Polarography
Definition: Polarography is an electrochemical method used to analyze substances by
measuring current as voltage is applied. It was invented by the Jaroslav Heyrovsky in
[Link] a technique in which electric potential is varied in a regular manner between the
two sets of electrode and current is monitored.
• It uses a Dropping Mercury Electrode (DME) to detect the reduction or oxidation of analytes.
• The current produced is related to the concentration of the analyte (usually a drug or ion).
Principle
As voltage increases, the analyte gets reduced at the DME. This reduction causes current to
increase until it reaches a limiting value. The voltage at which half of the max current flows is
called Half-Wave Potential (E1/2). This potential is unique for each substance and helps identify
it.
Theory of polarography
Polarography involves electrochemical reduction or oxidation at a Dropping Mercury Electrode
(DME). Electrons are transferred from the electrode to the analyte or vice versa. The resulting
current is plotted against voltage to form a polarogram. Analyte’s behavior is interpreted from the
shape and value of the current.
Polarogram: Voltage vs. Current
Ilkovic Equation (Simple Explanation)
id = 708 × n × D1/2 × m2/3 × t 1/6 × C
• id: Diffusion current (directly related to concentration)
• n: Number of electrons involved in redox
• D: Diffusion coefficient (mobility of molecules)
• m & t: Properties of mercury drop (rate of mercury flow through capillary and t is drop time of
hg in seconds)
What is H-cell
H-Cell is a glass apparatus shaped like 'H' used in polarography. One arm contains Working
Electrode; the other has Reference Electrode. The bridge allows ion flow via a salt bridge or porous
disk. Prevents mixing of solutions, stabilizes measurements. The working of H-cell is such that
sample solution is placed in sample cell I.e. DME and reference is placed at saturated calomel
electrode. The N2 gas is allowed to pass through sample to remove oxygen molecules. the voltage
is applied and gradually increased until electrolysis and reduction starts at DME. When the region
around DME is reduced then polarization of DME occurs. The diffusion current is used for
quotative determination of polarography.
• C: Concentration of the analyte (drug)
Applications in pharmacy
. Determination of drug concentration (e.g., antibiotics, vitamins).
• Identification of unknown drugs via half-wave potential.
• Stability testing and degradation studies.
• Detection of metal ions and impurities in formulations.
• Useful in quality control and pharmacokinetic studies.
MCQs
1. Who invented the technique of polarography?
A) Michael Faraday
B) Jaroslav Heyrovsky
C) Alessandro Volta
D) Marie Curie
Answer: B) Jaroslav Heyrovsky
2. In polarography, which type of electrode is mainly used for detecting reduction or oxidation?
A) Glass electrode
B) Saturated Calomel Electrode
C) Dropping Mercury Electrode (DME)
D) Platinum electrode
Answer: C) Dropping Mercury Electrode (DME)
3. What does the Half-Wave Potential (E₁/₂) in polarography represent?
A) The maximum diffusion current
B) The voltage at which the current becomes zero
C) The voltage at which half the maximum current flows
D) The starting point of voltage application
Answer: C) The voltage at which half the maximum current flows
4. What is the function of the H-cell in polarography?
A) To increase temperature
B) To prevent oxygen interference and stabilize measurements
C) To generate current
D) To mix two solutions quickly
Answer: B) To prevent oxygen interference and stabilize measurements
5. Which equation relates diffusion current to analyte concentration in polarography?
A) Nernst Equation
B) Beer-Lambert Law
C) Ilkovic Equation
D) Arrhenius Equation
Answer: C) Ilkovic Equation
