Why colloidal systems can be described by statistical mechanics: Some not very original comments on the Gibbs paradox

Abstract

Colloidal particles are distinguishable. Moreover, their thermodynamic properties are extensive. Statistical mechanics predicts such behaviour if one accepts that the configurational integral of a system of N colloids must be divided by N!. In many textbooks, it is argued that the factor N! corrects for the fact that identical particles (in the quantum mechanical sense) are indistinguishable. Clearly, this argument does not apply to colloids. This article explains why, nevertheless, all is well. The point has been made before, but has not yet sunk in. I also discuss the effect of polydispersity. © 2014 Taylor & Francis.