A priori prediction of thermodynamic properties of electrolytes in mixed aqueous-organic solvents to extreme temperatures.

The unified theory of electrolytes (J. Phys. Chem.

A high-temperature high-pressure calorimeter for determining heats of solution up to 623 K.

A high-temperature high-pressure isoperibol calorimeter for determining the heats of solution and reaction of very dilute substances in water (10(-4) m) at temperatures up to 623 K is described. The energies of vaporization of water at steam saturation pressure were measured as a function of temperature and the results agree with the corresponding values from steam tables to better than 0.08+/-0.

Thermodynamic properties of aqueous polyatomic ions at extreme temperatures and pressures.

Recently a theoretical treatment (J. Phys. Chem.

Standard state thermodynamic properties of completely ionized aqueous sodium sulfate using high dilution calorimetry up to 598.15 K.

Pabalan and Pitzer (Geochim. Cosmochim. Acta 1988, 52, 2393-2404) reported a comprehensive set of thermodynamic properties of aqueous solutions of sodium sulfate without using ion association or hydrolysis.

Standard state thermodynamic properties of completely dissociated hydrochloric acid and aqueous sodium hydroxide at extreme temperatures and pressures.

Standard state thermodynamic properties for completely dissociated hydrochloric acid were fixed by ionic additivity, using the data from other strong electrolytes perrhenic acid, sodium perrhenate, and sodium chloride from 298.15 to 598.15 K and at p(sat).

Standard state thermodynamic properties of aqueous sodium chloride using high dilution calorimetry at extreme temperatures and pressures.

In this communication, we report the first calorimetric data for the standard state enthalpies of a solution of sodium chloride obtained from high dilution, down to (10(-3) m), integral heats of solution measurements to 596.30 K. Although there are no comparable thermodynamic data available at such high dilutions in the literature, the present results for NaCl(aq) can be used for many thermodynamic studies by others to achieve a complete thermodynamic description of this key electrolyte over very wide ranges of concentration.

A unified theory of the thermodynamic properties of aqueous electrolytes to extreme temperatures and pressures.

A new theoretical treatment has been developed for predicting the thermodynamic properties of electrolytes up to and beyond the critical temperature of water (973 K and at pressures up to 1000 MPa). The model is based upon the classical Born equation corrected for non-Born hydration effects. The temperature and pressure behavior of electrolytes can now be accurately predicted from existing low temperature data.

Standard state thermodynamic properties of Ba2+(aq), Co2+(aq), and Cu2+(aq) up to 598.15 K, and temperature effect on ligand field.

Integral heat of solution measurements of barium chloride to 619.81 K, copper oxide in an excess of perrhenic acid to 585 K, and cobalt perrhenate in perrhenic acid to 573 K were measured in a high dilution calorimeter (< or =10(-3) m) at psat, from which the high temperature thermodynamic properties of aqueous barium chloride, copper perrhenate, and cobalt perrhenate were obtained. From the known differences between the corresponding properties for aqueous perrhenate and chloride ions, the thermodynamic properties of completely ionized aqueous copper and cobalt chloride were obtained from ionic additivity.

Thermodynamic properties of aqueous gadolinium perrhenate and gadolinium chloride from high dilution calorimetry at extreme temperatures and pressures.

The heat of solution of solid cubic gadolinium oxide has been measured in noncomplexing perrhenic acid solutions at very high dilutions (10(-4) m) up to 596.30 K, from which the standard state thermodynamic properties of aqueous gadolinium perrhenate were determined up to 623.15 K.