Interaction with thermal radiation in the free expansion and mixing of ideal gases and Gibbs' paradox in classical thermodynamics

Abstract

The standard theory of ideal gases ignores the interaction of the gas particles with the thermal radiation (photon gas) that fills the otherwise vacuum space between them. This is an unphysical feature of the theory since every material in this universe, and hence also the particles of a gas, absorbs and radiates thermal energy. The interaction with the thermal radiation that is contained within the volume of the body may be important in gases since the latter, unlike solids and liquids, are capable of undergoing conspicuous volume changes. Taking this interaction into account makes the behaviour of the ideal gases more realistic and removes Gibbs' paradox.