The ion-pair constant and other thermodynamic properties of HCl up to 350°C

Physics

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Scientific paper

Solubilities of silver chloride in aqueous hydrochloric acid solutions have been determined from 100 up to 350°C. From these measurements, the ionisation constant of HC1 has been evaluated up to 225°C. Evidence is presented to show that a protonated silver species, HAgCl 2 0 , exists at 275°C and above. Available experimental data up to 200°C have been firted to Pitzer's equation to generate an algorithm to calculate stoichiometric activity and osmotic coefficients of HCl up to 350°C and concentrations up to at least 3.0 m. Using the present results and those of et al . (1961), et al . (1963) and et al . (1976), the dissociation constant ( K d ) of HCl as a function of temperature is described by the equation log 10 K = 2136.898 + 1.020349 T -4.5045 × 10 -4 T 2 -50396.40/ T -901.770 10g 10 T ( T in ° K ) which is valid in the range 25-350°C. Calculated enthalpy ( H 0 ), entropy ( S 0 ) and heat capacity change ( C p 0 ) functions for HCl dissociation have been rationalized in terms of changing solute and solvent characteristics as temperature is raised.

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