POLAROGRAPHY AND

VOLTAMMETRY

POLAROGRAPHY AND
VOLTAMMETRY..general
Electrochemical method: measure
current as a function of applied
potential in electrochemical cell.
Analytical signal current (Faraday
current) which flows through cell during
the reaction of the analyte at the
working electrode with a small surface.

POLAROGRAPHY AND
VOLTAMMETRY..general
Analyte = cation/anion/molecule
Plot i as a function of potential (A vs V):
voltammogram (provide quantitative and
qualitative information)
Voltammetry: an electrochemical method in which
we measure current as a function of the applied
potential
Voltammogram: a plot of current as a function of
applied potential

POLAROGRAPHYgeneral
Earliest voltammetry technique: Polarography 1920
by J. Heyrovsky - a type of voltammetry that use
Dropping Mercury Electrode (DME) or Static
Mercury Drop Electrode (SMDE) as the working
electrode
Polarography current-potential curve polarogram.
Current-potential curve is recorded by using a liquid
working electrode whose surface can be renewed
periodically or continuously: Dropping Mercury
Electrode (DME) and static mercury drop electrode
(SMDE)

VOLTAMMETRYgeneral
Voltammetry
All methods in which current-potential
measurement are made at stationary and
fixed working electrode: Hanging mercury
drop electrode (HMDE), thin mercury film
electrode (TMFE), glassy carbon electrode
(GCE), carbon paste electrode (CPE) or other
solid electrodes

POLAROGRAPHYgeneral
Polarography : a form of voltammetry using DME or
SMDE as the WE
Measure the current that flow through DME during
a linear/direct voltage- direct current polarography
(DCP) together with counter electrode /reference
electrode
2 components of current - faradaic current (if) and
capacitive current (ic).
if provides measuring signal and ic is interference
signal

POLAROGRAPHY
2 components of current - faradaic current (if) and
capacitive current (ic).
faradaic current (if) : any current in an
electrochemical cell due to an oxidation or
reduction reaction of analyte
capacitive current (ic): any current from a flow of
electron that charge the mercury droplet with
respect to the solution ( + or -) (residual current or
nonfaradaic current no reduction/oxidation
process)

POLAROGRAPHY
From normal polarography;

2) Limiting current is measured from

the maximum current or average
current.

1) Limiting current or diffusion

current is obtained from
reduction / oxidation of
analyte in solution

POLAROGRAPHY
If if / ic = 1 useful signal cannot be separated
from interference signal can effect detection limit
of DCP = signal-noise ratio (LOD: 3 S/N)
maximum value for if which is obtained when all
the analyte particles transported to the surface of
the mercury drop by diffusion (reduced or oxidised)
is called diffusion current (iD)
Relationship between iD and the analyte
concentration is given by Ilkovic Equation

POLAROGRAPHY
Relationship between iD and the analyte s
concentration is given by Ilkovic Equation

iD = 0.607.n.D1/2.m2/3.td1/6.Ca
iD: Diffusion current (max)
n: No of electron exchanged in the charge-transfer
electron
D: Diffusion coefficient of the analyte
td: Dropping time of the mercury drop
Ca: Concentration of the analyte

POLAROGRAPHY
if / ic can be improved to get a higher sensitivity.
To increase if by stripping voltammetry in which
analyte is accumulated electrolytically at a
stationary working electrode before voltammetric
determination
To eliminate ic sampled DC polarography and
pulse method.

POLAROGRAPHY
sampled DC polarography :
current is measured at the end of a potential step
e.g at a constant potential and at an electrode
surface that remain constant and reduces the
contribution of ic to the measuring signal to a
minimum
gives smooth polarogram and more sensitive

POLAROGRAPHY
Types of pulse polarography

POLAROGRAPHY
1) Pulse polarography (normal, staircase and square
wave):
Substantial improvement in senstivity and
detection limit from normal polarography.
Limiting and peak currents are directly
proportional to the concentration of analyte. Half
wave and peqak potential are used for qualitative
purposes.

POLAROGRAPHY
Differential pulse polarography
Uses a series of potential pulse
characterised by a cycle of time,
, a pulse time of tp, a potential
pulse of Ep and potential step
per cycle, Es.
Typical = = 1 s, tp = 50 ms, Ep
= 50 mv, Es = 2 mV
Current is measured twice,
approximately 17 ms before
forward pulse and for
approximately 17 ms before the
reverse pulse. Difference in the
two currents gives rise to peakshape voltammogram

POLAROGRAPHY
Differential pulse polarography

POLAROGRAPHY
Peak currents are directly
proportional to the concentration of
analyte.
Half wave and peak potential are
used for qualitative purpose.
Pulse polarography is more popular
due to its sensitivity and detection
limit are improved

Is used for analysis of metal ions,

inorganic ions (IO3- and NO3-) and
organic compounds contains easily
reducible or oxidisable functional
(carbonyl, carboxylic acid and C=C)

POLAROGRAPHY: application 1
Example:
The DPP analysis of mixtures of indium and cadmium in
0.1 M HCl is complicated by the overlap of their
respective polarograms. The peak potential for indium
is at -0.557 V and that for cadmium occurs at a potential
of -0.597 V. When a 0.800 ppm indium standard is
analysed, the peak current is found to be 200.5 at 0.557 V and 87.5 at -0.597 V. A standard solution of
0.793 ppm cadmium gives peak current of 58.5 at
0.557 V and 128.5 at -0.597 V. What is the concentration
of indium and cadmium in a sample if the peak current
is 167.0 at potential of -0.557 V and 99.5 at a potential
of -0.597 V ?

POLAROGRAPHY
Answer:

[Indium] = 0.606 ppm

[Cd] = 0.205 ppm

POLAROGRAPHY: application 2
Example:
The concentration of As(III) in water can be
determined by DPP in 1.0 M HCl. The initial
potential set to -0.1 V versus the SCE, and is
scanned toward more negative potential at a rate of
5 mV/s. Reduction of As(III) to As(0) occurs at a
potential of approximately -0.44 V versus a SCE. The
peak currents corrected for residual current, for a
set of standard solution are shown in the following
table:

POLAROGRAPHY
As(III) / M
1.00 x 10-6
3.00 x 10-6
6.00 x 10-6
9.00 x 10-6

Ip / A
0.298
0.947
1.83
2.72

What is the concentration of As(III) in a sample of

water if the peak current (Ip) under the same
conditions is 1.37 A (answer: 4.49 x 10-6 M)

VOLTAMMETRY
- Time dependent potential is applied to an
electrochemical cell and the current flowing
through the cell is measured as function of that
potential.
Voltammogram is recorded: qualitative and
quantitative information about the species involved
in oxidation or reduction reaction

VOLTAMMETRY
Use to study:
a) oxidation and reduction processes in various
media

b) adsorption processes on surfaces

c) electron transfer mechanisms

VOLTAMMETRY
Voltammetric instruments:
Use 3-electrode immersed in a solution containing
the analyte and an excess of a non-reactive
electrolyte called a supporting electrolyte
a)WE : Hg, (HMDE or Hg film), DME / SMDE
b) AUX: Pt
c) RE: SCE, Ag/AgCl
Current is measured at WE versus std /ref electrode.

VOLTAMMETRY
Voltammetric instruments:

a)WE : kept small to enhance its tendency to

become polarised. Its potential versus a RE is
varied linearly with time
b) AUX: passes current between WE and AUX
electrode

VOLTAMMETRY E/chemical cell

Typical electrochemical
cell for voltammetry
3 electrodes (AUX, WE,
RE)
N2 purge line
Stir bar

VOLTAMMETRY: electrodes

a)
b)
c)

WE: Hg
3 types:
Hanging mercury drop electrode (HMDE),
Dropping mercury drop electrode (DME)
Static mercury drop electrode (SMDE)

VOLTAMMETRY: Hg as WE
Advantageous of Hg as WE:
a) High overpotential for reduction of H3O+ to
H2 (e.g -1.0 V)
b) Ability of metals to dissolve in the mercury
forming an amalgam
c) Ability to easily renew the surface of
electrode by extruding a new drop.

VOLTAMMETRY: Hg and others

Disadvantageous of Hg as WE:
cannot be used as at potential > negative than
-1.3 and more positive than +0.4 V (SCE)
depending on the composition of the
solution. > +0.4 V Hg is oxidised
Alternative: use other types of electrodes: solid
electrode (Pt, gold, silver, C, MCPE).

VOLTAMMETRY: Hg and others

Use other electrodes: solid electrode (Pt, gold,
silver, C).
Pt

Hg

VOLTAMMETRY: e/chemical cell

Other arrangement in voltammetric cell:
a) N2 purge line for removing dissolved O2.
(Why ?)
b) Optional stir bar (Why?)

c) Electrochemical cell in various sizes

(50 l to 100 ml)

VOLTAMMETRY: e/chemical cell

N2 purge line for
removing
dissolved O2.
To avoid any O2
peaks appear
due to reduction
of dissolved
oxygen
(2 peaks)

VOLTAMMETRY
Voltammetric wave:
A S shape wave obtained in current voltage
plot in voltammetry: linear sweep
voltammetry.
Limiting current:
Constant current which is limited by the rate at
which the reactant can be brought to the
electrode by mass transport processes

VOLTAMMETRY
Half wave potential:
Occur when the current is equal to one half of
the limiting current
Hydrodinamic voltammetry:
Type of voltammetry in which the analyte
solution is kept in continuous motion.

VOLTAMMETRY: Faradaic current

Current in voltammetry:
Faradaic current:
any current in an electrochemical cell due to an
oxidation or reduction reaction.
Due to reduction cathodic current
Due to oxidation anodic current

VOLTAMMETRY: Factors effect FC

Magnitude of FC is influenced by 2 factors:

a) Rate of the electrochemical reaction: the rate at

which the reactant and products are transported
to and from the electrode surface
(mass transport)
b) The rate at which electrons pass between electrode
and the reactants and products in solution.

VOLTAMMETRY: mass transport

Mass transport (reactant and
products are transported to
and from electrode surface):
3 modes diffusion,
migration and convection.
Diffusion
Diffusion creates diffusion
layer(DL). Width of DL ()
increase with time as the
concentration of reactant
near the electrode decrease.

VOLTAMMETRY: mass transport

Migration: charged particles in solution are
attracted or repelled from electrode that has
a positive and negative charge.
Convection: when a mechanical means is
used to carry reactants towards electrode
and remove products from electrode. (stir
the solution): hydrodynamic voltammetry.

VOLTAMMETRY: mass transport

Concentration gradient for the analyte
showing the effects of difussion and
convection as methods of mass transport

VOLTAMMETRY: other currents

Mass transport: the movement of material
toward or away from the electrode.
Diffusion: the movement of material in
response to a concentration gradient
Diffusion layer: the layer of the solution
adjacent to the electrode in which diffusion is
the only means of transport

VOLTAMMETRY: other currents

Nonfaradaic current: result from unrelated to
any redox reaction.
Residual current: a small inevitably flows
even in the absence of analyte (2
components/sources: i) faradaic current due
to oxidation or reduction of trace impurities
and ii) charging current). = background
current

VOLTAMMETRY: other currents

Electrical double layer: interface between a
positively or negatively charged electrode
and the negatively or positively charged layer
of the solution in contact with the electrode.

Charging current: a current in an

electrochemical cell due to the electricity
double layers formation.

VOLTAMMETRY
Quantitative and qualitative aspects
Quantitative: relating current to [analyte] in
bulk solution.
Qualitative: extracting std-state potential for
redox reaction

VOLTAMMETRY
Cyclic voltammetry; introductory step in
voltammetry analysis. To obtain information on
electrochemical behaviour of species in certain
solution.
Stripping voltammetry: a form of voltammetry in
which the analyte is first deposited on the electrode
and then removed or stripped electrochemically
while monitoring the current as a function of
applied potential
(anodic, cathodic and adsorptive stripping
voltammetry)

CYCLIC VOLTAMMETRY
Introductory step in voltammetry analysis.
Function;
To obtain information on electrochemical behavior of
species in certain solution.
To study electron transfer and to probe subsequent chemical
reaction

Study the oxidation or reduction reaction, the detection of

reaction of intermediate and the observation of follow up
reaction of products formed at electrode.

CYCLIC VOLTAMMETRY
Electrode is imposed
with a cyclic linear
potential sweep and
obtaining currentpotential curve (cyclic
voltammogram)

Apply triangular
waveform produces
forward (1) and then
reverse (2) scan

Schematic diagram of E
versus time for CV technique

CYCLIC VOLTAMMETRY

Potential is 1st varied linearly from +0.8 V to

-0.15 V vs SCE at which point the scan
direction is reversed and the potential is
returned to its original value of +0.8 V.

Scan rate = 50 mV/s.

Cycle = single/repeated
Potentials at which reversal take place are
called switching potentials. (-0.15 V =
switching potential)

A scan in direction of more negative

potential = forward reaction and more
positive potential = reverse reaction
(depend on direction of first scan)
Cycle time: 1 ms or less to 100 s or more
Example: 40 s

CYCLIC VOLTAMMETRY
Sweep /scan Initial (Ei), switching (Es) and
Final (Ef) potentials.
E = Ei + t (forward sweep)
E = Es t (reverse sweep)
( = sweep rate /scan rate in V/s).
Multiple cycles also used rather than single
cycle

CYCLIC VOLTAMMETRY
Possible cycles CV
waveforms:
A) reversible
B) irreversible
C) quasi-reversible
at Hg electrode
O =oxidised form
R = reduced form

CYCLIC VOLTAMMETRY

CV- Important parameters:

A) Cathodic peak potential, Epc
B) Anodic peak potential, Epa
C) Cathodic peak current, Ipc
D) Anodic peak current, Ipa

Reversible electrode reaction:

Anodic and cathodic peak currents are approximately equal
Ep = | Epa Epc | = 0.059/n (in V) where n = no of
electron involved in redox reaction
Irreversible:
Ep exceeding expected value

CYCLIC VOLTAMMETRY
CV response current vs potential
Forward: oxidised form is reduced while on reverse
sweep, the reduced form near electrode is reoxidised.
Major use: provide qualitative information about
electrochemical processes under various conditions.
E.g: CV of parathion in 0.5 M pH 5 sodium acetate
buffer in 50% ethanol. HMDE as WE at scan rate =
200 mV/s.

CYCLIC VOLTAMMETRY
CV of parathion in 0.5 M pH 5 sodium acetate buffer in 50% ethanol.
HMDE as W.E, s.rate = 200 mV/s.

CYCLIC VOLTAMMETRY
Switching potentials:
-1.2 V and +0.3 V
Initial forward scan from 0.0 V.
Produces 3 peaks: A, B and C.
A= cathodic peak from reduction
of parathion to give hydroxylamine
derivative
B = anodic peak from oxidation of
hydroxylamine to a nitroso
derivative during reverse scan
C= cathodic peak from reduction of
the nitroso compound to the
hydroxylamine

CYCLIC VOLTAMMETRY
Azo dye (reactive dye group)
Chemical name
[2,7-naphthalenedisulfonic acid, 4-amino-5hydroxy-3,6-bis ((4 - ( (2 (sulfoxy) ethyl)
sulfonyl) phenyl) azo)-tetrasodium salt],

Gives 3 cathodic peaks - 2nd peak is the well

and characteristic peak.
1

No oxidation peak.
[ref: M.H.Yaacob and Z. Nursyamimi (2012)
J of Health & Environmental Sc ]
2

CYCLIC VOLTAMMETRY
Azo dye (reactive dye group)
The first two obtained reduction peaks are
suggested due to subsequence reduction
process of the two azo groups to amines.
Both hydroxyl and amino groups are electron
donating substituent in the RB5 dye
compound. The first reduction peak is
suggested from reduction process of the azo
with the hydroxyl group and followed with
the reduction process of the other azo with
amino group, which gave second reduction
peak on the voltammograms.

STRIPPING VOLTAMMETRY
3 related techniques: anodic, cathodic and adsorptive stripping
voltammetry
Anodic stripping (ASV)
2 steps:
Step A) controlled potential electrolysis using HMDE or Hg film
electrode - is held at a cathodic potential sufficient to deposit metal
ion on the electrode.
E.g Cu2+ - deposition reaction : Cu2+ + 2e Cu (Hg)
Copper is amalgamated with Hg.
Function : pre-concentrating the analyte from larger volume of the
solution to a smaller volume of electrode.
Solution is stirred during electroylsis (why?)
Near the end of deposition time, stirrer is stopped (why?)
Deposition time = 1-30 min.

STRIPPING VOLTAMMETRY
Anodic stripping (ASV) .. cont
2 steps:
Step B) potential is scanned anodically toward
more positive potentials. With sufficient
positive potential, the analyte is stripped from
electrode, returning to solution as its oxidised
form:
E.g Cu2+ - deposition reaction :
Cu(Hg) Cu2+(aq) +2e

Current (i) during stripping step is monitored

as a function of potential giving rise to peakshaped voltammogram

STRIPPING VOLTAMMETRY
Application:

Bi, Cd, Cu, Ga, In, Pb, Sn, Zn

Can be determined simultanouesly

STRIPPING VOLTAMMETRY

Simultaneous determination of heavy metals

using DPASV of 25 ppm Zn, Cd, Pb and Cu

STRIPPING VOLTAMMETRY
Cathodic stripping (CSV)
2 steps:
Step A) deposition step involves the
oxidation of Hg electrode to 2Hg +1 which
then reacts with analyte to form insoluble
film at the surface of electrode.
E.g Cl- - deposition reaction :
2Hg (l) + 2Cl- Hg2Cl2 (s) + 2e

STRIPPING VOLTAMMETRY
Step B) stripping is accomplished by
scanning cathodically toward more
negative potential, reducing Hg+ back to
Hg and returning the analyte to solution;
Hg2Cl2 (s) + 2e 2Hg (l) + 2Cl- (aq)

STRIPPING VOLTAMMETRY
-applications:
bromide
chloride
iodide
mercaptan
sulfide
thiocyanate

STRIPPING VOLTAMMETRY
Adsorptive stripping (CSV)
deposition step occures without electrolysis.
Analyte adsorbs to the electrode surface. During
deposition the electrode maintained at a potential
that enhances adsorption.
E,g: adsorption of a neutral molecule on a Hg drop
is enhanced if the electrode is held at -0.4 V (SCE).
When deposition is complete, the potential is
scanned in an anodic or cathodic direction
depending on whether we wish to oxidise or
reduce the analyte

STRIPPING VOLTAMMETRY
Adsorptive stripping (CSV)
Application:
Bilirubin
Codiene
Cocaine
Testosterone
Aflatoxins

STRIPPING VOLTAMMETRY
DPP voltammogram for 5 x 10-10 M
riboflavin

Preconcentration for
(A) 5 min

(B) 30 min
at -0.2 V.

Ep almost constant but Ip incresead.

GTF 205/3
Thank you
Good luck in final exam !!