A new family of completely general equilibrium equations has been developed to represent the temperature dependence of reaction equilibrium constants in terms of the reaction standard thermodynamic function changes at a chosen reference temperature. Evaluation of these equilibrium equations by the method of least squares provides the best unbiased estimates for the standard thermodynamic function changes and their standard errors which are readily determined for the first time. Application of the equations to the ionization of aqueous cyanoacetic acid furnishes a more general representation of the data than comparable empirical relations. Use of the new equations is recommended when it is required to predict both the values and errors on standard thermodynamic function changes from the temperature dependence of reaction equilibrium constants.

A new weighted least-squares method is described which is generally applicable for the nonsubjective evaluation of the best set of thermodynamic functions from a given data set of equilibrium (ΔG) and calorimetric (ΔH, Cp) measurements. The method, applied to model a wide range of 2428 measurements for the water-sodium chloride system between −21 and 154 °C, accurately represents all measurements within experimental error. The resulting model is used to predict the thermodynamic functions and their standard errors for aqueous sodium chloride up to 110 °C. Tables are given for freezing point, solubility, boiling point, osmotic and activity coefficients, vapor pressure, apparent molal relative enthalpy, partial molal relative enthalpies, integral heat of solution, specific heat, apparent molal heat capacity, partial molal heat capacities, apparent molal relative heat capacity, partial molal relative heat capacities, standard thermodynamic functions, and their changes for dissolution.

A study has been made of the infrared 0-H bands for CH30H, DOH, and H z O in solution and of their correlation with hydrogen bonding and solvent basicity. Infrared bands for the three fundamentals and the first bending overtone of HzO and for the 0-H stretching fundamentals of DOH and C H 3 0 H have been measured between 30 and -40°C in a solvent range extending from weakly interacting fluorocarbons to strongly hydrogen-bonding organic amines. The 0-H stretching bands for the weakly acidic solutes CH30H, DOH, and H z O are mostly Lorentzian in shape and move to lower frequencies with higher extinctions in the more basic solvents. Many correlations are found between the stretching frequencies and band areas, and between the frequencies and solvent basicity. Monofunctional C H 3 0 H is found to be a stronger acid and forms stronger hydrogen-bonds with a given base than do the doubly bonded DOH and HOH which show equal dibasic acid strengths.The wide, overlapped, fundamental stretching bands for H 2 0 strongly hydrogen-bonded to the tertiary amines and for ice have been partially resolved and unequivocally assigned, showing that there is no cross-over of the v3 and v, bands despite the strong hydrogen-bonding.At higher temperatures in solvents containing both hydrophobic and strongly basic groups water was found with the lower C, type symmetry, in which unbonded 0-H groups gave sharp bands in the 3680-3650 cnl-' region in addition to the wide hydrogen-bonded bands at lower frequencies. Aux temperatures superieures dans les solvants contenant des groupes hydrophobes et fortement basiques I'eau possede la symetrie inferieure de type C, suivant laquelle des groupes 0-H non-lies procurent des bandes fines dans la region 3680-3650 cm-' en plus des bandes larges causees par les liaisons hydrogenes aux frkquences inferieures.

No abstract

Interaction of solid silver fli~oborate with the gaseous olehns ethylene, propylene, and the four butenes has been observed to provide 12 new stoichiometric solid coordination compounds (silver Huoborate -olefin con~plexes) of high stability. Esperimental investigation of the univariant press~lre-temperature stability lines for the complexes has been made and the thermodynamic functions calculated: the heat content change for complex dissociation is between 9 and 13 l~cal/mole of olefin liberated. Infrared spectra of the complesed olefins indicate that the strength of the silver-olefin bond is primarily dependent upon the basicity of the olefin and a comparison of the thermodynamics of clissociatio~i shows anomalous behavior on the part of isob~~tylene and lrans-2-b~rtene as compared with the regularity displayed by the other f o~~r olelins.