemical cells and

their notations
Pt H2
Zn

Ag

Ag

Reference electrodes
Standard Hydrogen Electrode (SHE), or Normal Hydrogen
Electrode (NHE)

E0 = 0 V
ASSUMED
Saturated Calomel Electrode (SCE)

E0 = 0.241 V
Silver-silver Chloride Electrode

E0 = 0.197 V
6

Oxidation and reduction processes

Electrode

Electrode

Solution

Vacant
MO

Potential

Solution

Energy level
of electrons

Occupied
MO

Representation of reduction process of a species in a solution

Electrode Solution

Potential

Energy level
of electrons

Electrode

Solution

Vacant
MO
e
Occupied
MO

Representation of oxidation process of a species in a solution

Potential difference across

electrode/solution interphase
Let us assume
Cu Cu2+ + 2eoccurs first

(vf)e = (vb)e
Equilibrium
state

At equilibrium across
electrode/solution interphase

Galvani potential difference across M/S

M

e e e
S

S
8

Measurement and calculation of the

open-circuit potential
A high impedance voltmeter (i.e., a voltmeter whose internal resistance is so
high that no appreciable current flows through it during a measurement) is
placed across the cell. This is called the open-circuit potential of the cell.
It is possible to calculate the open-circuit potential from thermodynamic data,
that is, from the standard potentials of the half-reactions involved at both
electrodes via the Nernst equation (chapter 2).
The key point is that a true equilibrium is established, because a pair of redox
forms linked by a given half-reaction (i.e., a redox couple) is present at each
electrode. (Cu/Cu2+; Zn/Zn2+; H2/H+)
We cant calculate a thermodynamic potential for the Pt/H+,Br- electrode,
because we cant identify a redox couple. (no H2 is introduced; deaerated)
9

Obtaining a current-potential curve (1)

Power
supply

Current

Cathodic

1.5
1.5

Ag
Pt

AgBr

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

Onset of H+
reduction on Pt
0.5

-0.5

Onset of Broxidation on Pt

Cell potential

Anodic

: (1) (2)
10

Obtaining a current-potential curve (2)

Potential of the Pt electrode is made more negative with respect to the Ag/AgBr
reference electrode.
Pt electrode: proton reduction; a cathodic current flows (working)
Ag/AgBr electrode: the oxidation of Ag in the presence of Br - form AgBr (reference)

Potential of the Pt electrode is made sufficiently positive with respect to the Ag/
AgBr reference electrode.
Pt electrode: Br- oxidation; anodic current flows (working)

Ag/AgBr electrode: the reduction of AgBr to form Ag and Br- (reference)

The background limits are the potentials where the cathodic and anodic currents
start to flow at a working electrode.
The open-circuit potential is not well defined in the system under discussion.
The open-circuit potential lies somewhere between the background limits.

11

Potentials for possible reductions at a

platinum and gold electrodes

least positive (or most negative E0)

be oxidized first, reductant

least negative (or most positive E0)

be reduced first, oxidant

12

Faradaic and Nonfaradaic process

Faradaic process
Charge transfer across the metal-solution interface
Oxidation or reduction occurs
Governed by Faradays law

Nonfaradaic process
No charge transfer across the metal-solution interface
Adsorption and desorption

13

Self readings and reviews of 1-1

Self readings
Discussion on the i-E curves of Hg/H+, Br- (1 M/AgBr/Ag) (pages 7-9)

Reviews
Electrode materials, electrolytes, notation of electrochemical cells
Standard electrode potentials (reduction scale), reference electrodes
tendency of oxidation and reduction
Formation of potential, measurement of open-circuit potential

14

Ideal polarized electrode (IPE)

An electrode at which no charge transfer can occur across the metal-solution
interface, regardless of the potential imposed by an outside source of voltage,
is called an ideal polarizable electrode (IPE).
While no real electrode can behave as an IPE over the whole potential range
available in a solution, some electrode-solution systems can approach ideal
polarizability over limited potential ranges.
Mercury electrode in contact with a deaerated potassium chloride solution approaches
the behavior of an IPE over a potential range about 2 V wide.

15

Brief description of the

electrical double layer
Inner Helmholtz plane (IHP)
locus of the electrical centers of the specifically
adsorbed ions
Outer Helmholtz plane (OHP)
locus of centers of the nonspecifically adsorbed
solvated ions
Diffuse layer
extends from the OHP into the bulk solution

16

A two-electrode cell and its approximated

linear circuit
Hg/K+, Cl-/SCE

Representation of the cell in terms of

linear circuit elements

Cd CSCE
CT
[Cd CSCE ]
series capacitance of Cd and CSCE

CSCE Cd

CT Cd
17

Potential step method for obtaining

the capacitance
E E R Ec iRs
Rs

Cd

dq
q
E

dt R s Cd Rs

q ECd [1 e

Applied (E)

E t / RsCd
e
] i
Rs

E/Rs
i

t / Rs C d

q
Cd

=time constant

0.37E/Rs
t

=RsCd

t 18

Current step method for obtaining

the capacitance
Rs

i
E iRs
Cd

Cd

dt
0

E i ( Rs t / Cd )
Constant current source
Applied
(i)
E

Slope= i/Cd

iRs
t

t 19

Self readings and reviews of 1-2

Self readings
Current step method for obtaining the capacitance (pages 16-18)

Reviews
Nonfaradaic process
Ideal polarizable electrode (large horizontal region, Hg electrode)
Structure of electrochemical double layer (EDL)
Methods for obtaining the capacitance

20

Galvanic and electrolytic cells

Galvanic cell

Electrolytic cell

reaction occurs spontaneously

imposition of an external voltage greater than

converting chemical energy to electrical

energy

the open-circuit potential of the cell

converting electrical energy to chemical energy

primary cells, secondary cells, fuel cells electrolytic synthesis, electroplating

21

Applying different voltage to a Galvanic cell

and the corresponding chemical reactions
Cd Cd 2 2e

Hg 2Cl2 2e 2 Hg 2Cl

Cd 2 2e Cd

Hg 2Cl2 2e 2 Hg 2Cl

When the voltage applied by the external power supply, E appl, is 0.64 V, i= 0.
When Eappl is made larger (i.e., Eappl>0.64 V, such that the cadmium electrode
is made even more negative with respect to the SCE, the cell behaves as an
electrolytic cell.

22

Relationship between the current and

the reaction rate

An electrode process is a heterogeneous reaction occurring only at the electrode-

electrolyte interface.
Since electrode reactions are heterogeneous, their reaction rates are described in
units of mol/s per unit area. (j is the current density)
23

Ideal polarizable electrode and ideal

nonpolarizable electrode
i

An ideal polarized electrode shows a very

large
change in potential upon the passage of a small
current.
Ideal polarizability is characterized by a

Ideal nonpolarizable electrode is an

electrode whose potential does not
change upon passage of current.
Nonpolarizability is characterized by
a vertical region on an i-E curve.

24

Pathway of a general electrode reaction

When a steady-state current is obtained, the rates of all reaction steps in a series are the
same.
The magnitude of this current is often limited by the inherent sluggishness of one or more

25

Processes in an electrode reaction

represented as resistances

Each value of current density, j , is driven by a certain overpotential, which can

be viewed as a sum of terms associated with the different reaction steps: mt, ct,
rxn, etc.
The electrode reaction can then be represented by a resistance, R, composed of a
series of resistances representing the various steps: Rm, Rct, etc.

26

Applying different voltage to a Galvanic cell

and the corresponding chemical reactions
Cd Cd 2 2e

Hg 2Cl2 2e 2 Hg 2Cl

Cd 2 2e Cd

Hg 2Cl2 2e 2 Hg 2Cl

When the voltage applied by the external power supply, E appl, is 0.64 V, i= 0.
When Eappl is made larger (i.e., Eappl>0.64 V, such that the cadmium electrode
is made even more negative with respect to the SCE, the cell behaves as an
electrolytic cell.

27

Distribution of the applied voltage

The extra applied voltage -0.80 V is distributed in two parts.
The potential of the Cd electrode, Ecd, must shift to a new value, e.g. -0.70 V vs. SCE.
The remainder of the applied voltage, -0.10 V, represents the ohmic drop required to drive
the ionic flow in the solution.
SCE is nonpolarizable at the extant current level and does not change its potential.

The ohmic potential drop in the solution should not be regarded as a form of
overpotential, because it is characteristic of the bulk solution and not of the
electrode reaction.

28

Two-electrode and three-electrode cells

Power
supply

Power
supply

i
Working
electrode

Eappl

Reference
electrode

Working
electrode

Counter
electrode
Reference
electrode

If the passage of current does not affect the Current is passed between the WE and CE.
Potential of the WE is monitored relative
potential of the RE, the E of WE is given by
to
the equation shown in last page.
a separate RE.
Under conditions when iRs is small (say less
than 1-2 mV), this two-electrode cell can be A negligible current is drawn through the
RE due to the high impedance of voltmeter.
used to determine the i-E curve.
Used in most electrochemical experiments.29

Self readings and reviews of 1-3

Self readings
Electrochemical experiments and variables affecting the rate of
electrode
reaction (pages 19-21)

Reviews
Faradaic process
Two-types of electrochemical cells
Relationship between current and reaction rate (unit mol s -1 cm-2)
i-E curves of typical ideal polarizable and non-polarizable electrodes
polarization and overpotential
Two-electrode and three-electrode systems

30

Mass transfer controlled reactions

The simplest electrode reactions are those in which the rates of all associated chemical
reactions are very rapid compared to those of the mass-transfer processes. Under these
conditions, the chemical reactions can usually be treated in a particularly simple way.
(a) the homogeneous reactions can be regarded as being at equilibrium.
(b) the surface concentrations of species involved in the Faradaic process are related to
the electrode potential by an equation of the Nernst form.

31

Mass transfer to the electrode:

The Nernst-Planck equation
Ci ( x ) zi F
( x )
J i ( x ) Di

DiCi
Ci v ( x )
x
RT
x
Term 1: Diffusion
Movement of a species under the influence of a gradient of chemical potential (i.e.,
a concentration gradient).
Term 2: Migration
Movement of a charged body under the influence of an electric field (a gradient of
electrical potential).
Term3: Convection
Nature convection: due to density gradient
Forced convection: due to pressure gradient (stirring, electrode rotating (RDE))
32

Illustration of the three types of

mass transfer

33

Semiempirical treatment of steady-state

mass transfer (1)
O ne R
Stirring is ineffective at the electrode surface (neglect convection term).
a stagnant layer of thickness o exists at the electrode surface (Nernst diffusion
layer), with stirring maintaining the concentration of at Co* beyond x = o.
An excess of supporting electrolyte (neglect migration term).
The rate of mass transfer is proportional to the concentration gradient at the
electrode surface

vmt Do ( dCo / dx ) x 0
34

Co*

1
Co

Co(x=0)

Concentration profiles (solid lines) and diffusion layer approximation (dashed lines).
x = 0 corresponds to the electrode surface and o is the diffusion layer thickness.
35

Semiempirical treatment of steady-state

mass transfer (2)
O ne R
i
Do
vmt
[CO * CO ( x 0)] mo [CO * CO ( x 0)]
nFA o
i
vmt
mR [CR ( x 0) CR *]
nFA
The largest rate of mass transfer of occurs when Co(x=0) = 0. The value of
the current under these conditions is called the limiting current.

il nFAm oCo

Co ( x 0)
i
1
*
il
Co

il i
Co ( x 0)
nFAm o
36

Case (a) R is initially absent

i
C R ( x 0)
nFAm R
RT CO ( x 0) Rapid electron
EE
ln
nF CR ( x 0) transfer kinetics
O'

E E 0'

RT mR RT il i
ln

(
)
nF mO nF
i

i=0.5il

E1

mO
RT
E
ln( )
nF
mR
O'

RT
il i
E E1
ln(
)
2
nF
i

37

Case (b) O and R initially present

ilc nFAm OCO *

ila nFAm RCR *

ilc i
CO ( x 0)
nFAm O

i ila
C R ( x 0)
nFAm R
mO
ila i
RT
RT
EE
ln(
)
ln(
)
nF
mR
nF
i ilc
O'

Eeq
38

Semiempirical treatment of
transient response (1)
The diffusion layer thickness is now a time-dependent quantity

i / nFA vmt Do [Co Co ( x 0)] / o (t )

*

The current flow causes a depletion of O

Moles of O electrocatalyzed [Co * Co( x 0)] A (t )
in diffusion layer
2

i
0 nF dt
t

[Co Co ( x 0)] Ad (t )
i
Do A *

[Co Co ( x 0)]
2
dt
nF (t )
*

d (t ) 2 Do

dt
(t )

1/ 2

(t ) 2 Dot

i
Do
*
1 / 2 [Co Co ( x 0)]
nFA 2t
39

(a)

(b)

(a) Growth of the diffusion-layer thickness with time

(b) Current-time transient for a potential step to a stationary electrode (no convection)
and to an electrode in stirred solution (with convection) where a steady-state
current is attained.
40

Comments on the results obtained by

using the Semiempirical treatment
This approximate treatment predicts a diffusion layer that grows with t l/2 and a
current that decays with t-l/2.
Without convection, the current continues to decay, but in a convective system,
it ultimately approaches the steady-state value characterized by (t)= o.
Even this simplified approach approximates reality quite closely; equation
1.4.34
differs only by a factor of 2/ 1/2 from the rigorous description of current arising
from a nernstian system during a potential step (section 5.2.1).
41

Self readings and reviews of 1-4

Self readings
i-E curve for a nernstian system where the reduced form is insoluble
(pages 19-21)

Reviews
Three types of mass transfer
Semiempirical treatment of steady-state mass transfer (3 cases)
Semiempirical treatment of transient response (vs. the results obtained
by using the methods described in chapter 5)

42

Homework
Brush upon the contents of chapter 1
Problem 1.9

43

References
A. J. Bard and L. R. Faulkner, Electrochemical methods: Fundamentals and Applications,
2nd ed., John Wiley & Sons, Inc., New York (2001).
J. Wang, Analytical Electrochemistry, 3rd ed., John Wiley & Sons, Inc., New York (2006).
K. C. Pillai, C. C. Liu, Technologies of Chemical Sensors, NTUST, Taipei, Taiwan
February 14-15 (2011).

44