Techniques

LIMITATION OF DC POLAROGRAPHY
Ever since the development of DC polarography a great
deal of efforts have been undertaken to compensate
several of the following three main limitations:
a) The drawback of direct current (DC) polarography as
regards sensitivity is the current required to change
the potential of the dropping mercury electrode
(DME) to the required value: at a depolarizer
concentration of 10-5 mol 1-1, this time-averaged
charging current is comparable to the Faradaic
current.
b) Lack of resolution of the sigmoid shaped waves (DC,
NPP, etc. polarographies). In order to sufficiently
distinguish two polarographic waves so as to be able
to measure their corresponding half-wave potentials
and limiting current values, it is necessary that the
former half-wave potentials should differ in more
than 200 mV. All subsequent polarographic
techniques, in which the obtained response is in the
form of a peak (derivative polarography, square-wave
polarography,
AC
polarography,
differential
polarography, differential pulse polarography, etc.)
present a higher resolution, being a difference of only
about 50 mV sufficient to be able to discriminate two
substances presenting close half-wave potentials.
c) As observed in figure 1 (DC polarography) the noise
of the oscillations increases considerably after the

reduction of a substance. Thus, making the calculation of

the limiting current of any other compound, which is
being reduced after the first substance difficult,
especially when this compound is present at low
concentrations. This difficulty decreases when peak
shaped polarograms are attained, for which the signal
returns to the baseline.
EVOLUTION OF POLAROGRAPHIC TECHNIQUES
In order to solve the above-mentioned drawbacks different
solutions have been proposed, although nowadays several can
be considered obsolete. In table I an account of the most
significant contributions is presented.
Table I. Polarographic techniques
Technique

Resolution

Limit of determination
(for lead) mol l-1

Polarograms with sigmoid shape

DC
200 mV
10-4
Rapid
200 mV
10-4
DC tast
200 mV
10-5
-6
NPP
200 mV
10 10-7
Polarograms with peak shape
Differential
50 mV
10-5
Derivative
50 mV
10-5
-6
AC
50 mV
10 10-7
SWP
50 mV
10-7 10-8
DPP
50 mV
10-7 10-8
DC: direct current; NPP: normal pulse; AC: altern
current, SWP: square wave; DPP: differential pulse

Figure 1. Several polarographic techniques obtained by means of a digital polarograph. The DC technique has been obtained
with a dynamic mercury electrode, whereas those of DC tast and AC have been attained with a static electrode and current
integration. Meaning of abbreviations: mt = measuring time, dl= drop life, t= time, A= electrode surface, V= voltage applied to
the working electrode. The scannings are cathodic, i.e., towards more negative voltages, giving rise to cathodic currents

One of the first interesting contributions was directed

towards the elimination of the noise produced by
capacitive current, which contributes, especially in the
beginning, to the growth of the mercury drop. This is due
to the fact that for a constant mass flow rate of mercury,
the variation rate of the drop surface is very fast, which is
comparable to a condenser whose plates are changing
their surface very rapidly and, therefore, the charging
current will be initially very high.

Figure 2.

Variation of the drop surface, and the

intensities of the capacitive (ic) and diffusion (id) currents
with time

The equations giving the intensity variations of both the

diffusion and capacitive currents, together with their
corresponding ratio are:
2/3 -1/3

ic = km t
id = km2/3t1/6
id/ic =kt1/2

[1]
[2]
[3]

which reveals that the signal/noise ratio improves with

time. Thus, in rapid polarography the first 20 ms of the
drop life are neglected in order to subsequently integrate
the current during the rest of the lifes drop. This option
implied the introduction of a synchronization element, the
knocker, nowadays present in all modern polarographs: a
blow of the knocker releases the previous drop and
defines the starting time of the new drop (from which the
first 20 ms are discarded before measuring the current).
The period of time between two successive blows of the
knocker will define the drop life. Tast polarography can
be considered as an evolution of rapid polarography, in
which the current measurement is carried out only at the
end of the drop life, in which the drop surface remains
almost practically constant with time.
ALTERNATING CURRENT (AC)
POLAROGRAPHY
This method is based on superimposition of a small
amplitude sine-wave voltage E~ over the linear voltage
ramp (see figure 1).
The E~ frequency ranges from 10 Hz to about 10
kHz. The resulting current contains, in addition to the
filtered-off DC component, the alternating current
component i which is proportional to the total cell
admittance
Y = Y+ jY

[4]

where Y and Y are the real and the imaginary

admittance components, respectively.
After amplification and rectification, the total
alternating current magnitude was originally recorded as a
function of DC voltage. The cell impedance in the
simplest case is composed of an ohmic solution resistance

Rs in series with the parallel combination of the electrode

double-layer capacity C and the Faradaic impedance
component ZF; the alternating current is a vector with a
definite phase in relation to the applied AC perturbation
voltage. Measurement of only total alternating current offers
no particular advantage during a detailed electrochemical
investigation. Alternating current polarography became
increasingly attractive after introduction of more
sophisticated instrumentation based on phase sensitive
detection with automatic solution resistance compensation.
This procedure consists of measuring the two curves: one
current component, also known as the real or the resistive
component which is in phase with E~ and the other, the
imaginary or the quadrature component which is phaseshifted 90 with respect to the E~ vector. If the amplitude of
E~ is precisely known, cell admittance Y()0 or impedance
Z() at a
given frequency
may
be
calculated as
E~
i~ =
= Y ( ) E ~
Z ( )
[5]
This information may be analogously obtained by finding the
absolute value of the alternating current vector and the phase
shift of i~ in reference to E. Appropriate Rs compensation is
crucial in phase-sensitive AC polarography because the IR,
drop causes phase error which is eliminated only after
laborious vector analysis. The in-phase component of a
phase-sensitive AC polarogram of a blank solution without
any electroactive compounds should be a zero line since
Y ' ( ) =

1
0
Rs

[6]

and the double-layer capacitance for the imaginary

component
Y " ( ) = C ( E )

[7]
Double-layer structure and adsorption of various surfaceactive substances may be examined by this method which
replaces cumbersome balancing bridge measurements.
The Faradaic peak-shaped contributions in both real and
imaginary AC curves, denoted as YF and YF, respectively,
are found in the potential region of the polarographic wave. A
general case with a finite charge-transfer rate relates these
Faradaic components to the kinetic parameters by
[8]

Y " F = nFA

k +e
k e

c ' Re d E c ' Ox E
2 + 2 + 1

[9]

Y ' F = nFA

k +e
k e
+1

c ' Re d E c ' Ox E
2 + 2 + 1

where c is surface concentration and

k +e
2DOx

k e
2DRe d

[10]

Both Faradaic components are proportional to bulk concentration and YF is a signal completely without charging
components, with a zero line ideally suited to analytical
applications. Furthermore, phase sensitive AC polarography
gives instantaneous information about reversibility at a given
by comparing the ratio of YF and YF.

A reversible electrode reaction corresponds to the limit

0, hence YF = YF. In contrast, the totally irreversible
process is characterized by 0 and YF 0. This AC
technique also determines double-layer capacity in the
presence of a quasi-reversible electrode reaction by
utilizing sufficiently high frequency, since is , and
hence Y 0 and Y c.
The kinetic parameters k and are evaluated by
plotting versus E:

Y "F
=
=
Y ' F Y "F

k +e
2DOx

k e
2DRe d

[11]

yielding two linear asymptotes at far positive and negative

potentials with respect to E1/2.
The transfer coefficient is calculated from the slope and
k0 and E from the coordinates of the asymptotes intercept. Due method for the determination is based on the
Faradaic phase angle
Y"
tan = F
Y 'F
[12]
which is plotted versus for the k determination. The
potential of the maximum on a cotan versus E plot yields
the value. Admittance or impedance data displayed as
complex plane plots are often used.
Electroactive species adsorption is sensitively indicated
by this method, which thus determines whether redox
system properties are obscured by a specific type of
interaction with the electrode. Strongly absorbable
electroinactive compounds yield peaks on the AC curves
located at potentials of the adsorption-desorption process.
However, they are much narrower and their frequency
dependence differs markedly from the Faradaic peaks.
Such peaks were also used for determination of surface
active compounds. In general, AC polarography is not
very sensitive, in particular in irreversible processes
without adsorption.

NPP keeps the DME at a constant potential before the start

of the Faradaic current; then, almost at the end of the drop
life, a voltage pulse is applied, the amplitude of
which gradually increases from drop the drop. The pulse
duration is about 200 ms. The current is usually measured
shortly and before the pulse end (about 20 ms after the pulse
edge) and is recorded versus the pulse amplitude. The
current-potential relationship for a reversible process is
i = nFcA

D 1

1 + P

[13]

where P = exp(nF/RT)(E-E1/2) and is the pulse duration. As

the pulse voltage becomes more negative than E1/2, the value
of P approaches zero, yielding a limiting current given by the
Cottrell equation:
i = nFcA

[14]

This mode is about seven times more sensitive than classical

DC polarography.
The shape of the curve is that of a normal DC polarogram.
In irreversible processes NPP may also determine the kinetic
parameter k0. Only the upper limit for k0 is higher than in DC
polarography since the time is now of the order of
milliseconds in contrast with the drop time t1 in DC
polarography.
Differential pulse polarography (DPP) (Figure 4) differs

PULSE POLAROGRAPHY

In pulse methods the procedures are based on the

application of pulse changes of potential and the current
response is measured at a suitable time relative to the time
of the pulse. The concept includes three methods: normal
pulse polarography (NPP), differential pulse polarography
(DPP) and square-wave polarography (SWP).
Pulse techniques improve detection limits since they
benefit from the different variation of diffusion and
capacitive current intensities with time: when carrying out
measurements at the pulse end, the capacitive current is
practicably negligible, being the value of the Faradaic
current still significant (see equation 3).

Figure 3. a) sudden variation of the potential, b) behaviour

of the diffusion (id) and capacitive (ic) currents with time. ta
and tb are the times used in the measurement of the current

Figure 4 DPP and NPP polarography. Variation of the

mercury drop area and voltage with time using the static
mercury electrode. dl: drop life, mt: measuring time; pt:
pulse time; A: electrode area, t: time; V: working electrode
voltage .

from NPP when prior the pulse application the potential is

not constant but is replaced by a ramp voltage with DC
polarographic characteristics. The pulse amplitude is
constant and the measured current is displayed as the
difference between the current sampled closely before
pulse application and the current sampled at the pulse end.
If the polarographic I-E equation is now differentiated
as
1
i = id
[15]
1+ P
and the Cottrell equation is substituted for id , the relationship for the DPP with a reversible process is
i=

n2F 2
D
P
AcE
.
RT
(1 + P )2

[16]

This equation is only valid for small values of pulse

amplitude E<RT/nF. The I-E curve is a derivative of the
classical DC polarographic wave. The peak current is

n2F 2
D
AcE
.
4 RT

i=

[17]

The peak potential is related to E1/2 by

E p = E1 / 2

E
2

[18]

The solution for i-E curves is also available for a slow

electrode reaction or for considering electrode sphericity.
In SWP, the polarization potential is a linear varying
voltage ramp over which a small amplitude square-wave
signal, usually 225 Hz and 1-50 mV amplitude, is
superimposed. This differs from NPP and DPP in that
perturbation continues during the whole drop life and the
response readout is positioned at a time of negligible time
change of the electrode surface. The signal, measured as a
function of the linear varying potential, is the difference
of current samples obtained at the end of each half cycle
of the square-wave signal; the DC signal component is
filtered off. The resulting i-E curve is a peak described for
a reversible reaction by the equation

i=

n2 F 2
D
P
.
cE
L
RT
(1 + P )2

[19]

In this equation L is the constant of the instrument defined

as

L=

( 1) m

m =0 (m + t

/ )1 / 2

[20]

E is the square wave amplitude, t is the time measured

from the half-cycle beginning and is the half-period of the
square wave. The peak half-width, W1/2, for small E is
given by

W1 / 2 = 3.52

RT 90 .5
mV at 25 C
=
nF
n

[21]

The theory of slow charge-transfer reactions reveals that

the peak height strongly decreases in the range of rate

10-1-10-4 cm s-1; below this value it is almost

completely insensitive toward the k0 change and yields peaks
about 20 times smaller than those in the reversible case.
constants k0

BIBLIOGRAPHY
Bard AJ and Faulkner LR (1980) Electrochemical Methods.
New York: John Wiley.
Bond AM (1984) Modern Polarographic Methods in
Analytical Chemistry. New York: Marcel Dekker.
Esteban M and Casassas E (2001) Tcnicas polarogrficas
Modernas. In: Blanco M, Cerd V and Lpez-Cueto G
(Edit). Mtodos Electroanalticos I. Palma de Mallorca.
Universitat de les Illes Balears
Henze G and Neeb R (1986) Elektrochemische
Analytik.Berlin: Springer Verlag.
Heyrovsky J and Kta J (1965) Principles of Polarography.
Prague: Publishing House of the Czechoslovak Academy
Sciences.
Kalvoda R and Volke J (1991) Differential pulse
polarography and voltammetry. In: Zyka J (ed.)
Instrumentation in Analytical Chemistry, vol. 1, p. 39. New
York: Ellis Horwood.
Vlek AA, Volke J, Pospiil L and Kalvoda R (1986)
Polarography. In: Rossiter BW and Hamilton JE (eds)
Physical Methods of Chemistry, vol. II, Electrochemical
Methods (2 edn), chap. 9, p. 39. New York: John Wiley.
Volke J and Lika F (1994) Electrochemistry in Organic
Synthesis. Berlin: Springer Verlag.
V.Cerd
Dep. Chemistry. University of the Balearic islands. Spain

i=

(1 + P )2
RT
.
c E
L
n 2F 2
D
P