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

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
– 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

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

Bulk 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

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:



Salt bridge

Cu electrode
Zn electrode
0.010M CuSO4
0.010M ZnSO4 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

measurement e-

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

 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
• At the electrode surface: an oxidation or a reduction
– Cathode: the electrode at which reduction occurs
– Anode: the electrode at which oxidation occurs
• “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:

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
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

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 ().
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