Polarography

Polarography is a technique used in electrochemistry to study the behavior of electroactive

species in a solution. It is based on the principle of measuring the current flowing through an
electrochemical cell as a function of an applied potential difference (voltage). The resulting plot,
called a polarographic curve, provides valuable information about the concentration, nature,
and behavior of the analyte (substance being analyzed).

The basic setup of a polarographic experiment involves an electrochemical cell consisting of a

working electrode, a reference electrode, and an auxiliary electrode. The working electrode is
typically made of a dropping mercury electrode (DME) or a solid electrode, while the reference
electrode is a standard electrode with a known and stable potential, such as a silver/silver
chloride electrode. The auxiliary electrode, also known as the counter electrode, completes the
circuit and provides a pathway for current flow.

The polarographic curve is obtained by applying a linearly increasing potential (known as the
scan rate) to the working electrode while measuring the resulting current. The potential is
increased from a negative value (cathodic scan) towards more positive values (anodic scan) or
vice versa, depending on the nature of the electroactive species being studied.

Interpretation of polarographic curves involves analyzing the different features observed. Here
are some common types of polarographic curves and their interpretations:

1. Diffusion-Controlled Reduction Wave: This type of curve appears as a sharp, well-

defined peak. It occurs when the electroactive species in the solution is reduced at the working
electrode, and the reduction process is controlled by diffusion. The peak current is directly
proportional to the concentration of the species, following the Cottrell equation. The peak
potential can provide information about the standard potential of the redox couple.

2. Adsorption-Controlled Reduction Wave: In this case, the reduction process is

influenced by the adsorption of the electroactive species onto the surface of the working
electrode. The polarographic curve exhibits a broad wave with slower rise and decay compared
to the diffusion-controlled wave. The peak potential is shifted to more negative values due to
the adsorption process. The adsorption behavior can give insights into the nature of the
electroactive species and the electrode surface.
3. Catalytic Wave: A catalytic wave appears as an increase in current density in the
polarographic curve due to the presence of a catalyst that enhances the rate of the
electrochemical reaction. The catalytic process can involve various mechanisms, such as the
facilitation of charge transfer or the involvement of intermediates. The magnitude of the
catalytic wave provides information about the efficiency of the catalyst.

4. Irreversible Reduction/Oxidation Wave: This type of polarographic curve shows a

current response without distinct peaks. It occurs when the electroactive species undergoes an
irreversible reduction or oxidation process, which involves complex reactions or multiple steps.
The absence of well-defined peaks makes it challenging to extract quantitative information, but
qualitative observations can still be made regarding the nature of the species and its behavior.

5. Wave Splitting: In some cases, a polarographic curve may exhibit multiple peaks,
indicating the presence of multiple electroactive species or complex reactions involving the
analyte. Each peak corresponds to a different reduction or oxidation process, and the separation
between the peaks provides insights into the kinetics and thermodynamics of the individual
species.

Interpretation of polarographic curves is a crucial aspect of analyzing electrochemical systems

and obtaining valuable information about the behavior of electroactive species in a solution.
Polarographic curves provide insights into the concentration, nature, and electrochemical
processes of the analyte. Here, we will discuss the key aspects involved in the interpretation of
polarographic curves.

1. Peak Current and Wave Height:

The peak current represents the maximum current observed during the reduction or oxidation
process. It is directly proportional to the concentration of the electroactive species, following
the Cottrell equation (i = nFAcD^0.5/rt). By measuring the peak current, the concentration of
the analyte can be determined. However, it is important to note that the relationship between
peak current and concentration is valid only when the reduction or oxidation process is
diffusion-controlled.
The wave height refers to the difference between the current at the peak and the baseline
current. The wave height provides information about the extent of the electrochemical reaction
and the efficiency of the electron transfer process. Higher wave heights generally indicate more
favorable electron transfer kinetics.

2. Peak Potential:
The peak potential (Ep) is the potential at which the peak current occurs. It is often used to
determine the standard potential (E^0) of the redox couple involved in the electrochemical
process. The peak potential can be compared to the standard potential of a known redox couple
to estimate the redox potential of the analyte. The Nernst equation (E = E^0 + (RT/nF)
ln([oxidized]/[reduced])) can be used to relate the peak potential to the analyte's redox
potential and the concentrations of the oxidized and reduced forms.

3. Half-Wave Potential:
The half-wave potential (E1/2) is the potential at which the current reaches half of the peak
current. It provides information about the thermodynamic stability and reactivity of the
electroactive species. The half-wave potential can be used to estimate the redox potential and
assess the electrochemical behavior of the analyte.

4. Shape and Symmetry of the Polarographic Curve:

The shape and symmetry of the polarographic curve can provide insights into the mechanisms
involved in the electrochemical reaction. Different shapes and symmetries indicate different
reaction mechanisms and kinetics.

- A well-defined, symmetrical peak suggests a diffusion-controlled process where the

electroactive species undergoes reversible reduction or oxidation.

- A broad, asymmetrical wave indicates an adsorption-controlled process where the species

interacts with the electrode surface.
- Multiple peaks or wave splitting may suggest the presence of multiple electroactive species or
complex reaction mechanisms.

5. Scan Rate Effects:

The scan rate, which determines the rate of potential change during the experiment, can
influence the shape and magnitude of the polarographic curve. Varying the scan rate can
provide information about the kinetics of the electrochemical process. Changes in the peak
potential and peak current with scan rate can indicate the presence of chemical reactions
occurring in parallel with the electrochemical reaction or other kinetic effects.

6. Background Current:
The baseline current observed in the absence of the analyte is known as the background
current. It can arise from several factors, including impurities in the solution, electrode surface
effects, and faradaic or non-faradaic processes. Understanding and subtracting the background
current is essential for accurately interpreting the polarographic curve.

7. Supporting Techniques:

Additional techniques, such as cyclic voltammetry, chronopotentiometry, and

chronoamperometry, can be used in conjunction with polarography to gather more information
about the electrochemical system. These techniques provide complementary data that aid in
the interpretation of polarographic curves.

In summary, interpretation of polarographic curves involves analyzing various parameters,

including peak current, peak potential, wave height, shape