Introduction to Electroanalytical

Nov 16, 2004

Chemistry
Lecture Date: April 27h, 2008

Reading Material

Skoog, Holler and Crouch:

Ch. 22 (An Introduction to

Electroanalytical Chemisty)

See also Skoog et al. Chapters 23-25.

Cazes:

Chapters 16-19

For those using electroanalytical chemistry in their work,

the following reference is recommended:

A. J. Bard and L. R. Faulkner, Electrochemical Methods, 2 nd

Ed., Wiley, 2001.

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 Nernst
equation (Nobel Prize
1920)

Michael Faraday
(1791-1867)

Walter Nernst
(1864-1941)

Jaroslav Heyrovsky:

the
invention of polarography:
(Nobel Prize 1959)
Jaroslav Heyrovsky
(1890-1967)

Main Branches of Electroanalytical Chemistry

Interfacial
methods

Voltammetry
(I = f(E))

Conductometry
(G = 1/R)

Dynamic
methods
(I > 0)

Static methods
(I = 0)

Potentiometry
(E)

Bulk methods

Controlled
potential

Amperometric
titrations
(I = f(E))

Constant
current

Electrogravimetry
(m)

Based on Figure 22-9 in Skoog, Holler and

Crouch, 6th ed.

Coulometric
titrations
(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-

eSalt bridge
(KCl)

Cu electrode
Zn electrode

0.010M CuSO4
solution

0.010M ZnSO4
solution

Zn Zn2+ (aq) + 2ea Zn 2+ = 0.010

Anode

Cu2+ (aq) + 2e- Cu(s)

a Cu 2+ = 0.010
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

e-

working electrode
indicator electrode
detector electrode

control
measurement

e-

reference 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

Leo the Lion Says Ger

Oxidationoccurswhenachemicalspecieslosesanelectron.
LEO=loseelectronisoxidation
Reductioniswhenaspeciesgainsanelectron.
GER=gainanelectronisreduction
Forexample,thechemicalreaction
canbedecomposedintotwohalfreactions:

Faradaic and Non-Faradaic Currents

Mass Transfer occurs by:
Convection
Migration
Diffusion

Figure 22-2

Faradaic (governed by Faradays 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 As 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

The Standard Hydrogen Electrode (SHE)

A universal reference, but is really a hypothetical

electrode (not used in practice)

Uses a platinum electrode, which at its surface
oxidizes 2H+ to H2 gas.
Very sensitive to temperature, pressure, and
H+ ion activity

Because the SHE is difficult to make, the

saturated calomel electrode (SCE) is used

instead.
Calomel = mercury (I) chloride

Electrode Potentials
Q: What is the electrode potential for
the electrode Ag/AgI(s)/I-(0.01 M) ?
Theoverallreactionforthiselectrodeis

Thisreactioncannotbefoundintablesofreductionpotentials.
Butthereactioniscomprisedoftwocomponents

Electrode Potentials
We can initially ignore the fact that the electrode
contains AgI and find E for the silver ion reduction.

The Glass pH Electrode

One of the most common

potentiometric measurements is pH
(a so-called p-Ion measurement).

The common glass pH electrode

makes use of junction potentials to

determine the hydronium ion
concentration in a sample solution.

A typical glass pH electrode is

configured as shown here:

The Glass pH Electrode

The glass pH electrode is used with a Ag/AgCl reference
electrode. For most modern pH electrodes the reference
electrode is incorporated with the pH indicator electrode.
A small frit or
hole connects
the reference
electrode and
the sample
solutions

pH Measurements

A combination pH electrode combines the indicator and

reference into a single unit.

The potential of this cell is:

where Eij and Eoj are the junction potentials at the inner
and outer layers of the glass membrane.

Junction potential:

occurs at the interface of two

electrolytes, caused by unequal diffusion rates of cation
and anions across the boundary (e.g the frit in a salt
bridge)

More About pH Measurements

The surface of the glass is hydrated, which allows

exchange of hydronium ions for the cation in the glass

(sodium or lithium).
There are four interface regions, the external solution and
hydrated glass, hydrated glass and dry glass on the
outside, dry glass and hydrated glass on the inside, and
hydrated glass and the internal solution.
If the glass is uniform, the two hydrated glass/dry glass
interfaces should be identical and should have the same
junction potential.
Since the glass interface junction potentials then cancel
each other, the junction potential is then the difference
between the internal and external solutions.

pH Measurements
aH + ,glass,in RT
aH + , glass,inaH + ,sol'n,out
aH + ,sol'n,out
RT
RT
=Emem = log
log
log
F
aH + ,sol'n,in F
aH + , glass,out
F
aH + ,sol'n,inaH + ,glass,out
If the two solutions are identical
a H+ ,glass,in = aH + , glass,out
aH + ,sol'n,out
RT
Emem = log
F
aH + ,sol'n,in
if the internal solution has a fixed composition, then
Emem = -

RT
RT
+
logaH + ,sol'n,out
logaH + ,sol'n,in = k + 0.05916pH
F
F

pH Measurements

For a real electrode, the two surfaces will not be identical and
the constant k needs to be determined experimentally. The
constant k is termed the asymmetry potential. The constant
is termed the electromotive efficiency.

pH Measurements

pH Measurements
Q: Why does the pH change the interfacial
potential of the glass/aqueous interface?
A: The motion of the sodium ions leave behind a
negatively charged glass layer that is neutralized
to a lesser or greater extent according to the pH.
More explanation about how a pH meter
really works: The sodium ions must move
through the dry part of the membrane and this
process is slow. For this reason, the membrane
is made very thin. Also, a nonperturbing (lowcurrent) voltmeter is used to read the cell
voltage so that only a few sodium ions must
move through the dry glass in a given time

pH Electrodes: Errors, Accuracy and Precision

Errors in pH measurements with glass electrodes arise from

the following effects:
Calibration problems (e.g. drift, or error in the calibration)
Junction potential
High [Na+] interacting with electrode
High acid concentration
Equilibration time
Temperature control

Typical electrodes have the following performance:

Accuracy = +/- 0.02 pH units
Precision = +/- 0.002 pH units

The Combination pH Electrode

Modern pH electrodes are usually of the
"combination" type, meaning that a single cylinder
contains both the reference electrode, and a glass
membrane electrode.
Schematically, the total cell may be expressed as
SCE//test solution ([H3O+]=a1)/glass
membrane/[H3O+]=a2, Cl-/AgCl(s)/Ag

A Modern Combination pH Electrode

Electrochemical pH Measurements Concluded

Consider a typical problem related to

the use of the combination pH
electrode. Recall that
Ecell = L - 0.0592 V pH
QUESTION: If Ecell = -0.115 V at a pH of
4.00,
what is the pH of a solution for which Ecell
is

ANSWER: First, find L from the measurement

of the standard:
-0.115 V = L -0.0592 x pH
-0.115 V = L -0.0592 x 4.00
Therefore, L = 0.122 V
Second, use this value of L to find pH:
-0.352 V = 0.122 V - 0.0592 V x pH
pH = (0.122 V -(-0.352 V))/0.0592
pH = 7.84

QUESTION: What does the pH meter read

if the pH is 7.00 in a 1 M salt solution having
1 M Na+ ions present?

ANSWER:
[H+]obs = 1 x 10-7 + 1 x 10-12
Conclusion -- the pH meter reads the true
pH under these conditions.

The Ion Selective Electrode (ISE)

An ISE generally consists

of the ion-selective
membrane, an internal
reference electrode, an
external reference
electrode, and a
voltmeter.
Example: an ISE for
fluoride (F-)

Automatic pKa and log P Determination

pKa (ionization constant) and log P (octanol/water partition) are
important physical parameters that play critical roles in determining
how compounds behave in physiological environments and how they
interact with enzymes, receptors and cell membranes
liquid
dispensors
reagents

The Sirius
GLpKa system:

combination pH
electrode

sample tray

Conductometry

Conductometry:

Detection of electrical

conductivity

Key analytical applications: conductometric detection

in ion-exchange chromatography (IEC or IC) and
capillary electrophoresis (CE)

Used to detect titration endpoints

Homework Problems (for Study Only)

Chapter 22:
22-1

Chapter 23:
23-11