NORMAL-PULSE VOLTAMMETRY

Presented to: Dr. Nadeem Zafar

Presented by: Faiza Afzal
Roll no. : 17471507-105
Course title: Analytical Chemistry-VI
Course code: CHEM-416
Program: BS Chemistry
Semester: VII (Fall-2020) University of Gujrat
Section: C Hafiz Hayat Campus
Department of Chemistry
Date: 14-December-2020
 Definition

 Normal-pulse voltammetry (NPV)

consists of a series of pulses of
increasing amplitude applied to
successive drops at a preselected
time near the end of each drop
lifetime.

Fig 1: Signal for Normal-Pulse

Voltammetry
(Analytical Electrochemistry, 2nd
edition, by Joseph Wang)
Working of NPV
 Between pulses, electrode is kept at constant potential,
each originating from the same initial potential (Ei).

 At this potential, no reaction of analyte occurs.

 The amplitude of pulse increases linearly with each drop,

 The potential step duration is tp.
 In this, the pulse time (tp) is 50 ms.
 The current is measured about 40 ms after the pulse is applied.
 It is denoted by an open circle superimposed on the E-t waveform
 At this point, charging current is nearly zero.
Fig 2: NPV Waveform
(https://onlinelibrary.wiley.com/doi/epdf/10.1002/9780470027318.a531)
Cont…
 After measuring current, the potential is then returned to
Ei for a waiting period tw.

 It is often useful to stir the solution so that the analyte

concentration is everywhere equal to original bulk
concentration.

 If tw ≫ tp , stirring may not be necessary.

 ∆Es is the fixed change in potential per cycle, and tp is the

pulse time.
Cont…

 Following the first step, the potential is stepped

incrementally to more extreme values, until Ef is reached.

 This sequence of evenly spaced, progressively more

extreme potential steps and corresponding current
measurements span the region of Eo’O/R.
Voltammogram

The resulting voltammogram has a sigmoidal shape, with a limiting current given
by a modified Cottrell equation:

Fig 3: Voltammogram of NPV

(https://chem.libretexts.org/Under_Construction/Purgatory/
Book%3A_Analytical_Chemistry_2.0_(Harvey)/11_Electrochemi
cal_Methods/11.4%3A_Voltammetric_Methods)
Advantages of Normal Pulse
Voltammetry
 Due to short pulse duration:

 diffusion layer is thinner

 higher faradaic current

 Almost zero charging current

 Diffusion layer is the region in the vicinity of an electrode where the

concentration of analyte is different from its value in the bulk
solution.
Cont…

 The time where current is measured is compared to that

measured in DC polarography:

 This ratio predicts that normal-pulse polarography will

be 5–10 times more sensitive than DC polarography.
References

 https://onlinelibrary.wiley.com/doi/epdf/10.1002/9780470027318.a5311
(visited on 8 Dec, 2020 at 3:20 PM)

 Analytical Electrochemistry, 2nd Edition, by Joseph Wang