LIQUID-LIQUID EXTRACTION 219

with the activity coefficient ratios of the ions in solutions of high

ionic strengths. In a series of exchanges of monovalent cations,

the observed order of K'ex. values was found to be:

Cs+ > Rb+ > K+ > Na+ > H+ > Li+

Except for the reversal of H* and Li+, this is the order that is

expected on the basis of the activity coefficients of these ions.

K'x for a general reaction,

nRMx + Mf+^ RnM2 + nM+

where R stands for the resin anion and Mx a monovalent cation

and M2 an n-valent cation, can be shown to be:

". (ym>Hin [mjj-yBr1+xM;

From this expression it is obvious that the highly charged ions

will have higher K'cx values.

"" These considerations apply to the operation of an ion ex-

change column since the rate of flow of eluent in most cases is

slow enough to permit the establishment of exchange equilibria

to a reasonable approximation.

- If for a series of metal ions values of Kx. are not sufficiently

different to provide for a good separation on a column of reason-

able length, complexing agents can be used to improve the sepa-

rability of the metals. Such a case might well arise with two

metal ions of the same charge and similar ionic radii. The addi-

tion of sufficient complexing agent to the eluent would result in

an increase in the total concentration of the metals in the aqueous

phase, CMj,and CMj. It would be possible to evalute the new posi-

tion of equilibrium by substituting /30 CM for [Mn+] for each of

the metal ions. The ratio of their distributions can be shown to

be: XM/CM

XM/C

M, K' /3O

^c = ir * a (xn-19)

From equation (XII-19) it can be seen that the difference in

degree of complexation (i.e. the /30 ratio) can serve to amplify

the difference in the exchange constants to bring about a greater

degree of separation of the two metal ions.

If the pair of metals involved each forms a single complex

having the same stoichiometry with the ligand and this is in

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