Complex chemical systems with power production driven by heat and mass transfer

In this paper, we investigate power production in complex multireaction systems propelled by either uncoupled or coupled multicomponent mass transfer. The considered system contains two mass reservoirs, one supplying and one taking out the species, and a power-producing reactor undergoing the chemical transformations characterized by multiple (vector) efficiencies. To establish a suitable basis for these efficiencies, an approach is applied that implements balances of molar flows and reaction invariants to complex chemical systems with power production. Reaction invariants, i.e., quantities that take the same values during a reaction, follow by linear transformations of molar flows of the species. Flux balances for the reacting mixture may be written down by equating these reaction invariants before and after the reactor. Obtained efficiency formulas are applied for steady-state chemical machines working at the maximum production of power. Total output of produced power is maximized at constraints which take into account the (coupled or uncoupled) mass transport and efficiency of power generation. Special attention is given to non-isothermal power systems, stoichiometric mixtures and internal dissipation within the chemical reactor. Optimization models lead to optimal functions that describe thermokinetic limits on power production or consumption and extend reversible chemical work Wrev to situations in which reduction of chemical efficiencies, caused by finite rates, is essential. The classical thermostatic theory of reversible work is recovered from the present thermokinetic theory in the case of quasistatic rates and vanishing dissipation.