Electrochemistry involves redox systems.

Therefore species amenable for analysis primarily

are red-ox systems.

Electro-Analytical Chemistry
Preliminaries

Terminology:
Red-ox reaction one species undergoes a loss
of electrons another gains electrons.
eFe(III) + V(II) Fe(II) + V(III)
oxidant reductant

Further the reaction is carried out so that oxidation and

reduction occur at different locations - electrodes - in
electrochemical set-ups.
Fe(III) + V(II) Fe(II) + V(III)
Two electrodes when coupled constitute an
electrochemical cell.
The electron movement; q = quantity of charge,
i = rate of movement of charge. The electrical
potentials of the electrodes, Eel and the potential
difference of the electrodes Ecell that are involved can
be measured.

Two types of cells are studied:

a.Galvanic (Voltaic) cell: Galvanic cell uses
spontaneous red-ox chemical reactions to produce
electrical energy; that would result in a flow of electrons.
G < 0.
b. Electrolytic cell: An electrolytic cell decomposes
chemical compounds by red-ox processes using
electrical energy - electrolysis. This is an energy
demanding process non-spontaneous. G > 0.
In any type of cell: Anode oxidation occurs
Cathode reduction occurs

Galvanic Cell

Analytical
Chemistry

Qualitative Analysis
property characteristic
to analyte

Cd + 2 AgCl(s) Cd+2 + 2Ag + 2Cl-

i rate of reaction
Ecell G of reaction

G = -nFEcell
Quantitative analysis
property related to
concentration of analyte

i, q

q = quantity of current
=it
=nF
n = #moles electrons
1 mol e- = 96485C = 1F

i
Oxidation

A
reduction

Cd + 2Ag+ Cd+2 + 2Ag

V

Half Cell Reactions:

Cd (s) + 2 AgCl (s) Cd+2 (aq) + 2Ag (s) + 2Cl- (aq)
Cd(s) Cd+2(aq) + 2e
anode; oxidation
2AgCl(s) + 2e 2Ag(s) + 2Cl-(aq) cathode; reduction
The above two equations (half reactions) involve a
physical transfer of electrons (Faradaic Process)
By convention: anode (oxidation half reaction) - left

Notation: Cd|Cd+2(aq)||Ag+1(aq)|Ag
phase boundary

i, ampere; A
R resistance,
E, volts, V
i = q/t

t, sec F = 96485 coulombs/mole

96485 C/mol

q = charge; C

1 C/sec = 1 A (quite a large charge flow rate)

Work (J) = Free energy from reaction = q E
Coulombs volts

Construction of electrodes:
The electrode is made out of species involved in
the half reaction. If a metal is not involved, Pt
provides electrical connectivity.

Convention
Negative terminal
Left Black
ANODE

Convention
Positive terminal
Right Red
CATHODE

G = -nF Ecell
i = E/R

Standard Hydrogen Electrode: SHE

Standard Hydrogen Electrode: SHE

In any cell, when electrons move (current flows) between

electrodes the potential difference drops to zero.

Ecell = Difference in electrical potentials of the two

electrodes.
Measured Ecell positive
if anode connected to
negative terminal,
Positive terminal
Red

pH meter is very close

to an ideal voltmeter.
Impedance
Draws negligible current.
Negative terminal
- reference electrode
slot.
- BNC outer connector

Negative terminal
COM - Black

Electrodes (Equilibrium) Electrode Potentials:

M(s)

M+

M+ (aq)

M(s)

M+(aq) + e

if

Metal acquires a negative

potential w.r.t. solution

Bayonet Neill Concelman connector

The equilibrium set up at the electrodes is not the

conventional chemical equilibrium, rather it is an
electrochemical equilibrium.
The potential difference developed across the
interface also controls the equilibrium position
of the half reaction.
This type of equilibrium is also referred to as
frustrated equilibrium.

M(s)
M+

Faradaic processes: an interfacial

phenomenon.

M+ (aq)

M(s)

M+(aq) + e

Depending on the position of equilibrium

the metal acquires a negative/positive
potential w.r.t. solution.
CM+ (aq) is one determinant of the
position of equilibrium.

How electrode potentials develops at an electrode:

Electrode Interface :

Ex: Cu/Cu+2(aq)
Electro-chemical potentials of the species Cu+2 ion is
not the same in the two phases, that has not attained
equilibrium. Natural tendency is to equalize the
electrochemical potentials of the two species.
In order to achieve such a state, ion concentration
must change in the two phases at the interface.
Cu(s)

Cu+2(aq) + 2e

If the electrochemical equilibrium shifts to right;

the excess e- would remain on the Cu metal making
it more negative w. r. t. solution and vice versa.

The higher the tendency for the oxidation process

to occur, the higher would be the electron density on
the metal.
For cases where the oxidation is dominant its
electrode potential is more negative.
The electrode potentials of red-ox systems are
tabulated, relative to the standard hydrogen
electrode (SHE).

An external power supply is capable of forcing an

excess or a depletion electrons from the metal of
the electrode, could lead to a non-equilibrium
condition at the interface - electrolysis.
In electrolysis, there is a net reaction forced by the
applied power source later topic.

IHL

OHL

Bulk

Equilibrium Electrode potential:

The magnitude of the electrode potential depends on
the excess charge that exists above that of the
metal alone.
If the excess of (negative charge) electrons is
present in the metal of the electrode the potential of
the electrode is negative, with the energy of the
electrons in the electrode high and vice versa.

Absolute individual electrode potentials cannot be

measured, only potential differences; i.e. only relative
values can be measured.
Electrode potentials are measured against a standard
electrode and tabulated ; electrode potential of the
standard hydrogen electrode (SHE) is defined as
0.00V at 250C.
Potentiometer

SHE|| Test electrode

Pt|H2(g) (p=1atm)|H+(aq) (a=1)

Etest or Eel

Hg(EDTA)-2(aq, 0.005M)+2eHg(l)+EDTA-4 (aq,0.015M)

Potentiometer
Ecell = ERHS ELHS
measures the potential
difference between
Ecell = Etest ELHS
two electrodes.
Ecell = Etest ESHE

= 0, definition

Potentiometer

pH2=1atm
SHE

Ecell = Etest for this set up.

Ecell = Etest = Eel
aH=1
Measured Ecell for this set up = Electrode potential
of test electrode

High Impedance Voltmeter

Standard Electrodes and Standard Electrode

Potential Eoel:
When the activity (~concentration) of all species
involved in the half reaction is unity in an electrode
standard electrode.
Potential of such electrodes are defined as its standard
electrode potential.
Potentiometer

SHE|| (Test) Standard electrode

Electrode reaction
Li+ + e Li
K+ + e K

.
.

Cs+ + e Cs

.
.

Al3+ + 3e Al

AgI + e Ag + I

2.925

Sn2+ + 2e Sn

2.923

2H+ + 2e H2

2.92

AgBr + e Ag + Br

Electrode reaction

3.045

Ba2+ + 2e Ba

E /V

E /V

0.152 2

0.136

1.67

I3 + 2e 3I

Zn2+ + 2e Zn

0.762 6

Fe3+ + e Fe2+

Ga3+ + 3e Ga

0.529

Hg22+ + 2e 2Hg

+ 0.796 0

0.44

Ag+ + e Ag

+ 0.799 1

0.424

Hg2+ +2e Hg22+

+ 0.911 0

0.042 5

Pd2+ + 2e Pd

+ 0.915

+ 1.358 3

V3+ + e V2+
Ni2+ + e Ni

0.255

Cl2 + 2e 2Cl

0.257

Au3+ + 3e Au

Reduction assumed
To occur at test electrode
If so Eoel = positive

+ 0.771
.

Cd2+ + 2e Cd

E+

+ 0.536

Cr3+ + e Cr2+

V>0

+ 0.071 1

Fe2+ + 2e Fe

E-

0 exactly

+ 1.52

Note: Large and negative electrode potential means

less tendency for reduction, tendency is to oxidize.
Electrode potential, by convention is a
measure of the ability to undergo reduction.

a=1
Hg(EDTA)-2(a=1), EDTA(a=1)/Hg

Electrode potential is an interfacial phenomenon.

Separation of charges across metal/solution interface
brings about the potential difference between the
solution and metal.
The position of equilibrium governed by the
activities (concentrations) of species (by way of
reaction quotient Q) involved in the half reaction;
determines the electrode potential and the inherent
tendency to undergo reduction.

Calculation of Electrode Potential (Nernst equation):

Eel Eel0

RT
ln Qel
nF

@ 25o C; volts

R = 8.314 J/K mol

T = temperature, K
n= number of electrons involved in half reaction
F = 96487 C
Qel = reaction quotient in activity
pure liquids, solvents, solids; a=1

Calculation of Electrode Potential:

By convention electrode potentials are expressed for
reduction reactions.
If potential is positive, all what it means is that the
reduction reaction of the test electrode has a higher
propensity to happen compared to the reduction at
the standard hydrogen electrode.

Calculation of Electrode Potential:

Electrode potentials are calculated for the reduction
process as reduction potentials Write the half
reaction as a reduction reaction, balanced in mass
and charge. Write the expression for Q, determine
the # electrons involved;
0
Substitute in the Nernst Equation. Eel Eel

RT
ln Qel
nF

E.g. MnO4- +8H+ +5e = Mn+2 + 4H2O

Tabulation
aMn2
RT
0
EMnO / Mn2 EMnO
ln

2
8
4
4 / Mn
5 F aMnO aH
4

Calculation of Electrode Potential (Nernst equation):

Calculation of Cell Potential:

Cell potentials are calculated for redox reaction.
Write the reaction, balanced.
Write the expression for Q of the reaction, recognize
the # electrons involved; for the reaction.
Substitute in the Nernst Equation.

Eg. Hg(EDTA)2-(aq)+ 2e = Hg(l) + EDTA4- (aq)

Eel Eel0

0
Ecell Ecell

a 4
RT aHg aEDTA4
RT
ln
Eel0
ln EDTA
2F
aHgEDTA2
2 F aHgEDTA2

Calculation of Cell Potential:

Calculation of E0cell
MnO4- +8H+ +5 Fe+2 = Mn+2 + 5Fe+3 + 4H2O
Electrode

Elect Pot

Reaction Pot

Fe 2 Fe 3 e

0
Fe3 / Fe2

0
MnO4 / Mn 2

E
-

0
MnO4 / Mn 2

Tabulated

MnO4 8 H 5e Mn 2 4 H 2O

0
Fe3 / Fe2

Eg. MnO4- +8H+ +5e = Mn+2 + 4H2O

Fe+2 = Fe+3 + e
Overall (all aqueous species)
MnO4- +8H+ +5 Fe+2 = Mn+2 + 5Fe+3 + 4H2O
0
Ecell Ecell

E0cell = E0red E0oxd

E0cell

E0+

RT
ln Qrxn
nF

0
Ecell Ecell

E0-

E0cell = E0MnO4-/Mn+2 E0Fe+3/Fe+2

Ecell can be calculated by calculation each electrode

potential (reduction) separately and subtracting the
potential at oxidation half from the reduction half.
Ecell = Ered process Eoxd process
Ecell = E+ E-

0
Ecell Ecell

0
Ecell Ecell

RT
ln Qrxn
nF

5
aMn2 aFe
3
RT
ln
8
5
5 F aMnO aH aFe
2
4

RT
ln Qrxn
nF

5
aMn2 aFe
3
RT
ln
8
5
5 F aMnO aH aFe
2
4

Electrons move from less positive electrode potential

electrode to more positive electrode potential
electrode, when connected by a conductor.

Alternate view of some electrodes:

Alternate view of some electrodes:

Ag/AgCl(s), HCl(aq)

Pb/PbF2(s), HF(aq)

AgCl(s) + e = Ag(s) + Cl-(aq)

PbF2(s), + 2e = Pb(s) + 2F-(aq)

0
Eel E AgCl
/ Ag

0.05916
log aCl
1

Ag+(aq) + e = Ag(s)
0
Eel E Ag
/ Ag

K
0.05916
1
0.05916
0
log
E Ag
log sp , AgCl
/ Ag
1
a Ag
1
aCl

0
Eel EPbF
2 / Pb

0.05916
log aF2
2

Pb+2(aq) + 2e = Pb(s)
0
Eel EPb
2 / Pb

K sp , PbF 2
0.05916
1
0.05916
0
log
EPb
log
2 / Pb
2
aPb
2
aF2

Use of electrodes in Analytical Chemistry

The fact that the electrode potential (and the cell
potential) is dependent on the concentration of
species allows the use of electrodes as chemical
probes.
The electrode potential at an electrode measures
the propensity of a reduction reaction to occur;
at the concentrations (activities) of the species that
has attained an electrochemical equilibrium at
the interface.

Not a viable
cell configuration.
Zn

ZnCl2 (aq)

Cu (NO 3)2 (aq)

Cu

Study of charge transfer reactions is the goal of most

techniques electrochemistry. The interfacial system of
is very complex and even in the absence of electron
transfer and processes other than electron transfer do
occur. Such processes can affect the electrical double
layer and therefore the electrode behavior.

Electrode Interface :

Such processes include phenomena such as adsorption,

desorption, and charging of the interface as a result of
changing electrode potential.
These are called non-faradaic processes.

Silver/Silver chloride/KCl reference

AgCl(s) +e- = Ag(s) + Cl- (aq)

The SHE is cumbersome to construct. Other half-cells

are being used as secondary standards.

Silver/silver chloride:
AgCl(s) +e- = Ag(s) + Cl- (aq)

Calomel:
Hg2Cl2(s) + 2e- = 2Hg + 2Cl-(aq)
Potential @ 25
vs. SHE vs. SCE

Ag/AgCl, KCl (0.1M)

Ag/AgCl, KCl (3M)

0.288
0.210

0.047
-0.032

Ag/AgCl, KCl (3.5M)

Ag/AgCl, KCl (sat'd)
Ag/AgCl, NaCl (3M)
Ag/AgCl, NaCl (sat'd)

0.205
0.199
0.209
0.197

-0.039
-0.045
-0.035
-0.047

Hg
Hg2Cl2(s)

KCl, Hg2Cl2 (aq,sat),

KCl(s)

frit

Calomel:
Hg2Cl2(s) + 2e- = 2Hg + 2Cl-(aq)

Mercury/mercurous sulfate:
Hg2SO4 (s) + 2e- = 2Hg + SO4-2 (aq)

Potential @ 25
vs. SHE
vs. SCE
Hg/Hg2Cl2, KCl (0.1M)
Hg/Hg2Cl2, KCl (1M)
NCE (Normal Calomel)
Hg/Hg2Cl2, KCl (3.5M)
Hg/Hg2Cl2, KCl (sat'd)
SCE (Sat'd Calomel)
Hg/Hg2Cl2, NaCl (sat'd)
SSCE

0.334
0.280

Potential @ 25

0.0925
0.0389

0.250

0.006

0.241

0.2360

-0.0052

vs. SHE

vs. SCE

Hg/Hg2SO4, H2SO4 (0.5M)

0.682

0.441

Hg/Hg2SO4, H2SO4 (1M)

0.674

0.430

Hg/Hg2SO4, K2SO4(sat'd)

0.64

0.40