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Voltammetry

Nov 16, 2004


Lecture Date: April 28th, 2008

Reading Material

Skoog, Holler and Crouch:

Cazes:

Ch. 25

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 Ohms 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
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
observed

www.drhuang.com/.../polar.doc_files/image008.gif

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
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 analysis

The limiting current is


proportional to analyte
concentration 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

Example:

the
hydrodynamic
voltammogram of
quinone-hydroquinone

Different waves are


obtained depending on
the starting sample

OH

+ 2H+ + 2e

OH

quinone

hydroquinone

Cathodic wave

Both reduction and


oxidation waves are
seen in a mixture

Anodic wave

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 + 4e4OHAt the Ag/AgCl anode:
Ag + ClAgCl + e-

O2
O2

dissolved
O2

id - measured current

O2

analyte solution

electrolyte

O2 permeable membrane
(O2 crosses via diffusion)

id = 4 F Pm A P(O2)/b
F - Faraday's constant
Pm - permeability of O2
A - electrode area
P(O2) - oxygen concentration
b - thickness of the membrane

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
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


From www.edaq.com/er461.html

Cyclic voltammetry cell with a


hanging mercury drop electrode
From www.indiana.edu/~echem/cells.html

Homework Problems and Further Reading

Optional Homework Problems:


25-1, 25-2, 25-5

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.

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