Abstract

Free volume present in condensed phases is either divided among the atoms present, or treated as independent holes. If a distribution of hole sizes is assumed, both approaches can be reconciled: smaller holes (interstitials) can be considered as being attached to atoms, while holes larger than a critical size (e.g. atomic) can be treated as independent. The distribution obtained depends on the choice of a free volume model. The model of Landau and Lifshits is studied in detail as an example. Numerical calculations are reported for liquid toluene in the 220–370K range. Temperature increase produces an increase in the number of independant holes which continually coalesce. Initially, interstitial holes grow slightly with a temperature increase, but then their size tends asymptotically to a limit.

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