Chiral chromatography by Thomas E Beesley; Raymond P W Scott

By Thomas E Beesley; Raymond P W Scott

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Although helpful, the capacity ratio is so dependent on the accurate measurement of extra column volume and on very limited solute Page 39 exclusion by the support and stationary phase, that it is less than ideal for solute identification. An alternative measurement, called the separation ratio ( α). For two solutes (A) and (B), the separation ratio was defined as: It is seen that the separation ratio is independent of all column parameters and depends only on the nature of the two phases and the temperature.

The Retention Volume of a Solute The retention volume of a solute is that volume of mobile phase that passes through the column between the injection point and the peak Page 35 maximum. It is therefore, possible to determine that volume by differentiating equation (10) and equating to zero and solving for (v)' Restating equation (10): Equating to zero and solving for (v): n - v = 0, or v = n At the peak maximum, (n) plate volumes of mobile phase have passed through the column. Now, remembering that the volume flow is measured in 'plate volumes' and not ml, the volume passed through the column in (ml) will be obtained by multiplying by the 'plate volume' (v m + Kvs).

The more random and the greater freedom the solute molecule has, to move in a particular phase, the greater its entropy in that phase. In system (B), the large entropy change indicates that the solute molecules are more restricted, or less random, in the stationary phase than they were in the mobile phase. Because the standard entropy is negative, this loss of freedom is responsible for a reduced distribution of the solute in the stationary phase and, thus, diminished solute retention. Inasmuch as the change in entropy in system (B) is the major contribution to the change in free energy, the distribution, in thermodynamic terms, is said to be "entropically driven".

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