The modelization of non methanogenic anaerobic environments can be particularly challenging owing to the variability of the metabolic products. In particular, both hydrogen production and consumption take place at the same time due to the simultaneous occurrence of Dark Fermentation (DF) and homoacetogenis. The goal of this study is to investigate the kinetic and thermodynamic aspects of the biochemical pathways involved in the fermentation of ultrafiltered cheese whey; to this aim, a continuous digester was operated under three different Hydraulic Retention Times (6, 9 and 12 h) and fixed pH (5.5). A mathematical model, based on a variable stoichiometry approach, was implemented and calibrated; the proposed model allowed the determination of the parameters governing the most relevant pathways, namely homoacetogenesis and butyric and ethanol-type DF. A special focus was given to the quantification of the hydrogen turnover rate; the model proved to be an effective tool, in addition to widely adopted techniques such as microbial and isotopic analysis, for obtaining a deeper comprehension of the crucial aspects governing the non-methanogenic process. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.