Journal of Colloid and Interface Science, Vol.262, No.1, 25-31, 2003
On thermodynamical inconsistency of isotherm equations: Gibbs's thermodynamics
It has been proven that all isotherm equations which include the expression 1 - Theta contradict the exact Gibbs thermodynamics. These contradictions have been discussed in detail in the case of the Langmuir (L) equation applied to gas/solid (G/S), solid/liquid (S/L), and gas/liquid (G/L) interfaces. In G/S adsorption the L equation can theoretically be applied only at low equilibrium pressures on condition that v(g) much greater than v(s) . v(g) is the molar volume of the adsorbed amount in the gas phase and v(s) is the same in the Gibbs phase. In S/L and G/L adsorption the L equation is practically applicable only in the domain of very low concentrations. The cause of these contradictions (inconsistencies) is that Gibbs thermodynamics takes excess adsorbed amounts into account; however, the L and other isotherm equations calculate with the absolute adsorbed amount. The two amounts may be practically equal to each other when the limiting conditions mentioned above are fulfilled. It is also discussed how these inconsistent isotherm equations can be transformed into consistent ones. (C) 2003 Elsevier Science (USA). All rights reserved.
Keywords:Gibbs thermodynamics;thermodynamical inconsistencies;G/S;G/L;and S/L interfaces;limits of inconsistencies;elimination of inconsistencies