Concept of thermodynamic capacity

Abstract

The thermodynamic capacity of a species (C_i) in a homogeneous phase is defined as (∂n _i/∂μ_i)_{P, T, nj}wheren n_i the total number of moles of i per unit quantity of the system irrespective of the actual system chemistry and µ_iis its chemical potential. Based on this definition, the thermodynamic capacity of oxygen in non-reactive and reactive gas mixtures and in binary and ternary liquid solutions has been computed. For reactive gas mixtures containing stable chemical species which do not undergo significant dissociation such as CO + CO₂, H₂ + H₂O and H₂ + CO₂, the capacity curves show a maximum at equimolar ratio and a minimum at higher oxygen potentials. If one of the chemical species partly dissociates as in the case of H₂S in H₂ + H₂S mixtures or SO₃ in SO₂ + SO₃ mixtures, capacity curves do not exhibit such maxima and minima, especially at high temperatures. It would be difficult to produce stable oxygen fugacities when the capacity has a low value, for example at compositions near the minimum. Oxygen capacities of non-ideal liquid solutions, Cu-O and Cu-O-Sn, and heterogeneous systems formed at saturation with the respective oxides are discussed.