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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Free Energies of Hydration for Metal Ions from Heats of Vaporization
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Free Energies of Hydration for Metal Ions from Heats of Vaporization

机译：从汽化热量的金属离子的水合作用水

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摘要

Consistent thermochemical data are of major importance for predicting and rationalizing stability and reactivity throughout chemistry. The free energy of hydration (Delta G(hyd)) substantially defines the aqueous chemistry of metal ions and aids our understanding of the properties of water and has thus been widely studied both theoretically and experimentally. This paper first shows that the experimental standard half reduction potential for the process Mn+ + ne(-) -> M is accurately described using a simplified version of Trasatti's thermochemical cycle involving the ionization potentials, Delta G(hyd) of Mn+, and the standard heat of vaporization (Delta H-vap) of M. This approximation, which neglects entropy, is shown to be valid both by actual performance (uncertainty similar to 0.1 V, R-2 similar to 0.99-1.00 for available data for M3+ and M2+ ions) and by application of Trouton's rule for entropies of vaporization. Second, application of the formula allows the identification of many Delta G(hyd) values not reported before. Together with previously determined values, the compiled lists of Delta G(hyd) are the most complete so far reported and are all thermochemically consistent; i.e., they agree with their corresponding thermochemical cycles. The numbers use the convention Delta G(hyd)(H+) =-1100 kJ/mol and SHE = +4.44 V but can be easily adjusted to other reference states as appropriate. Some of the new Delta G(hyd) values established here are for the catalytically important d-transition metal ions Rh3+, Re-3+,Re- Ir3+, Mo3+, W3+, Tc2+, Nb3+, Ta3+, 00+, and Ru2+. Some, such as Ir3+, are among the most inert aqua ions known. The AGhyd values have an accuracy of similar to 10 kJ/mol and are recommended for use in thermochemical calculations, for interpretation of the aqueous chemistry of the metal ions, and as benchmarks for theoretical chemistry.
机译：一致的热化学数据对于在整个化学性方面预测和合理化稳定性和反应性的主要重要性。水合的自由能量（Delta g（Hyd））基本上限定了金属离子的水化学，并有助于了解水的性质，并因此在理论上和实验中被广泛研究。本文首先表明，使用涉及涉及MN +的电离电位，Delta G（HYD）的MN +和标准的简化版本，精确地描述了该方法Mn + + Ne（ - ） - > M的实验标准半降低电位。 M.疏忽熵的蒸发热（Delta H-VAP）热量，其忽略了熵，通过实际性能（类似于0.1V，R-2类似于0.19-1.00，用于M3 +和M2 +的可用数据，这两种近似离子）并通过在汽化熵的熵中应用Trouton规则。其次，该公式的应用允许鉴定未以前未报告的许多ΔG（HYP）值。与以前确定的值一起，Delta G（HYD）的编译列表是最重要的报道，并且都是热化学上的;即，他们同意其相应的热化学循环。这些数字使用约定的ΔG（HED）（H +）= -1100 kJ / mol，她= +4.44 V，但可以很容易地调整到其他参考状态。在此建立的一些新的ΔG（HYD）值适用于催化重要的D-过渡金属离子RH3 +，RE-3 +，RE-IR3 +，MO3 +，W3 +，TC2 +，NB3 +，TA3 +，00+和RU2 +。一些，例如IR3 +，是最多惰性的惰性水腹部。 AGHYD值具有类似于10kJ / mol的精度，建议用于热化学计算，以解释金属离子的含水化学，以及理论化学的基准。

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