Earth and Atmospheric Sciences, Department of


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Published in Journal of Solution Chemistry, Vol. 24, No.4, 1995


The dissociation quotient of benzoic acid was determined potentiometrically in a concentration cell fitted with hydrogen electrodes. The hydrogen ion molality of benzoic acid/benzoate solutions was measured relative to a standard aqueous IiCI solution at seven temperatures from 5 to 250°C and at seven ionic strengths ranging from 0.1 to 5.0 molal (NaCI). The molal dissociation quotients and selected literature data were fitted in the isocoulombic (all anionic) form by a six-term equation. This treatment yielded the following thermodynamic quantities for the acid dissociation equilibrium at 25°C and 1 bar: log Ka = -4.206±0.006, ΔH=0.3±0.3 kJ-mol-1, ΔS=-79.6±1.0 J-mol-1-K-1, and ,ΔCp̊, a = -207±5 J-mol-1-K-1. A five-term equation derived to describe the dependence of the dissociation constant on solvent density is accurate to 250°C and 200 MPa.