ANODIC STRIPPING

VOLTAMMETRY

BY:
CHITRAKSHI GOEL
Voltammetry

 An electrochemical technique, used in analytical

chemistry.
 Information about an analyte is obtained by
monitoring the current at an electrode as a
function of potential applied to that electrode.
 The plot between the measured current and the
applied potential is known as Voltammogram.
 Application - quantitative analysis of trace of
metals (μg/L levels or less)
Voltammetry
 Measurement of current under conditions of
complete concentration polarization.
 The rate of oxidation or reduction of the analyte is
limited by the rate of mass transfer of the analyte
to the electrode surface.
 To enhance the polarization, the working
electrodes are relatively small with surface areas
of a few square millimetres at the most and, in
some applications, only a few square micrometres.
 A minimal consumption of analyte.
Voltammetry
 For analytical purposes several types of voltammetry
techniques are available.
 Stripping voltammetry is very significant these days
particularly for the determination of metals in the
environment.
 Linear Sweep Voltammetry is the simplest technique.
 The electrode potential is varied at a constant rate (20
– 100 mV/s) throughout the scan and the resulting
current is measured.
 The scanning starts before the discharging potential
and stops afterwards.
 Detection limits range at mg/l levels.
Linear Sweep Voltammetry

Linear potential sweep

Linear Sweep Voltammetry
Linear Sweep Voltammetry
 For potentials from 0 to -1 V, the current is small
and constant. This small current is due to the
electron flow necessary to maintain a charged
double layer at the electrode surface. This current
is often called the charging current.
 As the potential is varied beyond -1 V, an
electrochemical reaction occurs at the surface of
the electrode—that is, electrons transfer from the
electrode surface to the hydrogen ions in solution,
causing a reduction of H+ to H2 and a rapid
increase in current.
Linear Sweep Voltammetry
Linear Sweep Voltammetry
 With Cd2+ added to the HCl solution, the current
does not remain constant from 0 to -1 V.
 As the potential goes more negative, the reductive
power of the system increases. Thus, at potentials
where Cd2+ is reduced, the current increases.
 As the scan continues in a negative direction,
cadmium continues to reduce and the current
continues to increase.
 The current measured is a function of the
concentration of the Cd2+ at the surface of the
electrode.
Linear Sweep Voltammetry
Linear Sweep Voltammetry
 The addition of a second electro-active species to
the solution (in this case cadmium and lead)
produces multiple peaks.
 Each peak occurs at a potential characteristic of
the reacting species, the type of supporting
electrolyte and the working electrode type.
Anodic Stripping Voltammetry
 Voltammetric method for quantitative
determination of specific ionic species.
 It is one of the most sensitive, convenient, and
cost effective analytical method for detection and
quantitation of metal contaminants in rivers,
lakes, process streams and drinking water.
 Several metals such as Cu, Pb and Cd can be
analyzed simultaneously.
 ASV can be thought of as a small scale
electroplating experiment.
Anodic Stripping Voltammetry

 Incorporates three electrodes:

 a working electrode,

 an auxiliary electrode (sometimes called the

counter electrode), and

 a reference electrode.
Working Electrode - ASV

 It is the indicating electrode in an electrochemical

system on which the reaction of interest is
occurring.
 Common working electrodes can consist of inert
metals such as gold, silver or platinum, inert
carbon such as glassy carbon or pyrolytic carbon,
and mercury drop and film electrodes.
 For most standard tests, the working electrode is a
mercury film electrode.
Working Electrode - ASV

 The mercury film is formed over a glassy carbon

electrode.
 This film forms an amalgam with the analyte of
interest, which upon oxidation results in a sharp peak.
 In cases where the analyte of interest has an oxidizing
potential above that of mercury, or where a mercury
electrode would be otherwise unsuitable, a solid, inert
metal such as silver, gold, or platinum may also be
used.
Auxiliary Electrode - ASV
 Also called the counter electrode.
 The auxiliary electrode's potential is opposite in
sign to that of the working electrode, but its
current and potential are not measured.
 Rather, it is used to ensure that current does not
run through the reference electrode (three
electrode system), which would disturb the
reference electrode's potential.
Auxiliary Electrode - ASV
 The auxiliary electrode passes all the current
needed to balance the current observed at the
working electrode.
 It serves as a source or sink for electrons so that
current can be passed from the external circuit
through the cell. In general, neither its true
potential nor current is ever measured or known.
 Auxiliary electrodes are often fabricated from
electrochemically inert materials such as gold,
platinum, or carbon.
Reference Electrode - ASV

 Has a stable and well-known electrode potential.

 It can be taken as the reference standard against
which the potentials of the other electrodes
present in the cell can be measured.
 Its only role is to act as reference in measuring
and controlling the working electrodes potential
and at no point does it pass any current.
 Generally Ag/AgCl is used.
Anodic Stripping Voltammetry

 Concentrate metal ions by reduction:

 The metals, as ions in solution, are plated onto an
electrode by applying a negative potential
(deposition potential) for a specific period of time.
 The deposition serves to concentrate the metal ions
from the solution onto the electrode in the metallic
form.
 If the electrode is Hg, the metals often form an
amalgam.
 This pre-concentration leads to low detection limits.
Anodic Stripping Voltammetry
 Stripping
 After deposition, the potential is scanned toward
positive potentials. Current peaks appear at potentials
corresponding to the oxidation of metals as they are
oxidized (stripped) from the electrode back into the
solution.
 The current is measured during the stripping step.
 The peak height or area can be correlated with the
concentration of the metal ions in the solution. It is
necessary to calibrate the procedure with standard
solutions containing known quantities of the metal
ions.
Anodic Stripping Voltammetry
 Consider a sample containing copper and cadmium (the
two analytes).
 First concentrated in a mercury working electrode and
then sequentially reduced back to their metal ions and the
current time curves reported.
 The first stage is to reduce the metal ion to the metal that
will form an amalgam with the mercury working-
electrode.
 This can be depicted by the following equation.

Mn+ + ne- + Hg  M(Hg)

Anodic Stripping Voltammetry
 If a mixture of cations are present, the working
electrode should be maintained at a potential 0.3 -
0.5 V more negative than the standard potential of
that metal most difficult to reduce.
 The deposition of all the metal components of the
mixture will be determined by the magnitude of
the respective mass transport of each.
 The speed of deposition can be accelerated by
electrode rotation or by vigorously stirring the
electrolyte.
Anodic Stripping Voltammetry
 The concentration of the reduced metal(s) in the mercury will
be given by
il t d
C Hg 
nFVHg
 il: limiting current for the deposition (reduction) of the metal
 td: deposition time period
 n: the number of moles of electrons transferred in the half
reaction
 F: the Faraday constant (96,487 coulombs/mole of e-)
 VHg: volume of the mercury electrode
Anodic Stripping Voltammetry
 The time of the deposition will vary with a number of
factors including the analyte concentration and the
electronic parameters, but the conditions should be
adjusted so that the deposition takes from one to ten
minutes. 
 The pre-concentration step can the be followed by a
change in the electrolyte composition to make it more
amenable to the stripping procedure and this process
takes place in the rest period.
 Electrode rotation or stirring should be arrested
during this procedure.
Anodic Stripping Voltammetry
 In the third stage the metals are stripped from the mercury by
applying an appropriate voltage/time program. When the
applied working electrode potential reaches the standard
metal-metal ion redox potential the metal is stripped from the
amalgam according to the following equation.
M(Hg)  Mn+ + ne- + Hg
 In the current time curve, peaks are observed for the analytes,
cadmium and copper. The peak potential of each metal is
characteristic of the analyte and can be used to identify the
metal. The height of each metal peak (ip) is proportional to the
concentration of the metal in the test solution.
Anodic Stripping Voltammetry
 If a thin-film mercury electrode is employed, under
which circumstances the metal is rapidly depleted from
the amalgam, then the expression for the peak current
(ip) is given by,
n 2 F2 v1/2 AlCHg
ip 
2.7RT
 
 A: area of the film
 l: length of the film
 v: potential scan rate
Differential Pulse ASV
- Several metals in scan
- Extremely sensitive
- Hydrogen wave
- Mercury oxidation wave
Anodic Stripping Voltammetry
 Very sensitive and reproducible method for trace metal
ion analysis.
 Useful for the analysis of very dilute solutions, 10-11 M.
 Concentration limits of detection for many metals are in
the low ppb to high ppt range
 Approximately 12-15 metal ions can be analyzed for by
this method.
 The stripping peak currents and peak widths are a
function of the size, coverage and distribution of the
metal phase on the electrode surface (Hg or alternate).
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