Anodic and Cyclic Voltammetry

Stripping and Cyclic
voltammetry
Principles
Advantages and disadvantages
applications
Stripping Voltammetry
Two step technique

Deposition Step
- Preconcentration step
- Involves the electrolytic
deposition of a small portion
of metal ions in solution into
an electrode
Stripping Step
- Measurement step
- Involves the dissolution
(stripping) of the deposit
method
• Deposition: a mercury electrode is held at a negative
potential to reduce metal ions in solution and form an
amalgam with the electrode. The solution is stirred to
carry as much of the analyte metal(s) to the electrode
as possible for concentration into the amalgam.
• Stripping: After reducing and accumulating the

analyte for some period of time, the potential on the
electrode is increased to reoxidize the analyte and
generate a current signal.
Advantages
- Very sensitive for detection of trace metals
- Favorable signal to background ratio

- About four to six metals can be measured simultaneously
at levels as low as 10-10 M
- Low cost instrumentation
- Stable and selective
- There are different versions of stripping analysis
depending on the nature of the deposition and stripping
steps
Disadvantage
• Overlapping peaks- occurs if two metal ions with similar
redox potentials are present. Overcome by use of
complexing agents , careful selection of the deposition
potential and methametical calculations
• Formation of intermetallic compounds between metal and

Hg or two metals resulting in potential shifts
• Adsorption of unwanted organic which can affect peak

parameters
Solutions to overcome the above issues: short deposition

time to avoid high concentrations in Hg and modified
selective electrodes
Types
Based on the mode of accumulation and stripping
Accumulation during deposition: Electrolytic and adsorptive
Stripping: In principle all waveforms linear or pulsed) can be
used for stripping. Practice DPV and SQWV are use due to
their low detection limits
oxidative
Reduction
reduction of ligand / metal complex / catalytic processes

Anodic Stripping Voltammetry (ASV)
-The most widely used stripping analysis
- Preconcentration is done by cathodic (REDUCTION)

deposition at controlled potential and time
- Metals are preconcentrated by electrodeposition into a

small-volume electrode (Hg (HME,TFME), Modified
electrodes ( Bi, other modified electrodes)
- Deposition potential is usually 0.3 – 0.5 V more negative

than Eo for the analyte metal ion
ASV
- Metal ions reach the electrode surface by diffusion
and convection
- Electrode rotation or solution stirring is employed to

achieve convection
- Metal ions are reduced and concentrated as

amalgams Mn+ + ne- + Hg → M(Hg)
- Stripping M(Hg) → Mn+ + ne- + Hg
CHg = concentration of metal in the amalgam

ilt d
C Hg  il = limiting current
nFVHg td = deposition period
VHg = volume of Hg electrode
Anodic Stripping Voltammetry (ASV)
- Stripping voltammogram is current-potential plot showing
peaks for metal ions present
- Peak potentials are used to identify metals in sample
- Hg film is more sensitive and more efficient in preconcentration

than Hg drop (due to higher surface: volume ratio)
- Hg film gives sharper peaks and improved resolution for mixtures
- Bismuth and gold electrodes may also be used

Peak currents equations:
Hg Film: 2 2 1/2
n F ν AlC Hg Hg drop: i p  2.72 x 10 5
n 3/2
AD1/2 1/2
ν C Hg
ip 
2.7RT
A = area of film l = thickness of film = scan rate during stripping

Cathodic Stripping Voltammetry (CSV)
- Mirror image of ASV
- Involves anodic deposition of analyte and subsequent

stripping by a potential scan in the negative direction
An- + Hg ↔ HgA + ne-

(Deposition to the right and stripping to the left)
- Useful for measuring organic and inorganic compounds

that form insoluble salts with Hg (thiols, penicillin,
halides, cyanides)
Potentiometric Stripping Voltammetry (PSV)
- Known as stripping potentiometry
- Potentiostatic control is disconnected following

preconcentration
- Concentrated metals are reoxidized by an oxidizing agent

present in the solution [O2, Hg(II)]
- Oxidation is facilitated by stirring during stripping
M(Hg) + oxidant → Mn+

PSV
Oxidation may also be carried out by passing a constant
anodic current through the electrode
- Variation of the working electrode potential is recorded

during oxidation
- Stripping voltamogram is then obtained
- Potential measurements are used to identify metals in

sample
Adsorptive Stripping Voltammetry
(AdSV)
-Involves the formation, adsorptive accumulation, and
reduction of a surface-active complex of the analyte
metal
- Appropriate chelate agent (ligand) must be present in
solution
Adsorbed species are measured by:
- Voltammetric stripping with negative potential scan
or
- Potentiometric stripping with constant cathodic current
(AdSV)
Involves reduction of the metal in the adsorbed complex
- Response of surface-confined species is proportional to

surface concentration
- Detection limits as low as 10-10 – 10-12 M
- Used for measuring organic compounds

(anticancer drugs, nucleic acids, vitamins, pesticides
Abrasive Stripping Voltammetry
- Provides qualitative and quantitative analysis for

solid materials
- Involves mechanical transfer (by rubbing) of trace

amounts of a solid sample onto the electrode surface
- Electrode is usually paraffin-impregnated graphite

electrode
- Voltammetric measurement and stripping of the

transferred material follows
Abrasive Stripping Voltammetry
Used for studying

- Minerals, pigments, and pesticides
- Electrode processes of solid compounds
- Fingerprint identification of alloys
General Applications
- Analysis of gunshot residues, foodstuffs, beverages
- Screening for blood lead in children
- Monitoring trace metals in various water samples
Cyclic Voltammetry (CV)
• Primary usage
– Fundamental and diagnostic studies of
electrochemical reactions under various
conditions
– Characterisation of materials- determining
electrochemical activities
Recall:
Cathodic reduction
Anodic oxidation
Cyclic voltammetry (CV)
1) Method used to look at mechanisms of redox
reactions in solution.
a) reversibility
b) kinetics
 )
c) electro activity (n,
2) Looks at i vs. E response of small, stationary

electrode in unstirred solution using triangular
waveform for excitation
Cyclic voltammetry
excitation
The Peak current (ip) for a
reversible couple At 25 oc is
given by Randles-Sevcik
equation
Polarogram(CV) Where n- number of

electrons, A = electrode area
(Cm2), C =concentration, D =
the diffusion coefficient (Cm2S-
1
) and ν = Scan rate (Vs-1).
Randles-Sevcik equation
• Note that Current (ip)

• Directly proportional to
concentration and
electrode area
• Increases with the square
root of the scan rate and
square root of the
diffusion coefficient
• Characteristics of
Reverse reactions
Appearance of the polarogram
Depends on the
following:
1. Reversibility of the
reaction
2. Supporting
electrolyte
3. Scan rate
4. Type of working
electrode
Iron cyanide electrochemistry
Cyclic voltammogram of 6mM K3Fe(CN)6 in 1M KNO3

Diagnostic test to decide the reversibility
of a redox reaction by CV
What type of reaction are represented by this CV’s?
ii
iii
iv
Question
• Which type of reaction is represented by

this polarogram
a
b
Exercise
CV for Paranthion in 0.5M pH 5sodium acetate buffer in 50% ethanol on

HMDE Scan rate : 200MV
Interpret this voltamogram and explain how the

peaks are formed. (C H O) PSOC H NO
2 5 2 6 6 2
Supporting electrolyte- Complex
formation
• Potential shifts and current increases
and reversibility of the reaction E1/2 – more –ve than M+
changes
1.5 Can determine complex ion
1
Ce(IV)-DTPA
Ce(IV)-EDDS and formation constant
Ce(IV)-EDTA
Ce(IV)-NTA
Ce(IV)
0.5
Reverse reactions
I / mA
0 Mn+ + Hg + ne-   M(Hg)

-0.5
Mn+ + xA-    MAx(n-x)+

-1
500 700 900 1100 1300 1500
E /mV vs. Ag/AgCl
Effect of pH
PANI-IND 1
0.002
0.000
I/A
1.5
2.5
3.5
-0.002 4.5
5.5
6.5
7.5
-0.004
1000 500 E/mV 0 -500
Sketch the expected CV from this
reaction

Anodic and Cyclic Voltammetry

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Stripping and Cyclic

Two step technique

• Stripping: After reducing and accumulating the

- Favorable signal to background ratio

• Formation of intermetallic compounds between metal and

• Adsorption of unwanted organic which can affect peak

Solutions to overcome the above issues: short deposition

reduction of ligand / metal complex / catalytic processes

-The most widely used stripping analysis

- Preconcentration is done by cathodic (REDUCTION)

- Metals are preconcentrated by electrodeposition into a

- Deposition potential is usually 0.3 – 0.5 V more negative

- Electrode rotation or solution stirring is employed to

- Metal ions are reduced and concentrated as

CHg = concentration of metal in the amalgam

- Peak potentials are used to identify metals in sample

- Hg film is more sensitive and more efficient in preconcentration

- Hg film gives sharper peaks and improved resolution for mixtures

- Bismuth and gold electrodes may also be used

A = area of film l = thickness of film = scan rate during stripping

- Mirror image of ASV

- Involves anodic deposition of analyte and subsequent

An- + Hg ↔ HgA + ne-

- Useful for measuring organic and inorganic compounds

- Known as stripping potentiometry

- Potentiostatic control is disconnected following

- Concentrated metals are reoxidized by an oxidizing agent

- Oxidation is facilitated by stirring during stripping

M(Hg) + oxidant → Mn+

- Variation of the working electrode potential is recorded

- Stripping voltamogram is then obtained

- Potential measurements are used to identify metals in

Involves reduction of the metal in the adsorbed complex

- Response of surface-confined species is proportional to

- Detection limits as low as 10-10 – 10-12 M

- Used for measuring organic compounds

- Provides qualitative and quantitative analysis for

- Involves mechanical transfer (by rubbing) of trace

- Electrode is usually paraffin-impregnated graphite

- Voltammetric measurement and stripping of the

Used for studying

2) Looks at i vs. E response of small, stationary

Polarogram(CV) Where n- number of

• Note that Current (ip)

Cyclic voltammogram of 6mM K3Fe(CN)6 in 1M KNO3

• Which type of reaction is represented by

CV for Paranthion in 0.5M pH 5sodium acetate buffer in 50% ethanol on

Interpret this voltamogram and explain how the

0 Mn+ + Hg + ne-   M(Hg)

Mn+ + xA-    MAx(n-x)+

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