RUSCHEP302 – Advanced instrumental Techniques

Paper 2 Unit 4.4 STRIPPING VOLTAMMETRY

Anodic Stripping
Voltammetry

Ninad P. Tirlotkar
312
MSC – Part II
Physical Chemistry
 Stripping Voltammetry

 Most sensitive electrochemical technique for the quantitative

analysis.
 Stripping Voltammetry is the method for determination of
analytes which oxidize or reduce reversibly at solid electrodes
or form insoluble species at the electrode surface that can be
subsequently removed electrochemically and analysed.

 Basically two steps are involved in this technique :---

1. The analyte of interest is electrolytically deposited on the
working electrode by controlled potential electrolysis.
2. A reverse potential seal or stripping step is applied in which the
deposited analyte is removed from the electrode.

The first step is basically pre-concentration or electro-deposition

while the second one is the stripping step.
 Stripping Voltammetry

 Ways by which you can accumulate the Metal are as follows :----
1) As a metal.
2) As a sparingly soluble mercury compound
3) Absorbed as a complex compound.

 TYPES OF STRIPPING VOLTAMMETRY :---

o Anodic Stripping Voltammetry(ASV) :-----

In this type of Stripping voltammetry, the determination takes place by
oxidation of accumulated product.
o Cathodic Stripping Voltammetry(CSV) :----
In this type of Stripping voltammetry, the determination takes place by
oxidation of accumulated product
o Adsorptive stripping Voltammetry (AdSV) :---
In this type of Stripping voltammetry, the determination takes place by
adsorptive accumulation of product.
 Anodic Stripping Voltammetry

 Sensitive.
 Trace level analysis.
 Simultaneous multielement determination and cost effective.
 Used to determine trace amounts of metal ions. that can be pre-
concentrated at an electrode by reduction to the metallic state.
 The microelectrode behaves as a cathode during the deposition step and
as an anode during the stripping step.

 Three types of working electrodes can be used :-----

a) The Hanging Mercury-Drop Electrode (HDME)
b) The Thin Film Mercury Electrode (TFME).
c) Solid electrodes (gold, silver, surface modified carbon)
 Working

Hg deposition at – 1300mv Analyte Pre-concentration – 900mv ReOxidation

e- e- e-

C C C C C C C C C
Hg Hg HgCu HgCd HgCu HgCd
Hg HgPb HgPb

2e- 2e- 2e- 2e- 2e-

2e -

Hg2+ Cu2+
Hg2+ Cu2+ Cd2+ Cd2+
Hg2+ Pb2+ Pb2+
 Mechanism

 Analytic stripping voltammetry can be used to

determine all metals which are soluble in mercury With
the formation of amalgams or which can be deposited
electrolytically At carbon or noble metal electrodes.

 The mechanism for anodic stripping voltammetry can be

described using the following equation.

o Accumulation:--

Applied potential more negative than E1/2 of Mn+.

Mn+ + Hg + ne- M(Hg)

o Stripping:----
Scan in the positive direction, peak current is proportional to the
concentration of M.
M(Hg) Mn+ + ne-
Graph
 Calculations

 Amount of accumulated metal in the amalgam

𝑖𝑎𝑐𝑐 .𝑡𝑎𝑐𝑐
𝐶 𝑀 (𝐻𝑔)=
𝑉 𝐻𝑔 .𝑛 . 𝑓

= Concentration of the metal (accumulated analyte) in the amalgam.

= Electrolysis current during accumulation.
= Accumulation Time.
n = Electrons transferred during reduction of the analyte.
F = Faraday constant.
= Volume of the hanging mercury drop.
 Types of Anodic Stripping Voltammetry

1) Linear Scan Anodic stripping voltammetry :----

 Types of Anodic Stripping Voltammetry

2) Differential Scan Anodic stripping voltammetry :----

 Applications Limitations

• It is used for quantitative and qualitative analysis.

• Cannot detect metals that are complexed.
• ASV is widely used for testing drinking water quality,
• The presence of surfactants or high
surface water and sewage or waste water .
concentrations of other metals can cause
• Copper, Zinc, manganese present in the soil samples. underestimation of the target analyte.
• Lead present in the water can be analysed.
• Determination of food contamination, toxic metal
concentration , pesticide, fertilisers, trace essential
elements. Food additive dyes, etc

Metals that can be determined by ASV

Antimony Mercury Thallium
Indium Cadmium Gallium
Arsenic Silver Tin
Lead Copper Germanium
Bismuth Gold Zinc
 References

• Modern Polarographic Methods in Analytical Chemistry by A.M.Bond Deakin university, Australia.

• Principles of Instrumental Analysis (Second Edition) by Douglas M. Skoog and Donald M. West.

• Electrochemical Methods : Fundamentals and Applications by Allen J. Bard, Larry R. Faulkner, Department of
Chemistry and Biochemistry, University of Texas, Austin
• Analytical electrochemistry second edition by Joseph Wang.

Thank You