VOLTAMMETRY &

ITS APPLICATION

Kapita Selekta Kimia Analitik (KST407)

Program Studi Kimia
FST Universitas Airlangga
 Voltammetry

• an electroanalytical method that

measures the current in an analyte as
a function of the applied potential
under polarized working electrode
• Micro size electrode is used (m2 )
 Electrodes

1. Working electrode
▪ a microelectrode, place where redox occurs
▪ surface area in the level mm2 to limit current flow
▪ Pt, Au, C, GC, Hg, MFE
2. Reference electrode
constant potential reference (Ag/AgCl, SCE)
3. Counter electrode
inert material (Hg, Pt) plays no part in redox but completes circuit
 Principle of electrode work

❖ a potential is given between the working electrode and the

reference electrode
❖ Electrochemical reactions occur at the work electrode surface
❖ The resulting current is measured between the working
electrode and the auxiliary electrode
 Instrumentasi dalam voltammetri

sample vessel
 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
 Mekanisme Transpor
electrode solution • Transpor ion pada permukaan
elektroda
e- Pb2+ – Konveksi: ketika larutan
e- diaduk atau elektroda diputar
– Migrasi: adanya medan
listrik→ diminimalisasi
dengan penambahan larutan
elektrolit pendukung
– Difusi: disebabkan gradien
konsentrasi
Pb°
diffusion
layer
 Mass Transport vs Electrode
Kinetics

Experimentally rate of electron transfer is fast for many processes so

can be assumed:
- current depends only on mass transfer
- surface concentrations are in equilibrium with applied potential as
expressed by the Nernst equation

Processes which satisfy these assumptions

are known as electrochemically reversible
Potential applied on the working electrode is usually swept over (i.e. scan) a
pre-defined range of applied potential

0.001 M Cd2+ in 0.1 M KNO3 supporting electrolyte

Electrode become more and more
reducing and capable of reducing Cd2+
All Cd2+ around the electrode has
Cd2+ + 2e- Cd already been reduced. Current at
Current starts to be registered at the the electrode becomes limited by
i (A)
electrode the diffusion rate of Cd2+ from the
Working electrode is E½ bulk solution to the electrode.
no yet capable of Thus, current stops rising and
reducing Cd2+  levels off at a plateauid
Current at the working
only small residual
electrode continue to rise as
current flow through
the electrode become more
the electrode Base line
reducing and more Cd2+
around the electrode are being of residual
reduced. Diffusion of Cd2+ current
does not limit the current yet

-0.2 -0.4 -0.6 -0.8 -1.0 -1.2 -1.4

V vs SCE
 Classic voltammogram DC (direct current) on DME
(dropping mercury
3 electrode).

Qualitative information: half wave potential

Quantitative information: wave height
 Principle

• Increasing potential
U

Pb
• Measuring current
I Cd

DI

time

• Metal ionic is reduced on the

electrode surface and soluble in the
Reduction to metal mercury to form amalgam
(amalgam formation)
 Influence of the Kinetics of
Electron Transfer on the Faradaic
Current

• When electron transfer kinetics at the electrode

surface are fast, the redox reaction is at
equilibrium, and the concentrations of reactants
and products at the electrode are those specified
by the Nernst equation.
• Such systems are considered electrochemically
reversible.
• In other systems, when electron transfer kinetics
are sufficiently slow, the concentration of reactants
and products at the electrode surface, and thus the
current, differ from that predicted by the Nernst
equation. In this case the system is
electrochemically irreversible.
 Non faradaic Currents
• Currents other than faradaic may also exist in an electrochemical cell that are
unrelated to any redox reaction.
• These currents are called nonfaradaic currents
• The most important example of a nonfaradaic current occurs whenever the
electrode's potential is changed.
• When mass transport takes place by migration negatively charged particles in
solution migrate toward a positively charged electrode, and positively charged
particles move away from the same electrode.
• When an inert electrolyte is responsible for migration, the result is a structured
electrode-surface interface called the electrical double layer (EDL)
• The movement of charged particles in solution, gives rise to a short-lived, non-
faradaic charging current.
• Changing the potential of an electrode causes a change in the structure of the
EDL, producing a small charging current.
 Residual Current
• Even in the absence of analyte, a small current flows through an
electrochemical cell.
• This current, which is called the residual current, consists of two
components:
– a faradaic current due to the oxidation or reduction of trace
impurities,
– a charging current. it is the current needed to charge or discharge
the capacitor formed by the electrode surface-solution interface.
This is called the condenser current or charging current.
– It is present in all voltammetric and polarographic experiments,
regardless of the purity of reagents.
– As each drop of mercury falls, it carries its charge with it to the
bottom of the cell. The new drop requires more current for
charging.
 Half wave potential of the analyte

• Maximum possible working ranges of different electrode

types
Oxidation of electrode
Mercury

Glassy Carbon

Gold
H+ + e- H
Platinum

Potential (V) -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1 1.2
 Types of
Voltammetric
Technique
Polarography
– uses the dropping mercury
electrode (DME, SMDE)
– ppm level
Stripping) Voltammetry
– uses a stationary electrode
(HMDE, RDE)
– ppb level with deposition
 Voltammetric Techniques
Polarography Stripping Voltammetry

U U

Pb Pb

I Cd I Cd

DI DI Electrolysis

time time

Reduction to metal Reduction to metal Oxidation to ion

(amalgam formation) (amalgam formation) (determination)
 Method
• Excitation signal applied
– Wave response based on method
• Linear
• Differential pulse
• Square wave
• Cyclic
– Developed current recorded
Circuit and
Signals
 DC-Polarogram with DME

I U

U t
 Differential Pulse: DP

• developed to decrease capacitive current more than

DC
• resulting curve shows peaks
– better to evaluate
– more sensitive because of lower background
• Pulses applied before the end of the voltage step
• Current measured before pulse (1) and before the end
of pulse (2)
• Currents are subtracted --> peak shape
• Detection limit until 10-8 M
Direct current and differential pulse

quantitative information

U
I
quantitative information

U½ U
qualitative information
 Properties

1. two step measurement

Stripping • electrochemical deposition
(enrichment)
voltammetry • determination (stripping step)
2. high sensitivity
3. for trace analysis (down to ppt range)
4. mainly for metal analysis.
 Stripping Voltammetry
1. Deposition of the analyte on the electrode.
• Constant potential is applied, solution is stirred
• Example: Cd, Pb ions are reduced to metal
2. Intermediate: Equilibration without stirring but with deposition potential
3. Stripping step:

• Without stirring
• Potential ramp is applied, analyte is reduced or oxidized
• Example: Cd, Pb metal is reoxidized again.

• Advantage:
Sensitivity increase due to increase in deposition time --> Trace Analysis

• Two types of Stripping Voltammetry:

Anodic Stripping Voltammetry (ASV)
Cathodic Stripping Voltammetry (CSV)
 Anodic Stripping Voltammetry (ASV)
ANODIC because the stripping step is an oxidation sweep goes to positive potentials

2 step

1. deposition (metal reduction)

Cd2+ → Cd0(Hg)

2. determination (Stripping)
Cd0(Hg) → Cd2+
Cathodic Stripping Voltammetry (CSV)
CATHODIC because the stripping step is an reduction sweep goes to
negative potentials

2 step

▪ deposition (metal oxidation, precipitate on mercury

drop surface)
• 2 Hg + 2 CN- → Hg2CN2
▪ determination (Stripping) 2 steps
• Hg2CN2 → 2 Hg + 2 CN-
Adsorptive Stripping Voltammetry (AdSV)
• Deposition is now an adsorption of a metal complex
• Stripping step is the reduction of the adsorbed metal complex.

• Can also be called CSV = Cathodic Stripping Voltammetry

• cathodic because the stripping step is an reduction
• sweep goes to negative potentials
• or AdCSV = Adsorptive Cathodic Stripping Voltammetry

• deposition (adsorption)
• Ni2+(DMG-)2 → Ni2+(DMG-)2ads

• determination (Stripping)
• Ni2+(DMG-)2 ads → Ni2+ + 2 DMGred

• DMG: Dimethylglyoxime, complexing agent

 • Pengukuran arus listrik dilakukan sebagai aluran
potensial dengan rentang potensial yang
memiliki potensial awal dan akhir sama.

• Voltametri siklis adalah teknik yang serbaguna

dalam studi spesi elektroaktif
• special mode for research: investigations of
electrode kinetics and reversibility of
Cyclic electrochemical reactions

voltammetry • potential is increased and decreased (forward

(CV) and backward sweep)
• Reaction and reverse reaction are registered
(upper and lower part of right curve)

• eksperimen pertama dalam studi elektrokimia

suatu senyawa, material biologi, atau studi
permukaan elektroda Di sekitar permukaan
elektroda terjadi beberapa proses, yaitu transfer
elektron, difusi dan reaksi kimia
Cyclic voltammogram
 Overpotential
• Overpotential h always reduces theoretical cell
potential when current is flowing
– h = Ecurrent - Eequilibrium
• Overpotential due to electrode polarization:
– concentration polarization - mass transport
limited
– adsorption/desorption polarization - rate of
surface attach/detachment
– charge-transfer polarization - rate of redox
reaction
– reaction polarization - rate of redox reaction of
intermediate in redox reaction
• Overpotential means must apply greater potential
before redox chemistry occurs
 Voltammograms
• Current against applied voltage
• Increase in current at potential at which analyte
is reduced
• Reaction requires electrons
• supplied by potentiostat
• Half wave potential (E1/2) is close to
• E0 for reduction reaction

• Limiting current proportional to analyte activity

Application
• Ultra Trace range metals (sub ppb)
• Wastewater Analysis
• Industrial Water/Liquor Analysis
• “Polarographic Determination of
Sulfur Compounds in Pulping Liquors”
; Sulfur compounds in weapons
• Pharmaceutics
• Environmental Studies
• Biological/Biochemical Analysis
• Plating Analysis