Voltammetry

Reading Material

● Skoog, Holler and Crouch: Ch. 25

● Cazes: Chapter 17
● For those using electroanalytical chemistry in their work,
see:

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

Ed., Wiley, 2001.
 Voltammetry

 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
 Polarization
 Some electrochemical cells have significant
currents.
– 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
cell
 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 Ohm’s law, and is governed by
the resistance of the cell:

Ecell  Eright  Eleft  IR

IR Drop

Electrodes
 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
 Overvoltage: 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

www.drhuang.com/.../polar.doc_files/image008.gif
If an electroactive species is
capable of undergoing a redox
process at the DME, then an S-
shaped current-potential trace (a
polarographic wave) is usually
observed
 Voltage-Time Signals in Voltammetry

 A variable potential
excitation signal is applied
to the working electrode

 Different voltammetric
techniques use different
waveforms

 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
potential.
– 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 A + n e-  P

following reduction of “A”

into a product “P” is shown Half-wave potential

A + n e-  P Limiting current

 The half-wave potential

E1/2 is often used for
qualitative analysis
 The limiting current is
proportional to analyte Remember, E is scanned
linearly to higher values as
concentration and is used a function of time in linear
for quantitative analysis 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
 Example: the O OH

hydrodynamic
voltammogram of + 2H+ + 2e
quinone-hydroquinone
O OH

 Different waves are quinone hydroquinone

obtained depending on Cathodic wave

the starting sample

 Both reduction and

oxidation waves are
Anodic wave
seen in a mixture

Diagram from Stroebel and Heineman, Chemical Instrumentation, A Systematic Approach 3 rd Ed. Wiley 1989.
 Oxygen Waves in Hydrodynamic Voltammetry
 Oxygen waves occur in
many voltammetric
experiments
– Here, waves from two
electrolytes (no sample!)
are shown before and after
sparging/degassing
 Heavily used for analysis
of O2 in many types of
sample
– 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 3 rd 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
– Medicine
 The Clark Voltammetric Oxygen Sensor

At the platinum cathode:

O2 + 2H2O + 4e- 4OH-

O2 At the Ag/AgCl anode:

Ag + Cl- AgCl + e-
dissolved O2
O2 id = 4 F Pm A P(O2)/b
id - measured current
O2 F - Faraday's constant
Pm - permeability of O2
A - electrode area
analyte solution electrolyte P(O2) - oxygen concentration
b - thickness of the membrane

O2 permeable membrane platinum electrode

(O2 crosses via diffusion) (-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
potential

 CV is one of the most widely used electroanalytical

methods because of its ability to study and
characterize redox systems from macroscopic
scales down to nanoelectrodes
 Cyclic Voltammetry
 The waveform, and the resulting I-E curve:

 The I-E curve encodes a

large amount of
information (see next
slide)
 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
reactions
P. T. Kissinger and W. H. Heineman, J. Chem. Ed. 1983, 60, 702.
 Spectroelectrochemistry (SEC)
 CV and spectroscopy can be combined by using optically-
transparent electrodes
 This allows for analysis of the mechanisms involved in
complex electrochemical reactions
 Example: ferrocene oxidized to ferricinium on a forward CV
sweep (ferricincium shows UV peaks at 252 and 285 nm),
reduced back to ferrocene (fully reversible)

Y. Dai, G. M. Swain, M. D. Porter, J. Zak, “New horizons in spectroelectrochemical measurements: Optically transparent carbon electrodes,” Anal. Chem., 2008, 80, 14-27.
 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
From www.edaq.com/er461.html hanging mercury drop electrode
From www.indiana.edu/~echem/cells.html
 Further Reading

 Further Reading:
– C. Amatore and E. Maisonhaute, “When voltammetry reaches
nanoseconds”, Anal. Chem., 2005, 303A-311A.
– Y. Dai, G. M. Swain, M. D. Porter, J. Zak, “New horizons in
spectroelectrochemical measurements: Optically transparent
carbon electrodes,” Anal. Chem., 2008, 80, 14-27.