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preface to fifteenth edition

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PRACTICAL LABORATORY INFORMATION 11.39<br />

concentration distribution ratios are inversely proportional <strong>to</strong> the solution concentration of the resin<br />

counterion.<br />

To accomplish any separation of two cations (or two anions), one of these ions must be taken<br />

up by the resin in distinct preference <strong>to</strong> the other. This preference is expressed by the separation<br />

fac<strong>to</strong>r (or relative retention), K/Na , using K and Na as the example:<br />

(D c) K kK/H<br />

K/Na<br />

K<br />

(D ) k<br />

c Na<br />

The more deviates from unity for a given pair of ions, the easier it will be <strong>to</strong> separate them. If the<br />

selectivity coefficient is unfavorable for the separation of two ions of the same charge, no variation<br />

in the concentration of H (the eluant) will improve the separation.<br />

The situation is entirely different if the exchange involves ions of different net charges. Now the<br />

separation fac<strong>to</strong>r does depend on the eluant concentration. For example, the more dilute the counterion<br />

concentration in the eluant, the more selective the exchange becomes for the ion of higher<br />

charge.<br />

In practice, it is more convenient <strong>to</strong> predict the behavior of an ion, for any chosen set of conditions,<br />

by employing a much simpler distribution coefficient, D g , which is defined as the concentration<br />

of a solute in the resin phase divided by its concentration in the liquid phase, or:<br />

D g<br />

Na/H<br />

K/Na<br />

concentration of solute, resin phase<br />

concentration of solute, liquid phase<br />

% solute within exchanger volume of solution<br />

Dg<br />

<br />

<br />

% solute within solution mass of exchanger<br />

D g remains constant over a wide range of resin <strong>to</strong> liquid ratios. In a relatively short time, by simple<br />

equilibration of small known amounts of resin and solution followed by analysis of the phases, the<br />

distribution of solutes may be followed under many different sets of experimental conditions. Variables<br />

requiring investigation include the capacity and percent cross-linkage of resin, the type of<br />

resin itself, the temperature, and the concentration and pH of electrolyte in the equilibrating solution.<br />

By comparing the ratio of the distribution coefficients for a pair of ions, a separation fac<strong>to</strong>r (or<br />

relative retention) is obtained for a specific experimental condition.<br />

Instead of using D g , separation data may be expressed in terms of a volume distribution coefficient<br />

D v , which is defined as the amount of solution in the exchanger per cubic centimeter of resin bed<br />

divided by the amount per cubic centimeter in the liquid phase. The relation between D g and D v is<br />

given by:<br />

Dv<br />

Dg<br />

where is the bed density of a column expressed in the units of mass of dry resin per cubic centimeter<br />

of column. The bed density can be determined by adding a known weight of dry resin <strong>to</strong> a graduated<br />

cylinder containing the eluting solution. After the resin has swelled <strong>to</strong> its maximum, a direct reading<br />

of the settled volume of resin is recorded.<br />

Intelligent inspection of the relevant distribution coefficients will show whether a separation is<br />

feasible and what the most favorable eluant concentration is likely <strong>to</strong> be. In the columnar mode, an<br />

ion, even if not eluted, may move down the column a considerable distance and with the next eluant<br />

may appear in the eluate much earlier than indicated by the coefficient in the first eluant alone. A

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