Department of Chemistry, Nagpur University, Amravati Road Campus, Nagpur-440 010, India

A methodology has been described to develop an irreversible
thermodynamic framework based on the laws of thermodynamics
and exemplified by applying it to a spatially uniform chemically
reacting closed system with no irreversibility in the energy exchanges.
It is shown that if in the Gibbs reration the chemical composition
determining extensive parameters appear as independent
thermodynamic variables and if their variation includes the changes
due to chemical reaction, then it, in fact, is an irreversible thermodynamic
description. The de Donderian thermodynamic framework
is basically a nonequilibrium description in which the chemical
affinity containing term is the manifestation of the irreversibility in
chemical interactions. This confirms that the Gibbs function
primarily takes care of the chemical interactions and hence the
quantification of the irreversibility in the latter need to be achieved
through the former function by identifying its suitable expression.