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The use of characteristic volumes to measure cavity terms in reversed phase liquid chromatography

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Summary

In the correlation of reversed-phase liquid chromatography capacity factors through the equation,

$$\log k' = log k'_0 + mV/100 + s\pi _2^* + b\beta _2 + a\alpha _2 $$

the use of McGowans characteristic volume, Vx, which can be trivially calculated, is entirely equivalent to the use of Leahy's computer-calculated intrinsic volumes, V1, for the cavity term mV/100. It is shown that for 209 gaseous, liquid, and solid solutes, the two sets of volumes are related through the equation,

$$V_1 = 0.597 + 0.6823 V_x $$

with a standard deviation of only 1.24cm3 mol−1, and a correlation coefficient of 0.9988.

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Authors and Affiliations

  1. Department of Chemistry, University of Surrey, GU2 5XH, Guildford, UK

    M. H. Abraham

  2. 13 Moreton Avenue, AL5 2EU, Harpenden, Hertfordshire, UK

    J. C. McGowan

Authors
  1. M. H. Abraham
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  2. J. C. McGowan
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Abraham, M.H., McGowan, J.C. The use of characteristic volumes to measure cavity terms in reversed phase liquid chromatography. Chromatographia 23, 243–246 (1987). https://doi.org/10.1007/BF02311772

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  • DOI: https://doi.org/10.1007/BF02311772

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