Abstract
On the basis of a free energy correlation between distribution coefficients and the number of carbon atoms found in a series of nine nitrosamines, the column dead volume was determined for different column-mobile phase systems, using methanol and acetonitrile as the organic components of the mobile phase. Application of the interaction index model for reversed-phase liquid chromatography yielded a quadratic equation as the expression of the selectivity, α, without it being possible to dispense with the second degree term. It is shown that the variation in the capacity factor, k′, with the composition of the organic component cannot be dealt with simplistically, since the relationship between the volumes of the stationary and mobile phases, ϕ( x), varies considerably with composition. The existence of a convergence zone in plots of ln k′ against the number of carbon atoms in the solute chain should not be interpreted as a characteristic property of the series, and may result from a compensation effect of the terms governing the dependence of the capacity factor on the eluent composition.
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