CHAPTER - I

BASIC PRINCIPLES OF
POLAROGRAPHY
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Polarography is an important type of voltammetry which is concerned with the

nature and application of current voltage curves obtained during electrolysis with micro

electrodes under conditions of concentration polarization of the electroactive species.

The technique was developed by late Professor Jaraslov Heyrovsky of Charles University,

Prague, Czechoslovakia. From the current-voltage curves, it is possible to identify and

determine the concentrations of several or all of the electro oxidisable or electro reducible

substances. Thus it is possible to obtain both qualitative and quantitative analysis of the

solution containing a wide variety of organic and inorganic compounds. The technique

can be applied to solution in water (aqueous), semi-aqeuous and non-aqueous solvents

and molten media.

PRINCIPLES OF POLAROGRAPHY

Concept and definition

In polarography, a gradually increasing voltage is applied between a micro­

electrode (mercury or platinum) and some reference electrode and the corresponding

current changes are measured. The reference electrode used may be calomel electrode or

mercury pool or any other non-polarisable electrode. For reduction process, the micro

electrode generally employed consists of a series of mercury droplets which emerge at a

constant rate (2 to 5 seconds per drop) from the tip of the glass capillary (diameter 0.06-

0.08 mm) attached to a constant head device. The micro electrode generally employed

for oxidation process is a micro platinum electrode which rotates at high speeds (600

rpm). The basic electric circuit is shown in Fig. 1.1.1.

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In polarographic studies, it is necessary to remove the dissolved oxygen from the

solution before electrolysis, since oxygen undergoes reduction very easily yielding two

polarographic waves of equal height extending over a considerable voltage range.

Therefore removal of oxygen is very essential otherwise the oxygen waves will mask the

waves of other electro active species in the solution. Removal of oxygen can be achieved

by passing an inert gas like nitrogen or hydrogen through the experimental solution for

sufficient time. The current-voltage curves, appearing before and after the removal of

oxygen, are presented in Fig. 1.1.2.

In polarography, the depolariser is transported to the micro electrode both by

electrical migration and diffusion. The current due to “migration is eliminated by the

addition of neutral or inert electrolyte to the solution electrolysed”. The concentration of

the inert electrolyte is many times (1000 times) larger than the concentration of the

depolariser. This inert electrolyte is called “supporting electrolyte”. The addition of

supporting electrolyte helps to increase the conductivity of the solution too. The curve

representing the current-voltage relationship is called “polarogram” or “a polarographic

wave”. It exhibits an ‘s’ shape as shown in Fig. 1,1.3. The potential corresponding to the

mid point of the wave is referred to as “half-wave potential” (Em). This is a characteristic

property of the depolariser. The current corresponding to the plateau region of the wave

is known as “limiting current” (it).

Nature of the limiting current

In polarographic processes, the limiting currents are classified as :

i) diffusion controlled currents

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ii) kinetic controlled currents

iii) catalytic currents and

iv) adsorption currents

i) Diffusion controlled currents

The limiting current controlled by the diffusion process of the depoiariser to the

electrode surface, is referred to as diffusion controlled one. In such cases, the limiting

current depends on the concentration of the depoiariser undergoing reduction or

oxidation at the electrode. Ilkovic1 derived the following equation for diffusion controlled

limiting currents

id = 607nDI/2m2/3t1/6C --- (1)

Where

n = number of electrons transfered in the process,

m = rate of mercury flow in mg/sec,

D = diffusion constant of the depoiariser in cm2/sec,

t = drop time in seconds,

c = concentration of the depoiariser in millimoles/litre,

id = diffusion current in microamperes.

The equation suggests that the diffusion current is directly proportional to the

concentration of the electro active species (C) as well a: to (mMtl/6). The limiting current

increases linearly with the concentration of the depoiariser as well as with mfflt!/6 But

mMt1/6 is proportional to the square root of mercury column height. Thus in the case of

diffusion controlled currents, it can be formulated that the limiting current varies linearly
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with the concentration as well as with the square root of the mercury column height. The

linear plot passes through the origin.

Nature of the electrode process

The polarographic processes are classified as reversible or irreversible on the basis

of the magnitude of the rate of electron exchange process between the depolariser and the

electrode (charge transfer process). If the rate of this process is large, the process is

termed ‘reversible’. Heyrovsky and Ilkovic2 derived the following relationship between

the voltage applied to the dropping mercury electrode, Eame and the current for such a

reversible diffusion controlled polarographic process.

Edm, = Em + 0,059 log i ----- (2)

n, id-i
Where

Edme = Potential applied to the dropping mercury electrode,

E1/2 — Half-wave potential of the depolariser,

i = Mean current at the applied potential

id = the limiting current and

n, = number of electrons exchanged in the process

(i) Reversible process

The reversibility of an electrode process is generally tested making use of this

equation. Edme is plotted against log i (id - i). A straight line plot with slope equal to

±0.059/11* suggest a reversible process. n«, calculated from the slope is usually an integer

1 or 2 or 3.
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Criteria of Reversibility

1. EdnK Vs log i/(i d - 0 plots are linear and the n value will be an integer (1, 2 or 3).

2. The half-wave potential of the oxidised and reduced forms of the depolariser are

identical.

3. A mixture of the oxidised and the reduced forms of the depolariser will yield a single

combined cathodic-anodic wave.

4. The half-wave potential will not change with the concentration of the depolariser.

5. The half-wave potential agrees well with potentiometrically determined standard

potential or the formal potential.

6. The half-wave potential is nearly independent of temperature.

(ii) Irreversible process

A Polarographic process is termed irreversible when the rate of the charge transfer

process is slow. However, the rate limiting step may be the diffusion controlled one.

Such processes are known as irreversible diffusion controlled processes. Ilkovic equation

has been modified for such process as shown below.

E<une= E1/2 -0.059 log _j__ — (3)

an* (id - i)

for cathodic process

Edme^Eia -0.059 log _j--- ----- (4)

pna (id - i)

For anodic process

Where a and 3 are called the ‘transfer coefficients’ for the reduction and

oxidation processes respectively.

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Indications for irreversibility

1. The n, calculated from the slope of the semi-logarithmic analysis plot will not be an

integer.

2. E\a shifts towards more negative values with rise in pH of the medium.

3. E/1/2 shifts to more negative values with increase in the depolariser concentration3.

4. The heterogeneous forward rate constant (K°r,h) of the electrode process calculated

from the Meites-lsrael equation4.

E1/2 =-0.2412 +0.05915 log 1.349 KV -0 059IS log D„m

ana ana

is less than 10-4

5. The AG* values computed from the relation

K°fh = KT On exp (-AG*) --- (5)

h (RT)

increase with increase in the pH.

6. Tome’s criteria5 is employed to determine the irreversible nature of the polarographic

wave. It gives the relationship between Ei/4 and E3.4 us follows.

Ei,4 - Ev4 = 0.0564 V for reversible — (6)

an.

Ei/4 - Ej,4 = 0.05172 V for irreversible — (7)

an,

It is seen from the equation that the number of electrons (na) exchanged in

elementary process depends upon the potential difference between Ei,4 and E3/4.
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Kinetic parameters of the irreversible electrode reaction

The heterogeneous rate constant K°f.h (cm sec'1) value is evaluated from the

equations proposed by Meites-lsrael, Oldham Parry and Gaur and Bhargava for the totally

irreversible waves at 25°C.

Meites and Israel4 proposed the following equation for the calculation of K0fj,.

-El* = -0.2412 + 0.05915 log 1.349 K°f,h tmDm (8)

an*

In this equation Em is referred to the SCE and the currents are those at the end of

the drops.

Where

K.% = heterogeneous formal rate constant for the forward reaction (cm/sec)

The value of otn, is generally deduced from the slope (0.05915/an*) of the linear

plot, -Edme versus log i(Ld - i).

The intercept of the plot gives the value of -Em from which the value of K°th can

be obtained..

Oldham-Parry6 deduced the following relationship.

Em - Edme = 0.0592 log 2 (3-X)

an* 5 (1-X)

Where

X = i/ij i.e., the ratio of the current at any potential along the polarogram to the

limiting diffusion current.

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The plot of log 2(3-X) versus -Edme is a straight line with a slope of 0.0592/ana

volts'1 at 25°C and the intercept Em. The half-wave potential is in turn used to calculate

K°fj, by the equation.

E1/2 = Et + 0.0592 log 1.35 K°f.h tm Dia --- (9)

an.

Where

K°fj, is the formal rate constant at some convenient reference potential of ET.

Recently, Gaur and Bhargava7 considered that the diffusion to the electrode

surface is spherical and not a linear process as assumed earlier and they extended the

Koutecky’s* treatment and deduced the following equation for an irreversible wave..

E,w = E,„ -0.0569 log i at 25°C --- (10)

an, (id - i)

With EI/2= -0.2412 + 0.0562 log K°fJlt1/2 1.128D1/2 (11)

an.

The diffusion coefficient (D) value required for the calculation of K°fj, is

calculated from Stoke-Einstein9 equation.

D = 3.38 x 10'5at 30°C ... (12)

Vj/’q

Where r\ = viscosity of the solution

Vm = apparent molar volume

The activation free energy change, AG* is obtained from the relation

K°Ch = KT o0 exp (-AG*1 (13)

h (RT)
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Where
K = Boltzmann constant (erg. Deg1 molecule ’)

h = Planck’s constant (erg.sec)

u„ - mean distance between the depolarised ions in bulk solution (cm)

and is

generally equal to 2 x 1 O'8 cm ^

AG* = activation free energy change

R = gas constant (cal.)

T = absolute temperature

Effect of temperature

The temperature coefficient of the diffusion current is calculated from the

expression

Temperature coefficient = 2.303 log ij — (14)

(AT) i,

Where

it = diffusion current at lower temperature (pA)

i2 = diffusion current at higher temperature (pA)

AT = Temperature difference.

Thermodynamic parameters

The thermodynamic parameters - enthalpy of activation (AHP*), heat of activation

at constant volume (AHV*), and the entropy of activation (AS*)-are calculated as follows:
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Enthalpy of activation (AHP*)

This is calculated by substituting the value of the slope of the plot (log K°ch Vs

1/T) in the Van’t Hoffs equation10.

AHp* = -2.303 x R x (-) slope --- (15)

Heat of activation at constant volume (AHV*)

This is evaluated from the relation

AHp* = AHV* + RT --- (16)

Activation free energy change (AG*)

This is determined by the relationship

K0n. = KT u„exp(-AG*) --- (13)

h (RT)

Entropy of activation (AS*)

This is calculated using Helm holtz relation

AS* = (AHV*- AG*)/T --- (17)

Evaluation of number of electrons

Millicoulometric method

The millicoulometer described by De Vries and Kroon11 consisting of a mercury

pool cathode was used to determine the number of electrons.

n2 = m (AwcadXidSub) CjVi (18)

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(idcad)( Aidsub) C2V2

Where

id = diffusion current (pA)

Aij = change in the diffusion current (jj.A) of polarograms obtained, when the

experimental solution is subjected to polarography.

ni = number of electrons involved in the reduction of cadmium ions and

n2 = number of electrons involved in the reduction of substrate.