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Nov 16, 2004

Lecture Date: March 27th, 2006

Reading Material

Skoog, Holler and Crouch:


Ch. 25

Chapter 17

For those using electroanalytical chemistry in their work,

A. J. Bard and L. R. Faulkner, Electrochemical Methods, 2 nd
Ed., Wiley, 2001.


Voltammetry techniques measure current as a

function of applied potential under conditions that

promote polarization of a working electrode

Polarography: Invented by J. Heyrovsky (Nobel

Prize 1959). Differs from voltammetry in that it

employs a dropping mercury electrode (DME) to
continuously renew the electrode surface.

Amperometry: current proportional to analyte

concentration is monitored at a fixed potential


Some electrochemical cells have significant


Electricity within a cell is carried by ion motion

When small currents are involved, E = IR holds
R depends on the nature of the solution (next slide)

When current in a cell is large, the actual potential

usually differs from that calculated at equilibrium
using the Nernst equation

This difference arises from polarization effects

The difference usually reduces the voltage of a galvanic
cell or increases the voltage consumed by an electrolytic

Ohmic Potential and the IR Drop

To create current in a cell, a driving voltage is

needed to overcome the resistance of ions to move

towards the anode and cathode

This force follows Ohms law, and is governed by

the resistance of the cell:

Ecell Eright Eleft IR

IR Drop

More on Polarization

Electrodes in cells are polarized over certain

current/voltage ranges

Ideal polarized electrode: current does not vary

with potential

Overvoltage and Polarization Sources


the difference between the equilibrium

potential and the actual potential

Sources of polarization in cells:

Concentration polarization: rate of transport to
electrode is insufficient to maintain current
Charge-transfer (kinetic) polarization: magnitude
of current is limited by the rate of the electrode
reaction(s) (the rate of electron transfer between
the reactants and the electrodes)
Other effects (e.g. adsorption/desorption)

DC Polarography
The first voltammetric technique
(first instrument built in 1925)

DCP measures current flowing

through the dropping mercury

electrode (DME) as a function of
applied potential

Under the influence of gravity (or

other forces), mercury drops grow

from the end of a fine glass
capillary until they detach

If an electroactive species is

capable of undergoing a redox

process at the DME, then an Sshaped current-potential trace (a
polarographic wave) is usually

Voltage-Time Signals in Voltammetry

A variable potential

excitation signal is applied

to the working electrode

Different voltammetric

techniques use different


Many other waveforms

are available (even FT
techniques are in use)

Linear Sweep Voltammetry

Linear sweep voltammetry (LSV) is performed by applying a

linear potential ramp in the same manner as DCP.

However, with LSV the potential scan rate is usually much

faster than with DCP.

When the reduction potential of the analyte is approached,

the current begins to flow.

The current increases in response to the increasing
However, as the reduction proceeds, a diffusion layer is
formed and the rate of the electrode reduction becomes
diffusion limited. At this point the current slowly declines.

The result is the asymmetric peak-shaped I-E curve

The Linear Sweep Voltammogram

A linear sweep

voltammogram for the

following reduction of A into
a product P is shown
A + n e- P

A + n e- P

Half-wave potential

Limiting current

The half-wave potential E1/2

is often used for qualitative

The limiting current is

proportional to analyte
and is used for

quantitative analysis

Remember, E is scanned
linearly to higher values as
a function of time in linear
sweep voltammetry

Hydrodynamic Voltammetry

Hydrodynamic voltammetry is performed with rapid

stirring in a cell
Electrogenerated species are rapidly swept
away by the flow

Reactants are carried to electrodes by migration in

a field, convection, and diffusion. Mixing takes
over and dominates all of these
Most importantly, migration rate becomes
independent of applied potential

Hydrodynamic Voltammograms


voltammogram of

Different waves are

obtained depending on
the starting sample

Both reduction and

oxidation waves are

seen in a mixture


+ 2H+ + 2e




Cathodic wave

Anodic wave

Diagram from Stroebel and Heineman, Chemical Instrumentation, A Systematic Approach 3rd Ed. Wiley 1989.

Oxygen Waves in Hydrodynamic Voltammetry

Oxygen waves occur in

many voltammetric

Here, waves from two

electrolytes (no sample!)
are shown before and after

Heavily used for analysis

of O2 in many types of

In some cases, the

electrode can be dipped in
the sample
In others, a membrane is
needed to protect the
electrode (Clark sensor)
Diagram from Stroebel and Heineman, Chemical Instrumentation, A Systematic Approach 3rd Ed. Wiley 1989.

The Clark Voltammetric Oxygen Sensor

Named after its generally recognized inventor (Leyland Clark,

1956), originally known as the "Oxygen Membrane
Polarographic Detector

It remains one of the most commonly used devices for

measuring oxygen in the gas phase or, more commonly,

dissolved in solution

The Clark oxygen sensor finds applications in wide areas:

Environmental Studies
Sewage Treatment
Fermentation Process

The Clark Voltammetric Oxygen Sensor

At the platinum cathode:
O2 + 2H2O + 4e-

At the Ag/AgCl anode:


Ag + ClO2


id = 4 F P

AgCl + em

A P(O2)/b

id - measured current


analyte solution


F - Faraday's constant
Pm - permeability of O2


A - electrode area
P(O2) - oxygen concentration
b - thickness of the membrane

O2 permeable membrane
(O2 crosses via diffusion)

platinum electrode
(-0.6 volts)

The Clark Voltammetric Oxygen Sensor

General design and modern miniaturized versions:

Hydrodynamic Voltammetry as an LC Detector

One form of electrochemical LC detector:

Classes of Chemicals Suitable for Electrochemical Detection:

Phenols, Aromatic Amines, Biogenic Amines, Polyamines, Sulfhydryls,
Disulfides, Peroxides, Aromatic Nitro Compounds, Aliphatic Nitro
Compounds, Thioureas, Amino Acids, Sugars, Carbohydrates,
Polyalcohols, Phenothiazines, Oxidase Enzyme Substrates, Sulfites

Cyclic Voltammetry

Cyclic voltammetry (CV) is similar to linear sweep

voltammetry except that the potential scans run from

the starting potential to the end potential, then
reverse from the end potential back to the starting

CV is one of the most widely used electroanalytical

methods because of its ability to used to study and
characterize redox systems

Cyclic Voltammetry

The waveform, and the resulting I-E curve:

Cyclic Voltammetry

A typical CV for a simple

electrochemical system.
CV can rapidly generate
a new oxidation state on
a forward scan and
determine its fate on the
reverse scan
Advantages of CV
Controlled rates
Can determine
mechanisms and
kinetics of redox

Instrumentation for Voltammetry

Sweep generators, potentiostats, cells, and data

acquistion/computers make up most systems

Basic voltammetry system suitable for undergraduate laboratory work


Cyclic voltammetry cell with a

hanging mercury drop electrode