The analysis of the equivalence between the minimum entropy generation (MEG) rate and the maximum conversion rate for a reactive system is the main purpose of this paper. While being used as a strategy of optimization, the minimum entropy production was applied to the production of propylene glycol in a Continuous Stirred-Tank Reactor (CSTR) with a view to determining the best operating conditions, and under such conditions, a high conversion rate was found. The effects of the key variables and restrictions on the validity domain of MEG were investigated, which raises issues that are included within a broad discussion. The results from simulations indicate that from the chemical reaction standpoint a maximum conversion rate can be considered as equivalent to MEG. Such a result can be clearly explained by examining the classical Maxwell-Boltzmann distribution, where the molecules of the reactive system under the condition of the MEG rate present a distribution of energy with reduced dispersion resulting in a better quality of collision between molecules with a higher conversion rate. (C) 2013 Elsevier Ltd. All rights reserved.