Chapter 3

POLAROGRAPHIC SETUP AND PLAN OF WORK

POLAROGRAPHIC CIRCUIT

Polarographic technique constitutes a unique type of electrolysis which involves the study of current voltage relationships at a dropping mercury electrode under certain controlled conditions. A current-voltage curve can be obtained by gradually increasing the applied voltage and measuring the corresponding mean currents; plotting the currents against voltage. In order to avoid time consuming measurements and curve plotting, automatic recording polarographs are available. These instruments serve for recording based on

electrochemical polarization. Any electrolysis involves two main types of processes, e.g., transference of matter through a solution towards and away from electrodes and electrochemical processes involving the exchange of electrons at the electrode surfaces. During an electrolysis, three mass transfer processes are of importance, namely, migration, diffusion and convection. The first of these is an electrical effect depending upon the charge carried by an electro active species and upon its transference number. Thus, the effect is encountered only with charged species. Since processes of diffusion

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are nonelectrical in origin, these are for all species in solution, whether they are charged or not. Convection effects include motion of small particles under the influence of stirring, mechanical agitation, and temperature gradients.

Significance of Diffusion Current While studying the polarographic' work, the migration effect is usually eliminated and it is usual to study the oxidation or reduction of electroactive species in solution under conditions such that the latter arrives at the indicator electrode by natural diffusion only. Suppression of migration effect is achieved by mixing together with the species under study, an excess of supporting "electrolyte" which is normally 50-100 fold is excess of the electroactive component of the solution. This added electrolyte is so chosen that no electrode reactions characteristic of it interferes with those of the species under investigation. Supporting electrolytes serve as current carriers and, by virtue of being in excess effectively reduce their transference numbers to zero. Convection effects are eliminated by carrying out the electrolysis in adequately controlled thermostats so as to protect the apparatus from all forms of shocks and vibrations.

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Basically, consists
ve

polarographic electrolyzing a

of

solution cations

containing between a

several dropping

mercury electrode and some reference

+ve

electrode. mercury

The electrode

dropping

(DME) usually functioning as

Fig. 3.1 Polarographic Circuit

cathode. A potential is applied

between these electrodes and increased in a step-wise manner. During this process, corresponding current changes being observed at each applied potential. Essentials of the electrical circuit required are shown in the Fig. 3.1. The applied potential is varied by means of a potential divider circuit while the current flowing is indicated on a sensitive galvanometer. Diffusion-controlled currents observed in polarography are usually of the order of a few micro-amperes, since the electro active material used is of the order of 103 molar. A dropping mercury electrode consists of a series of small mercury droplets which emerge, at a constant rate, from the tip of a capillary attached to a constant head device. The life-duration of each drop

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normally lies between 3-7s. A saturated calomel electrode (SCE) or some other reliable reference electrode whose potential is independent of the imposed potential is used. To examine the nature of the current voltage relationships observed on reduction of a metal ion in solution, it is necessary to flush the working solution with some inert gas, usually nitrogen so as to remove dissolved oxygen which may cause interference by itself undergoing reduction, in two stages, within the normal potential working range. When this interference is removed the current-voltage curve for the reduction of the metal ion will have the appearance of that shown in Fig. 3.2.
C Decomposition (Potential) D

Current

B A Applied Potential Fig. 3.2 Current Voltage Curve

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At first, as the potential is increased continuously from zero, only a very small current flows. This is called the residual current. This is essentially a charging current arising from the charging of the double layer at each drop and is non-Faradic. The residual current may also contain small (Faradic) components due to the presence of reducible impurities in the solution. These may be introduced through the high concentration of the supporting electrolytes used. Only the residual current flows until the decomposition potential of the reducible ionic species is reached. At this point the ions designated Mn+ begin to be discharged owing to their reduction by the process:
Mn + + ne

M ( Hg ) (Product of electrode reaction)

Very often the metal atoms produced are absorbed into the mercury drop in the form of amalgam. A steep rise in current is now observed and, with a further small increase in applied potential, the rise will continue. However, the Mn+ ions arrive at the DME by the relatively slow process of natural diffusion. Since, the rate of reduction increases with the applied potential, a point is eventually reached at which the ions are reduced as fast as they diffuse across the concentration gradient set up at the electrode surface.

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The importance of polarographic for quantitative analysis lies in the direct proportionality which exists between the limiting diffusion current and the concentration of the reducible species or "depolarizer". It is to be noted that at the foot of the current voltage curve, or "polarographic wave", and at the limiting current plateau, the dropping electrode behaves in accordance with the definition of a "polarized" electrode. That is to say, the potential applied to it may be altered at will within these regions without significantly altering the current flow. On the rising part of the, wave, the current changes considerably for only a small variation in applied potential and the DME is said to be "depolarized". In the region of the plateau current, id, the dropping electrode is completely "concentration polarized", since the electrode reaction rate is controlled by the diffusion rate and hence by the concentration gradient at the electrode surface. The potential corresponding to the mid-point of the wave, where the current is exactly one-half of the maximum value id/2, is known as the "Half-wave potential", represented as E1/2. It is the potential at which the reducible species under consideration is depolarized under fixed solution condition. Measurement of half-wave potentials, therefore, serves as a means of identification of different reducible species.

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Polarographic Cell Assembly A diagrammatic sketch of the polarographic cell assembly is shown in Fig. 3.3. It consists of a dropping mercury electrode (DME), a saturated calomel electrode (SCE) and the solution to be electrolyzed.

R Mercury D

E B

N2

N2

Calomel A electrode Test solution Fig. 3.3 Polarographic Cell Assembly

The test solution containing about 103 to 104 M concentration of the reducible species and about 1 M concentration of the suitable supporting electrolyte is taken in the cell and is deaerated by passing pure nitrogen through the side tube S. This is essential otherwise the dissolved oxygen begins to be reduced at the dropping mercury electrode, thus interfering with analysis.

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Pure mercury from the reservoir R is allowed to fall through the test solution at the end of the capillary tube C, at a rate of 20 to 30 drops per minute. Each drop which is held at the end of the capillary tube for 2-3 seconds acts as the cathode. When one drop falls, the second takes its place, and so on. There is, thus, a continuous renewal of the mercury drops. A calomel electrode which forms a part of the cell through a cintered glass frit A as shown, serves as the anode. The calomel anode and mercury cathode are joined, respectively, to the positive and negative poles of a battery B. The applied voltage can be easily varied by moving the sliding contact D along the potentiometer wire EF. The current strength is measured by means of a sensitive galvanometer or micrometer G, across the terminals of which is connected a shunt K. This makes provision for varying the sensitivity of the instrument. The potential of the cathode is easily determined by subtracting from the applied EMF the potential of the calomel electrode. The test solution contains a single electro active species, the current-voltage curve, which is commonly known as a polarogram, will be of the shape as shown in Fig. 3.4. The limiting current, which is given by the height of the wave, corresponds to the concentration of the electroactive species. The potential at the centre of the rising part of the

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wave, referred to as the half-wave potential, is characteristic of the species being discharged and is independent of its concentration. The half-wave potential,

designated as E1/2 is thus used to

Fig. 3.4

identify the particular species. Advantages of Using DME There are a number of advantages of using dropping mercury electrode (DME) as the microelectrode in polarography. Some of these advantages are as follows. 1. 2. Its surface area is reproducible with any given capillary. It furnishes ideal conditions for obtaining a completely diffusion controlled limiting current. 3. The current falls when the drop falls. Hence, an oscillation is observed. However, the oscillation is so uniform that it is easy to observe the average current. The average current becomes reproducible soon after the applied voltage is changed. In contrast, a stationary solid microelectrode requires several minutes before steady current can be obtained. This difference in behaviour arises
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from the fact that whereas the diffusion layer in the DME is very thin, in the case of stationary solid microelectrode is thick. As a result, in the latter case a decrease in current is observed; the current becomes steady only after a stable diffusion layer is formed. No doubt, current variations occur with the DME, too, but the current becomes steady very soon since the mercury drop is reformed quickly. 4. Since the electrode surface is constantly renewed, the surface poisoning effects are minimized. 5. Mercury forms amalgam with many metals, thereby lowering their reduction potential and decreasing their tendency to redissolve. 6. Since the over voltage of hydrogen gas on mercury is very high, the DME is useful for polarographic reduction of a large number of ions in acidic solution.

Limitations A serious limitation of DME is that metallic mercury gets oxidized easily. It can, therefore, be employed for the analysis of only the reducible and easily oxidisable substances.

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Disadvantages of Dropping Mercury Electrode (a) The area of the microelectrode is constantly changing as the size of the drop changes. (b) Mercury may be easily oxidized and thus limits the feasible range of the electrode. (c) The capillary may be easily plugged, the care must be taken to avoid touching the tip of the capillary with any foreign material. Polarographic Cell The polarographic cell

used is show in Fig 3.5. The left hand side of the cell contains saturated potassium chloride

solution and a pool of mercury into which a stainless steel wire dips to make electrical contact. The horizontal tube that
Fig. 3.5 Polarographic Cell

connects the two halves of the cell is closed at the right hand end by a porous sintered glass disc which is backed by a plug of agar gel 2-3 cm long. The capillary is mounted in a rubber stopper, a small groove is cut in the side of the stopper to let the

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nitrogen escape. The nitrogen inlet in provided with a stopcock (not shown in the figure) so that the gas stream can be stopped while readings are being taken. Calomel Electrode Calomel electrode consists of mercury, solid mercurous chloride and a solution of potassium chloride. The electrode is represented as: Hg, Hg2 Cl2 (s); KCI (solution) It can be easily set up in the laboratory as follows: Mercury of high grade purity is placed at the bottom of a glass tube having a side tube on each side (Fig. 3.6). Mercury is covered by a paste of mercurous chloride (calomel), solution as of shown. A Fig. 3.6 Calomel electrode potassium chloride is introduced above the paste through the side tube shown on the right. The concentration of the solution is either decinormal, normal or else the solution is fully saturated. The solution also fills the side tube
KCl Solution Paste of Hg2Cl2 Hg Platinum Wire

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ending in a jet on the left. A platinum wire sealed into a glass tube serves to make electrical contact of the electrode with the circuit. If the electrode reaction involves reduction, the Hg22+ ions mercurous chloride would be discharged at the electrode. Hence, more and more of calomel would pass into solution. The result is an increase in the concentration of chloride ions. The reaction may be represented as follows:
Hg 2Cl2 ( s ) + 2e
+ Hg 2 2 ( aq ) + 2e

2Hg (1) + 2Cl ( aq ) 2 g (1)

Hg 2Cl2 ( s )

2+ g 2 ( aq ) + 2Cl ( aq )

If, on the other hand, the electrode reaction involves oxidation, it

+ 2+ would liberate electrons and send g 2 2 ; ions into solution. The g 2

ions would combine with Cl ions to form Hg2Cl2. The result is a fall in the concentration of chloride ions in the solution. The reaction may be represented as follows:
2Hg (1)
+ g 2 2 ( aq ) + 2e

+ g 2 2 ( aq ) + 2Cl ( aq )

Hg 2Cl2 ( s )

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Thus, in the case of the calomel electrode, the, electrode reaction may be represented as
Hg 2Cl2 ( s ) + 2e 2Hg (1) + 2Cl ( aq )

The electrode, therefore, is reversible with respect to chloride ion.

POLAROGRAPHIC MAXIMA Sometimes, the current-voltage curve obtained with the DME is found to be deformed in shape. There are sharp peaks or rounded humps in the curve before the limiting value is reached. Such curves are said to exhibit maxima, which are reproducible. A sudden increase in current in the polarographic wave is sometimes observed, which falls abruptly with slight increase in applied potential. That means a pronounced maximum in current is observed within a narrow potential range. The polarographic maxima are caused by increased transport of the electroactive species towards the electrode by a streaming motion of the solution. These maxima are considered a nuisance during polarographic measurements. Typical maxima observed in polarograms are shown in Fig. 3.7.

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A (First type) Current

B (Second type)

Potential Fig. 3.7 Polarographic maxima (A) first type; (B) second type

The maxima of the first kind (curve A, Fig. 3.7) appears as sharp peaks within a narrow potential range, and are more pronounced at lower concentration of the supporting electrolyte. These appear practically independent of the mercury pressure. If the mercury drop is then examined by a microscope, a vigorous streaming of the solution is observed around the drop. This results in transport of more depolarizer molecules or ions than is possible under diffusion process only. The maximum, thus caused, can also be called a streaming maximum. The maxima of the second type appear over a longer potential range and are rounded in appearance. These usually occur at higher concentrations of electrolyte and are more pronounced at high pressure of mercury. The maximum of the second kind practically disappears at low

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pressure of mercury. Such maxima are also known as non-streaming maxima. It must be suppressed by the addition of small quantity of a surface-active substances1 such as gelatine, Triton-X 100 etc. which are called Maxima Suppressors. The streaming movement2 of the diffusion layer at the mercury-solution interface is the probable cause for maxima. The suppressor forms an adsorbed layer3 on the aqueous side of the interface which resists compression. The maxima suppressive efficiency of different compounds have been investigated by several workers in the field4,5. Various other workers have investigated the factor controlling the maxima6,7 and have suggested ways for removing it. Some studies on polarographic maxima of Co(II) and Ni(II) have also been carried out by Gaur and Maheshwari8 at Rajasthan University, Jaipur.

PLAN OF WORK The electrochemical behaviour of some transition metal ions such as Cd(II), Pb(II), Cu(II), Zn (II), Mn(II), In(III), Co (II) & Ni (II) and Inner Transition element Eu (III) with Pyridine carboxylic acids ( Pyridine2carboxylate and pyridine3carboxylate ions) in aqueous

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medium and 2-aminopyrimidine in aqueous-organic mixtures carried out at D.M.E. The interaction will be studied at constant temperature and constant ionic strength. The composition and formation constants of the complexes would be calculated by Linganes9, Deford & Humes10 and Mihailovs11 method, whichever applicable. The effect of temperature on the electrode process will be studied and for this purpose the experiments will be carried out at different temperatures. The thermodynamic parameters for the electrode process and complex formation will be calculated and the results will be explained. In case of irreversible or quasi-reversible electrode process, the kinetics of the electrode process will be studied by Kouteckys12, Meites and Israel13, Gaur and Bhargavs14 modified method, whereas Gellings15, Matsudas16 and Korytas17 method were applied in quasi-reversible electrode processes. The kinetic parameters were calculated. The analytical applications of the results obtained will be discussed and methods will be developed for estimation of some metal ions in the presence of the ligands selected for study.

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REFERENCES

1.

Schimdt, R.W. and Reilley, C.N.: J. Am. Chem. Soc. 80, 2087 (1958).

2. 3.

Heyrovsky, J. and Simunek, R. : Philoso. Mag., 7, 951 (1929). Barker, G.C. and Faircloth, R.L., : Advances in Polarography, Vol. I., 325 (I.S. Longmuir, ed.) pergamon Press, London (1960).

4.

Rusznak, J. Kralik J. and Bukker K.: Collect czechoslov. Chem.. communs. 26, 1262 (1961).

5.

Zuman, P.: Chem Listy, 48, 102 (1954) Collect, Czeck. Chem. Communs., 20, 883 (1955).

6. 7.

Mallik, W.U. and Haque, R.: J. Polarograp Soc., 8, 36 (1962). Stackelberg, V.M. and Droppelfeld, R.: Advances in

Polarography, P. 68, I.S. Longmuir, Ed. Pergamon Press, London (1960). 8. Gaur, J.N., Maheshwari, A.K. : Ind. J. Chem. Vol. 12, 390-392, (1974). 9. 10. 11. Lingane, J. J. : Chem. Rev., 29, 1 (1941). DeFord, D. D. and Hume, D.N. : J. Amer. Chem. 73, 5321 (1951). Mihalilov, M.H. : J. Inorg. Nucl. Chem. 36, 107, 114 (1974).

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12.

Koutecky, J.: Coll. Czech. Chem. Communs. 18, 597 (1953) and 21, 836 (1956).

13. 14.

Meites, L. and Israel, Y.: J. Amer. Chem. Soc., 83, 4903 (1961). Gaur, J. N. and Bhargava, S.K.: Bull. Chem. Soc., Japan, 46, 3314 (1973).

15.

Gellings, P.J. : Elektrochem. Ber. Bunsenges, Physik. Chem., 66, 477, 481, 799 (1962) and 67, 167 (1963).

16.

Matsuda, H.: Elektrochem. Ber. Bunseriges, Physik. chem., 61 (1957), 977 (1958) and 63, 1164 (1959).

17.

Koryta, J. : Chem. Zvesti., 8, 644 (1954).

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