By Edward B. Stuart, Alan J. Brainard, Benjamin Gal-Or

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67). 7–2 kg dm−3 , the corrections are smaller (from −3 to 6 J K−1 mol−1 ) than the usual experimental uncertainties associated with the statistical analysis of the data. 68. Note that Kc = Km when the sum of the stoichiometric coefﬁcients is zero. 68) Although there is no theoretical reason to consider the second law method a less reliable way of evaluating thermochemical values in solution compared to the ﬁrst law method, in practice we are compelled to make a number of assumptions that may lead to signiﬁcant errors.

In the differential set-up, the pressure over the The Thermodynamic Background 23 sample is determined by measuring the boiling temperature of a reference liquid (for which the pressure-temperature curve is accurately known) contained in a second ebulliometer. One of the critical issues in vapor pressure methods is the choice of the procedure to calculate the vaporization enthalpy. For instance, consider the vapor pressures of ethanol at several temperatures in the range 309–343 K, obtained with a differential ebulliometer [40].

3, the perfect gas mixture was assumed, and K ‡ related to an equilibrium constant given in terms of the partial pressures of the reactants and the activated complex [1]. This Kp is then easily connected with ‡ H1o and ‡ S1o . As stated, the perfect gas model is a good assumption for handling the results of the large majority of gas-phase kinetic experiments. In solution reactions, K ‡ is also deﬁned in terms of concentrations of A, B, and ‡ C , which means, of course, that the ideal solution model is adopted, no matter the nature or the concentrations of the solutes and the nature of the solvent.