The document discusses voltammetry and polarography, outlining various types, including normal and differential pulse voltammetry, and their instrumentation involving a three-electrode system. It highlights different electrodes used, such as the dropping mercury electrode, alongside explanations of measurement techniques and the role of each electrode type. Additionally, it recognizes Jaroslav Heyrovsky as the inventer of the polarographic technique and his contributions to electro-analytical methods.

1. Voltammetry
and
polarography
1. NORMAL PULSE VOLTAMMETRY
2. DIFFERENTIAL PULSE VOLTAMMETRY
By
Shobana.N.S
Queen Mary’s College, Chennai

2. Voltammetry
 It is an Electro- analytical technique.
 It gives information about the analyte.
 We can even measure the amount of current by varying the
voltage.
 The change in current with the varying voltage gives the
plot and is known as uoltammogram
 There is a minimum potential required to initiate an
oxidation or reduction reaction at an electrode.

3. Instrumentation
 It is a three electrode system.
 1. Working electrode ; 2. Reference electrode and
3. Auxiliary electrode.
(1) working electrode;
(2) auxiliary electrode;
(3) reference electrode

4. Working Electrode
 Ranges from small mercury drop to flat platinum disc.
Platinum disc
DME

5.  Other commonly used electrode materials gold, platinum and
glassy carbon.
Glassy carbon Gold electrode

6.  Depending on the choice of working electrode, the type of voltammetry is
decided.
 Example :
We use Dropping Mercury Electrode (DME) in Polarography technique
We use Platinum electrode in Cyclic Voltammetry
We use Glassy Carbon as electrode in Linear Sweep Voltammetry.

7. Reference Electrode
 Usually Standard electrode is used as Reference electrode.
 Its potential is constant.
 It provides potential to the Working electrode.
 Common reference electrode are :
Calomel electrode and Ag/AgCl electrode

8. Auxiliary Electrode
 It is usually a thin platinum wire.
 It serves merely to carry the current flowing through the cell.
 Usually redox reaction occur simultaneously at the
auxiliary electrode.

9. Type of Voltammetry
 LINEAR SWEEP VOLTAMMETRY
 STAIRCASE VOLTAMMETRY
 CYCLIC VOLTAMMETRY
 SQUAREWAVE VOLTAMMETRY
 ANODIC STRIPPING VOLTAMMETRY
 CATHODIC STRIPPING VOLTAMMETRY
 ABSORPTIVE STRIPPING VOLTAMMETRY
 ALTERNATING CURRENT VOLTAMMETRY
 POLAROGRAPHY
 ROTATED ELECTRODE VOLTAMMETRY
 NORMAL PULSE VOLTAMMETRY
 DIFFERENTIAL PULSE VOLTAMMETRY
 CHRONOAMPEROMETRY.

10. Linear Sweep Voltammetry
 In linear sweep voltammetry (LSV) a fixed potential range.
 the voltage is scanned from a lower limit to an upper limit.

11.  In LSV measurements the current response is plotted as a function of voltage
rather than time.
 The scan begins from the left hand side of the current/voltage plot where no
current flows.
 As the voltage is swept further to the right (to more reductive values) a current
begins to flow and eventually reaches a peak before dropping

12. Normal Pulse Voltammetry
 Normal polarography has been replaced by
various forms of pulse polarography.
 It uses a series of potential pulses.
 Here the pulse time (tp) is 50ms.
 Each potential has different amplitude

13. Differential Pulse Voltammetry
 If potential pulse is applied periodically to the Linear Sweep Voltammetry, then it is
known as Differential Pulse Polarography.
 Hence it is denoted as the differential of linear sweep voltammetry.

14.  The current is measured twice per cycle.
 Here the pulse time (tp) is 17ms.
 The difference in the two currents gives rise to the peak-shaped voltammogram.
 consistent enhancement of the signal is achieved.
 Detection limit is as low as 10-8 M
 Each potential step has the same amplitude

15. Polarography
 Polarography is the branch of
voltammetry in which a dropping
mercury electrode (DME) is used as the
working electrode.

16.  Conventional DC
 Wide cathodic potential range and a renewable surface
 Hence widely used for the determination of many reducible species
 Reduction begins at sufficiently negative potential
 voltage applied to the polarisable electrode is increased over the range of 0-2V
 It is known as incomplete electrolysis.

17. Jaroslav Heyrovsky
 He was the inventor of Polarographic technique.
 He received Nobel Prize in 1959
 He is known as father of electro analytical
method.

18.  Polarography has a special characteristic :
1. Use of polarized electrode.
2. Use of depolarized electrode.
 POLARIZED ELECTRODE : DME
 DEPOLARIZED ELECTRODE : SCE

20. Dropping Mercury Electrode
 It is the working electrode in one of the voltammetry technique known as
polarography

21. Advantages of DME
 Clean Surface generated
 Rapid constant current achievement
 Even metal with high negative standard voltage systems can be studied without
hydrogen.
 Amalgam formation more favourable.

22. THANK YOU !!