Electrochemical

methods of analysis
Electrochemistry
 Electrochemistry
• Electrochemistry
– deals with interconversion between chemical
and electrical energy
– involves redox reactions
• electron transfer reactions
basic concepts of electrochemistry

Electrochemistry:
a science that studies the relationship between
electric and chemical phenomena and the conversion
disciplines between electric and chemical energy
Differences between the ordinary oxidation-reduction
reaction (redox reaction) occurring in solution and in the
electrochemical cell.

2Fe3+ + Sn2+  2Fe2+ + Sn4+

To harvest useful energy, the oxidizing and reducing agent has
to be separated physically in two different compartments so
as to make the electron passing through an external circuit

half-reactions:
oxidation / anode reaction:
Sn2+ - 2e-  Sn4+
reduction / cathode reaction:
2Fe3+ + 2e-  2Fe2+
Reaction takes place at
electrode/solution interface
Electrochemical apparatus:

chemical  electric: electric  chemical:

primary cell (Galvanic cell) electrolytic cell

Electrode: anode, cathode

positive electrode; negative electrode
 Advantages of Electroanalytical Methods

• Matched against a wide range of spectroscopic and

chromatographic techniques, the techniques of
electroanalytical chemistry find an important role for several
reasons:
– Electroanalytical methods are often specific for a
particular oxidation state of an element
– Electrochemical instrumentation is relatively inexpensive
and can be miniaturized
– Electroanalytical methods provide information about
activities (rather than concentration)
 History of Electroanalytical Methods

• Michael Faraday: the

law of electrolysis
– “…the amount of a substance deposited
from an electrolyte by the action of a
current is proportional to the chemical
equivalent weight of the substance.”

• Walter Nernst: the Michael Faraday

(1791-1867)
Walter Nernst
(1864-1941)
Nernst equation
(Nobel Prize 1920)
• Jaroslav Heyrovsky:
the invention of
polarography: (Nobel
Jaroslav Heyrovsky
Prize 1959) (1890-1967)
 Main Branches of Electroanalytical Chemistry

Interfacial
Bulk methods
methods

Static Dynamic Conductometry

methods methods (G = 1/R)
(I = 0) (I > 0)

Based on Figure 22-9 in Skoog, Holler

Potentiometry and Crouch, 6th ed.
(E) Controlled Constant
potential current

Amperometric Electro- Coulometric

Voltammetry
titrations gravimetry titrations
(I = f(E))
(I = f(E)) (m) (Q = It)

 Key to measured quantity: I = current, E = potential, R = resistance,

G = conductance, Q = quantity of charge, t = time, vol = volume of a
standard solution, m = mass of an electrodispensed species
 Main Branches of
Electroanalytical Chemistry

 Potentiometry: measure the potential of electrochemical cells without

drawing substantial current
– Examples: pH measurements, ion-selective electrodes,
titrations (e.g. KF endpoint determination)

 Coulometry: measures the electricity required to drive an electrolytic

oxidation/reduction to completion
– Examples: titrations (KF titrant generation),
“chloridometers” (AgCl)

 Voltammetry: measures current as a function of applied potential under

conditions that keep a working electrode polarized
– Examples: cyclic voltammetry, many biosensors
 Electrochemical Cells
 Zinc (Zn) wants to ionize more than copper (Cu).
 We can use this behavior to construct a cell:

Voltmeter

e-
e-

Salt bridge
(KCl)

Cu electrode
Zn electrode
0.010M CuSO4
0.010M ZnSO4 solution
solution

Zn  Zn2+ (aq) + 2e- Cu2+ (aq) + 2e-  Cu(s)

a Zn 2+ = 0.010 a Cu 2+ = 0.010
Anode Cathode
 Electrochemical Cells and Analytical Methods
Potentiometry: Measures equilibrium E
Amperometry: Control E, measures I as function of time
Coulometry: Control E, measure total Q over a period of time

control
measurement e-
e-

working electrode
indicator electrode reference electrode
detector electrode counter electrode
 Electrochemical Cells
 Galvanic cell: a cell that produces electrical
energy

 Electrolytic cell: a cell that consumes

electrical energy

 Chemically-reversible cell: a cell in which

reversing the direction of the current
reverses the reactions at the two electrodes
 Conduction in an Electrochemical Cell
• Electrons serve as carriers (e.g. moving from Zn through
the conductor to the Cu)
• In the solution, electricity involves the movement of
cations and anions
– In the salt bridge both chloride and potassium ions
move
• At the electrode surface: an oxidation or a reduction
occurs
– Cathode: the electrode at which reduction occurs
– Anode: the electrode at which oxidation occurs
 Nomenclature
• “Redox” Chemistry: Reduction and Oxidation

• Oxidation: Loss of electrons

• Reduction: Gain of electrons

(a reduction in oxidation number)

LEO goes GER

Loss of Electrons is Oxidation
Gain of Electrons is Reduction
 “Leo the Lion Says Ger”
Oxidation occurs when a chemical species loses an electron.
LEO = lose electron is oxidation

Reduction is when a species gains an electron.

GER = gain an electron is reduction

For example, the chemical reaction

can be decomposed into two half reactions:

Redox Reaction
 Faradaic and Non-Faradaic Currents
Mass Transfer occurs by:
Convection
Migration
Diffusion

Figure 22-2

• Faradaic (governed by Faraday’s law): direct

transfer of electrons, i.e. oxidation at one and
reduction at the other electrode
• Non-Faradaic: increasing charge of the double
layer
 Fundamentals
Electrical charge, q, is measured in coulombs (C). The
charge associated with chemical species is related to the
number of moles through the Faraday constant,
F=96,485.3 (~96,500) C/mole.

Electrical current, I, is measured in Amperes (A). Current is

the amount of charge that passes in a unit time interval
(seconds).

Ohm's law relates current to potential (E) through the

resistance (R) of a circuit by E=IR. The potential is
measured in Volts (V) and the resistance in Ohms ().
 Fundamentals
Power (P) is measured in Watts (W = J/s) and is related to
the current and potential by P= IE.

The work is measured in Joules (J) and is related to the

potential and the amount of charge by work=q E.

The relationship between the standard Gibb's free energy

change, G° (J/mole), and the standard electromotive force
(EMF), E° (V), is given by

G°=-n F E°

where n is the number of electrons transferred and

superscript on E0 refers to ‘standard state.’
 Fundamentals: The Nernst Equation
● The Nernst equation gives the cell potential E (in volts):
F = faraday (constant)
n = # moles electrons in process
E0 = standard potential for cell
● Q (the activity quotient) is the ratio of products over reactants
as in equilibrium calculations. For the generic reaction:

● Q is given by:

● The A’s are activities. For low-concentration solutions (low

ionic strengths):
 Electrode Potentials

• The reactions in an electrochemical cell can be

thought of as two half-cell reactions, each with its
own characteristic electrode potential
– These measure the driving force for the reaction
– By convention, always written as reductions

• Standard electrode potential (E0): the measure of

individual potential of an electrode at standard
ambient conditions (298K, solutes at a
concentration of 1 M, and gas pressure at 1 bar).
 Some Standard Electrode Potentials

Reaction E0 at 298K (Volts)

Cl2(g) + 2e-  2 Cl2 +1.359
O2 (g) + 4H+ + 4e-  2 H2O +1.229
Ag+ + e-  Ag(s) +0.799
Cu2+ + 2e-  Cu(s) +0.337
Hg2Cl2 + 2e-  2Hg(l) + 2 Cl2 +0.268
2H+ + 2e-  H2 (g) 0.000
AgI(s) + e-  Ag(s) + I2 -0.151
Cd2+ + 2e-  Cd(s) -0.403
Zn2+ + 2e-  Zn(s) -0.763

See appendix 3 in Skoog et al. for a more complete list