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Working of Normal Pulse Voltammetry

Normal pulse voltammetry involves applying a series of voltage pulses of increasing amplitude to sequential mercury drops. The working electrode potential is held constant between pulses at an initial potential where no reaction occurs. Each pulse causes the potential to increase by a fixed amount, with the current measured after a brief time period. This sequence is repeated with incrementally higher pulse amplitudes to map out the region of potential where oxidation/reduction reactions occur, producing a characteristic sigmoidal voltammogram curve with a limiting current defined by a modified Cottrell equation.

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117 views3 pages

Working of Normal Pulse Voltammetry

Normal pulse voltammetry involves applying a series of voltage pulses of increasing amplitude to sequential mercury drops. The working electrode potential is held constant between pulses at an initial potential where no reaction occurs. Each pulse causes the potential to increase by a fixed amount, with the current measured after a brief time period. This sequence is repeated with incrementally higher pulse amplitudes to map out the region of potential where oxidation/reduction reactions occur, producing a characteristic sigmoidal voltammogram curve with a limiting current defined by a modified Cottrell equation.

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Normal Pulse Voltammetry

In normal pulse voltammetry, a series of pluses of increasing amplitude is applied to sequential drops
after preselected time near the end of lifetime of each Hg drop.
Working of Normal Pulse Voltammetry
Electrode is retained at constant potential between the pulses which emerge from the same initial potential
(Ei). The reaction of analyte does not occur at this initial potential. The potential step duration is denoted
by tp which is almost 50 ms. When pulse is applied, about almost 40 ms current is measured. This point is
denoted by an open circle. Charging current is almost zero at this point.

Figure 1: NPV Waveform

(Carter, M. T., & Osteryoung, R. A. (2006). Pulse Voltammetry. Encyclopedia of Analytical Chemistry: Applications,
Theory and Instrumentation.)

When current is measured, then the potential starts to drop to E i for waiting period tw. It is preferred to stir
the solution so that analyte concentration becomes equal to original bulk concentration. Stirring does not
necessary when tw ¿ tp. ∆Es is the fixed change in potential per cycle. Following the first step, the potential
is stepped incrementally to more extreme values, until Ef is reached. The amplitude of pulses increases
linearly with each drop. This sequence of evenly spaced, progressively more extreme potential steps and
corresponding current measurements span the region of E o’ O/R.

Voltammogram
The resulting voltammogram has a sigmoidal shape, with a limiting current given by a modified Cottrell
equation:
Figure 2: Voltammogram of NPV

(https://chem.libretexts.org/Under_Construction/Purgatory/Book
%3A_Analytical_Chemistry_2.0_(Harvey)/11_Electrochemical_Methods/11.4%3A_Voltammetric_Metho
ds )
References

 Carter, M. T., & Osteryoung, R. A. (2006). Pulse Voltammetry. Encyclopedia of Analytical


Chemistry: Applications, Theory and Instrumentation. (visited on 8 Dec, 2020 at 3:20 PM)
 Analytical Electrochemistry, 2nd Edition, by Joseph Wang

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