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excluded volume
The concept of excluded volume was introduced by Werner Kuhn in 1934 and applied to polymer molecules shortly thereafter by Paul Flory.
== In liquid state theory ==
In liquid state theory, the 'excluded volume' of a molecule is the volume that is inaccessible to other molecules in the system as a result of the presence of the first molecule.〔Hill T. L., ''An Introduction to Statistical Thermodynamics'',Dover Publications, New York, 1986, p 288〕 The excluded volume of a hard sphere is eight times its volume—however, for a two-molecule system, this volume is distributed among the two particles, giving the conventional result of four times the volume;〔Mortimer, Robert G., ''Physical Chemistry'', Academic Press, 3rd Edition, p 423〕 this is an important quantity in the Van der Waals equation of state. The calculation of the excluded volume for particles with non-spherical shapes is usually difficult, since it depends on the relative orientation of the particles. The distance of closest approach of hard ellipses and their excluded area has been recently considered.
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