International Journal of Modern Analytical and Separation Sciences, 2013, 2(2): 61-70

International Journal of Modern Analytical and Separation Science ISSN: 2167-7778

Journal homepage: www.ModernScientificPress.com/Journals/IJMAS.aspx Florida, USA
Article

Recent Advances in the Application of Polarographic

Techniques in Chemical Analysis

U. Lawal and E. E. Etim *

Department of Chemical Sciences, Federal University Wukari, Nigeria

* Author to whom correspondence should be addressed; E-Mail: emmaetim@gmail.com.

Article history: Received 30 January 2013, Received in revised form 8 June 2013, Accepted 18 June
2013, Published 6 July 2013.

Abstract: Created in 1922 by the 1959 Nobel prize winner in chemistry, Jaroslav
Heyrovsky, polarography a simple study of solutions by the means of electrolysis rose to
become one of the five most used methods of chemical analysis in the post world war one,
finding variety of uses even in the development of the atomic bomb ‘the Manhattan
Project’. The application of polarography has spread to almost all branches of chemistry.
The use of the brilliantly shining and pure liquid metal, mercury, an unlikely candidate for
an electrode material ushered in a new era in electrochemistry during the last century. At a
time when the solid electrode materials were dogged by the problems of irreproducibility
due to surface heterogeneity and impurity, mercury, which is largely free from such
malaise, became a new benchmark to study many fundamental electrochemical processes
quite accurately and with great precision. This paper aims at reviewing the principle, types
and recent advances in the application of polarography.

Keywords: chemical analysis; polarography; electrolysis; metal; mercury.

1. Introduction

Polarography no doubt is one of the most advanced and enhanced methods used in chemical
analysis, and its increasing accuracy and compatibility make it a competitive tool in instrumentation of

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Int. J. Modern Anal. Sep. Sci. 2013, 2(2): 61-70 62

analysis. A majority of the chemical elements can be identified by polarographic analysis, and the
method is applicable to the analysis of alloys and to various inorganic compounds. Polarography is
also used to identify numerous types of organic compounds and to study chemical equilibria and rates
of reactions in solutions. The impact of this technique in electrochemistry was extended far beyond the
routine electroanalysis. With the discovery of this technique the face of electrochemistry, which was
mostly referred to in the context of ionic equilibria, Debye-Huckel theory and solution
electrochemistry in general, started changing [1]. Polarography extended its influence in the study of
such diverse phenomena as electrocatalysis, electrochemical energy sources, batteries, fuel cells,
biological processes such as ion transport across membranes, solar cells, etc. The technique had a
major impact in the study of the mechanism of electrode reactions and consequent theoretical
developments of electrode processes such as studies of electrolytic diffusion processes and other
transport phenomena.

2. Principle of Polarography

The classical polarography method is based on the measurement of current as a function of

applied voltage where a current-voltage plot is referred to as a polarogram. A simple schematic of a
classical polarographic setup is shown in Fig. 1. The DME will continuously release mercury drops
that range in diameter from 0.1 to 1 mm in a preset frequency. In case of analyses that involve metal
ions, metal ions are reduced at the negatively charged mercury drops due to diffusion of positive ions.
Mn+ + ne = M (Hg)

D C s our ce

Vari able res is tanc e

V
 
_

D ME

H g pool
+

Figure 1. A simple schematic of a classical polarographic setup

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Int. J. Modern Anal. Sep. Sci. 2013, 2(2): 61-70 63

From the measurements of the current-potential curves resulting from electron transfer
processes at the surface of a DME, the identity and concentration of the reactant substance can be
determined. One of the features of polarography is that solutions as dilute as 10 -8 M can be analyzed
and sample volumes as small as 0.05 mL can be manipulated. Thus, the position of a wave in a
polarogram along the potential axis gives the identity of the substance while the magnitude of the
limiting current gives picture of the concentration variation of this material [2].
A very pure mercury patch can be obtained through distillation under vacuum (99.99 % pure).
Each drop represents a fresh electrode with a new exposed surface. The reproducibility of geometry of
each drop with the laps of time is another advantage of the DME over other electrodes. The large
activation overpotential for hydrogen gas evolution makes this electrode valuable for the study of
cathodic processes. One of the most important drawbacks of the Hg as electrode is its ease of
oxidation. Thus, Hg undergoes anodic dissolution at +0.25 V vs. SCE and is oxidized to insoluble
Hg2Cl2 in presence of chloride ions at zero V vs. SCE so it cannot be used for anodic oxidation above
+0.25 V vs. SCE. Also it is important to mention that mercury vapors are very poisonous besides Hg
itself is considered to be one of the major pollutants of the environment [2-4].

i av

i
i d

i
r
E

Figure 2. Typical polarogram

The slowly increasing current at the foot of the wave is known as the residual current. This
current is non faradaic in nature. The diffusion current id is, as shown, the distance between the
limiting diffusion plateau and the residual current. The potential at the midpoint of the wave, where the
current is exactly half its limiting value, is known as the half-wave potential E1/2 and its quantity is
characteristic of a particular species under fixed experimental conditions [5,6]. Thus E1/2 value serves
as finger-print for the species undergoing redox. Furthermore, the limiting current is usually

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Int. J. Modern Anal. Sep. Sci. 2013, 2(2): 61-70 64

proportional to concentration of the species being reduced or oxidized and thus serves for quantitative
analyses. Over the diffusion current plateau region the DME is behaving as a completely polarized
electrode since it adopts any applied potential to it with no change in current flow. It is interesting to
note that polarization always results from slow stage in the overall electrode process. The slow stage
here is the diffusion process which occurs very much slower than the electron transfer. This type of
polarization is known as concentration polarization and the DME is said to be concentration polarized.
At potentials corresponding to the rising part of the wave the electrode is depolarized since here the
current flow is strongly dependent on the applied potential. At this stage it is important to emphasize
that in any electrolysis two types of processes are encountered [7,8]: (1) mass transfer process which
brings the electroactive material to the electrode surface, and (2) electrochemical process which
involves the act of electron transfer between the surface of electrode and the electroactive species.
The mass transfer is usually achieved through: (a) migration, (b) diffusion, and (c) convection.
Migration is an electric field effect and depends upon the charge on the species, concentration and
mobility in a field of force. Diffusion depends upon differences in concentration between species at the
surface of the electrode and in the bulk of solution. Finally convection arises from any mechanical or
thermal disturbance in the solution. For a redox process to occur it is essential that electrons pass
between the electrode and the species in solution. However, by no means electron transfer in its crude
definition acts alone, thus adsorption, rearrangement of electronic configuration within the species to
give a suitable form for the electron exchange is a normal observable sequence [9]. After the electron
exchange a primary product is formed which re-undergoes an electronic rearrangement, desorption and
may suffer further side reactions to form the final product. These electrolytic processes may be
reversible or irreversible in nature depending on the activation energy values.

3. Types of Polarography

Various types of polarography are evaluated according to their sensitivity (the minimum
concentration that can be determined) and resolution (the permissible ratio of concentrations of the
supporting component to the component being determined) and depend on the shape and rate of
change of the polarizing voltage.

3.1. Direct–Current Polarography

In direct-current (classical) polarography, which is based on the dependence of Ie on the slowly

varying polarizing Edir, Ie is proportional to the number of electrons n that take part in the reaction. The
sensitivity in determining reversibly reactive substances is 10 -5 mole per liter (M), and resolution is
about 10. In alternating-current polarography, based on the dependence on Edir of the alternating

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current Ialt that arises upon superimposition of various forms of a voltage Ealt ((low-amplitude
rectangular, trapezoidal, and sinusoidal), Ialt is proportional to n2. The high sensitivity of alternating-
current polarography (10-7M) results from the possibility of separating the effective signal Ialt from Ic,
and its high resolution (up to several thousand) results from the bell shape of the polarogram (the
ordinate rapidly tends toward zero upon a deviation of Edir from peak potential) and by the possibility
of determining reversibly reactive substances in the presence of components with irreversible
reactivity (sensitivity in determining the latter is low) [7-9].

3.2. High-Frequency Polarography

High-frequency polarography involves the superimposition of Edir and a high-frequency E

modulated by a low-frequency E. In this case Imf, the component of the current for the modulated
frequency, depends on Edir and is proportional to n3. The difference in variation between Imf and Ic
upon application of a high frequency is used to separate the effective signal Imf from Ic [5,6]. High-
frequency polarography makes it possible to determine the rate constant of fast reactions.

3.3. Pulse Polarography

Pulse polarography is based on the measurement of the current Ip, which arises upon
application of a 0.04-sec voltage pulse at the moment when the surface of the mercury drop is
maximal. The current Ip is separated from Ic by measuring Ip at the moment of damping of Ic. Pulse
polarography has a sensitivity of 1–5 × 10-8 M and resolution ~5 × 103 [3-5].

3.4. Oscillographic Polarography

Oscillographic polarography is based on measurement of the dependence of I, on the rapidly

varying Edir (0.1–100 volts per sec). The polarograms produced in oscillographic polarography, which
are recorded by means of a cathode-ray tube, have a distinct maximum. In this type of polarography Ie
is proportional to n2/3, sensitivity is 10-6 M, and resolution is ~400. In addition to the DME, stationary
mercury and solid electrodes are also used in polarography [4,5]. A distinction is made between direct
and inversion polarography, depending on the nature of the current being measured. In inversion
polarography, the accumulation method is used to increase sensitivity (up to 10-9 M) and resolution (5
× 105 and higher). In this case electrodes with a constant surface are used: at limiting current potentials
or upon formation of an insoluble compound, the substance being analyzed accumulates on the
electrode surface (the pre-electrolysis stage), and the accumulated solid compound is subsequently
dissolved upon a change in Edir. Electrodes made of mercury, graphite, and noble metals are used.

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4. Advances in the Application of Polarography

The majority of the chemical elements can be identified by polarographic analysis, and the
method is also applicable to the analysis of alloys and various inorganic compounds. In addition,
polarography is useful in identifying numerous types of organic compounds and in the study of
chemical equilibria and the rates of reactions in solutions. The measurement of polarographic current
provides a simple method for the estimation of the rate of several fast electrode reactions. The
technique has contributed substantially to the study of adsorption of several surface active molecules
on a mercury surface.

4.1. Analyses of Pharmaceuticals

A large number of pharmaceuticals can be reduced or oxidized in the available potential range
and their waves can be used in their determination. It seems that often the therapeutical activity is
paralleled by electrochemical reactivity. Some drugs can be determined using polarography directly,
without separation, in some physiological liquids, for example in blood, lymph and saliva. Numerous
examples of such applications have been reported early. In some cases, nevertheless, simple separation
procedures, such as extraction, have to be used. In numerous cases of this type the uses of
polarography would result in procedures which are as selective, but faster and less expensive to use
than applications of the most widely used chromatographic methods. On the other hand, in analyses of
complex mixtures like urine or in the following of metabolic products, the use of separation techniques
is definitely preferable [12].
The situation is different, when the content of the drug is to be determined in matrices, in which
the drug is the only electroactive species. Such situation is often faced in analyses of tablets, solutions
like eye drops or those used for injections, but also in analyses of some creams and ointments. In such
cases the solution to be analyzed should contain the electroactive species at concentrations varying
between 1 × 10–5 and 1 × 10–3 M. In such situations, DC polarography is the preferable technique of
choice. The method is sufficiently sensitive and measurements of limiting currents are less affected
than those of peak currents, used in other electroanalytical procedures, by the presence of
electroinactive components of the sample. Presence of components in the sample, like that of starches,
of some polymers or long-chain saturated compounds, has little effect on limiting currents, but can
affect peak currents, as obtained in differential pulse or square wave variants.
Use of chromatographic methods for analyses of such simple matrices resembles using a canon
on a fly. Use of polarographic methods for analyses of such simple matrices yields results often much
faster, with a better accuracy and without using organic solvents. But, in addition to the lack of trained

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supervising personnel, mentioned above, there is another, administrative hurdle preventing a wider use
of polarographic methods in the determination of drugs. Pharmaceutical companies will use, whenever
possible, officially approved methods of analysis. In the past, some polarographic analytical
procedures were listed in numerous pharmacopoeias [12]. It should be a goal of electroanalytical
chemists around the world to have them listed again. The lower costs, faster results, and the possibility
for quickly detecting mishandlings by technicians, are powerful arguments.

4.2. Basic Studies

Polarography proved to be useful for determination of oxidation states of metals, both in the
ionic form and in complexes. Both the equilibria of labile complexes and properties of substitution
inert complexes as well as characteristics of metalorganic compounds may be investigated by DC
polarography (DCP). Structure-reactivity relationships for such species can be established [12]. In
investigations of organic compounds, polarography enables distinguishing the degree of the role of
conjugation, effects of ring size, substituent effects in linear free energy relationships and other
structure reactivity relationships. Recently, the comparison of polarographic half-wave potentials
indicated limited conjugation in compounds containing the >C=N–N=C< grouping, as opposed to the
extensive conjugation for those containing groupings –N=C–C=N–.

4.3. Rapidly Established Equilibria

Polarography is also a useful tool in investigations of solution chemistry, in particular of

equilibria and kinetics. Thus for rapidly established equilibria, both acid-base and of formation of
complexes, involving reducible heavy metal ions and a variety of ligands, the equilibrium constants
can be determined based on shifts of potentials, using graphs in which these measured quantities are
plotted as a function of pH or of a logarithm of ligand concentration [12]. In some instances this
enables determination of values of equilibrium constants of reactions involving organic compounds
that would be difficult to obtain by other techniques. Similarly, from the shifts of half-wave potentials
of the reduction of metal ions, it is possible to obtain information about stability constants of formation
of some labile complexes. Polarographic investigations also enabled detection of some unusual species
formed in acid-base equilibria, for example of the diprotonated forms of hydrazones and oximes.
Whereas DC polarography is well suited for investigation of chemical equilibria preceding the electron
transfer (systems denoted as CE) and for identification of relatively stable intermediates in consecutive
electroreductions, for investigation of faster chemical reactions following the electron transfer (EC
systems) and for studies of properties of short-lived intermediates, cyclic voltammetry is the technique
of choice.

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4.4. Slowly Established Equilibria

At the other extreme, when investigated equilibria are established slowly, as compared to the
rate of the electrode process, the equilibrium constants can be determined based on measurements of
limiting currents. The rates of dissociation of OH, SH or NH3 + type acids are too fast to be followed
in this way, but some equilibria involving cleavage of the C–H bond are established relatively slowly
and can be investigated based on the dependence of the limiting current of the conjugate acid on pH.
This approach was possible in establishing the acid-base properties of 3-thianaphthenone, ethyl
benzoylacetate, ethyl benzoylbenzoates,ω-cyanoacetophenone and of 1-phenyl-1,3-butanedione.
Another group of processes, where the equilibria are not completely shifted in the favor of the products
and are established relatively slowly, are some nucleophilic additions to carbonyl groups. Thus the
formation of a separate wave of an imine at more positive potentials than that of the reduction of the
carbonyl group, made it possible to determine equilibrium constants of additions of amines to
aldehydes and ketones. The intermediate of such reactions is a carbinolamine, the presence of which
was demonstrated and properties followed in the reactions of benzaldehyde and terephthalaldehyde
with hydrazine.

4.5. Kinetics of Fast Reactions

Finally, there are some equilibria which are established neither extremely rapidly nor
extremely slowly. The rates of their establishments are comparable with the rate of the electrode
process. In these cases, where the rate of the establishment of a chemical equilibrium, that takes place
before the electron transfer, is comparable with the rate of the transfer of the electron, the rate of the
re-establishment of the chemical equilibrium perturbed by electrolysis controls the limiting current.
When the equilibrium is perturbed by removal of the electroactive component by reduction or
oxidation, the re-establishment of such equilibrium takes place [12]. The rate constant of the
establishment of the equilibria can be obtained, provided that the value of the equilibrium constant is
known, or obtained by another technique, such as potentiometry or spectrophotometry. For such
reactions taking place within the reaction layer in the vicinity of the dropping mercury electrode (a
layer which is much narrower than the diffusion layer), it is possible to obtain rate constants of the
order of 104 to 1010 L mol–1 s–1. In those cases, where the same reaction was followed by relaxation
techniques, good agreement was found. The condition must be fulfilled that the reaction studied
electrochemically takes place as a homogeneous process in the solution in the vicinity of the DME.
The currents controlled by the rate of a chemical reaction are called kinetic and are observed
particularly for compounds undergoing chemical reactions belonging to two large groups: some acid-
base equilibria and some hydration-dehydration processes. Investigations of acid-base equilibria by

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means of DC polarography are possible, because the reductions of conjugate acids invariably take
place at potentials more positive than those of the conjugate base. On i-E curves of such reducible
acids, obtained at varying pH-values, it is possible to observe waves of the acid form decreasing with
increasing pH and the waves of the corresponding base increasing at more negative potentials with the
total limiting current remaining constant [11,12]. When the wave of the acid form becomes smaller
than about 25% of the diffusion limiting current, it becomes controlled purely by the rate of
protonation of the base and a kinetic current result. The value of the pH, at which the reduction wave
of the acid reaches 50% of the diffusion current, is denoted pK’, which is larger than pKa of the acid
obtained for example by spectrophotometry. From values of pK’ and p- Ka it is possible to calculate
the rate constant of the reaction: base + H+ = acid. In this way the rate constants of protonations of
anions of some α-ketoacids or maleic and fumaric acids for example, have been determined.

4.6. Bulk Reactions

Polarography can also be used as an analytical tool in the study of kinetics of reactions, where
τ1/2 > 0.5 min, often as a complementary method to spectrophotometry. For reactions with half-lifes
τ1/2 between about 0.5 min and 5.0 min it is possible to record the current continuously as a function
of time at a constant potential, corresponding usually to the limiting current. For reactions with τ1/2 >
5 min the segments of the i-E curve, where changes of waves occur with time, are recorded after
chosen time intervals. On such curves the limited currents at individual times are plotted as a function
of time or as a function of a log t. Such approach is possible when dealing with simple zero, first or
second order reactions [11,12]. For the treatment of higher order or more complex reactions solutions
can be found in treatises on reaction kinetics. The rate constants obtained from these plots at varying
compositions of the reaction mixture can be used in interpretation of the mechanism involved.

5. Conclusions

Despite the pass of its glorious days in the 1950s and 1960s, polarography still enjoy variety of
application in some aspects of chemistry with full relevance like in analysis of pharmaceuticals
containing a single components, which is both physiologically and electrochemically active, yielding a
reduction or oxidation wave and in determining an electroactive species in heterogeneous suspensions.
Polarography is also a useful technique in physical organic chemistry, and can be used for
investigation of equilibria and reaction kinetics. In some cases polarography can offer quantitative
information about equilibrium and rate constants, where use of other techniques would be difficult or
impossible.

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