Exercises

1. Paper Chromatographic Separation of Ag (I), Hg2 (II) and Pb (II) Ions Materials required
The following materials are required for the separation of Ag (I), Hg (II) and Pb (II) ions. (a) Chromatography paper: Whatman No. 1 filter paper strip of 25 cm x 7 cm is used. (b) Jar : Paper chromatographic jar is used whose height is 30 cm and diameter 10 cm. (c) Salt solution: Aqueous 1 % solution of silver nitrate, mercurous nitrate and lead nitrate are prepared. These solutions are slightly acidified with dilute nitric acid. (d) Developing solvents: One can use any one of the following solvents: (i) Tertiary butanol (40 ml) + acetone (30 ml) + water (12 ml) + cone. Nitric acid (8 ml). (ii) Methyl n-propyl ketone (85 ml) + 10 N HC1 (15 ml). (III) n-Butyl alcohol mixed with 5 percent (V/V) of glacial acetic acid followed by water to turbidity. (iv) distilled or deionised water. (e) Visualising agents: One may use any one of the following visualising agents: (/) Colourless ammonium sulphide solution is prepared by bubbling H2S in dilute NH4OH. (ii) 0.5% dithizone in chloroform solution is used. The paper chromatogram may also be developed by exposure to H2S gas but the results are not satisfactory as with dithizone. (iii) K2CrO4 and ammonia solution.

Procedure
Whatman No. 1 filter paper strip 25 cm * 7 cm is cut with a pair of stainless steel scissor. Then a line is drawn horizontally across the width of filter paper strip using a lead pencil. This line should be about 2 cm from the end of the filter paper. Location of the sports is marked with "x " on this line with pencil so that each " x " is at ieast 2 cm from each other as shown in Fig. 6.

Pb (II), Ag (I) and Hg2 (II) salt solutions are applied at spots A, B and C respectively with fine capillary tubes. On the spot D, a mixture of Pb (II), Ag (I), Hg2 (II) salt solution is applied. After dry ing the spots, the filter paper strip is fixed vertically by means of a clip attached to the inner cover of the chromatography jar. After this, the paper is lowered carefully into the chromatographic jar in such a way that the lower 1 cm portion dips into the developing solvent which is either a mixture of tertiary butyl alcohol (40 ml), acetone (40 ml), water (12 ml) and nitric acid or methyl n-butyl ketone (85 ml) and 10 N hydrochloric acid or n-butyl alcohol mixed with 5 percent (V/V) of glacial acetic acid, followed by water to turbidity. When the solvent has travelled a reasonable distance (say 15 cm), the filter paper is taken out and allowed to dry. The spots can be visualised by either of the following reagents : If the spots are sprayed with ammonium sulphide solution, silver, mercury and lead spots become dark brown and then their positions can be compared with the spots obtained from the mixture spot (at D). The paper chromatogram may also be developed by exposure to hydrogen sulphide gas, but the results are not as satisfactory as with dithizone. (//) If the spots are sprayed with 0.5 percent of dithizone in chloroform the different colours produced on the spots indicate various cations, i.e.. Silver spot: Orange Mercurous spot: Pink Lead spot: Rose pink (Hi) At the end of the run, the paper is removed from the jar. Then, it is dried carefully. Now it is dipped into 0.25 molar K2Cr04 solution when the following colours will be seen : Pb* Yellow + Ag Orange-red + Hg2 Orange (i)

The surplus K2Cr04 is removed by washing with water. Now the paper is held over the top of an open 0.880 ammonia bottle, the colour of the silver of the chromate will fade whereas that of the mercurous compound will turn black. Record the R/r values of the separated components in the mixture.

RF values : Note down the R/r values. For solvent system involving tertiary butyl ketone, etc. the sequence of the ions is as follows : Pb (II) < Ag (I) < Hg2 (II)
For solvent system involving n-butanol, glacial acetic acid and water, the Rp values of these cations are :

Cation Pb2+ Ag+ Hg2+

Rp values 0.08 0.16 0.85

Colour of band Rose pink Orange Pink

For the solvent system involving methyl-n-propyl ketone etc., the sequence of Kp values is as follows.

Hg2(II) > Ag(I) > Pb(II).