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首页> 外文期刊>Chemistry: A European journal >Directly Relating Gas-Phase Cluster Measurements to Solution-Phase Hydrolysis, the Absolute Standard Hydrogen Electrode Potential, and the Absolute Proton Solvation Energy
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Directly Relating Gas-Phase Cluster Measurements to Solution-Phase Hydrolysis, the Absolute Standard Hydrogen Electrode Potential, and the Absolute Proton Solvation Energy

机译：将气相相簇测量与溶液相水解，绝对标准氢电极电势和质子绝对溶剂能直接相关

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摘要

Solution-phase, half-cell potentials are measured relative to other half-cell potentials, resulting in a thermochemical ladder that is anchored to the standard hydrogen electrode (SHE), which is assigned an arbitrary value of 0 V. A new method for measuring the absolute SHE potential is demonstrated in which gaseous nanodrops containing divalent alkaline-earth or transition-metal ions are reduced by thermally generated electrons. Energies for the reactions 1) M-(H2O)(24)(2+)(g) + e(-)(g)-> M(H2O)(24)(+)(g) and 2) M(H2O)(24)(2+)(g) + e(-)(g)-> MOH-(H2O)(23)(+)(g)+H(g) and the hydrogen atom affinities of MOH(H2O)(23)(+)(g) are obtained from the number of water molecules lost through each pathway. From these measurements on clusters containing nine different metal ions and known thermochemical values that include solution hydrolysis energies, an average absolute SHE potential of +4.29V vs. e(-)(g) (standard deviation of 0.02V) and a real proton solvation free energy of -265 kcal mol(-1) are obtained. With this method, the absolute SHE potential can be obtained from a one-electron reduction of nanodrops containing divalent ions that are not observed to undergo one-electron reduction in aqueous solution.
机译：相对于其他半电池电位，测量溶液相半电池电位，从而产生固定在标准氢电极（SHE）上的热化学阶梯，该阶梯被指定为0 V的任意值。一种新的测量方法证实了绝对SHE势，其中热产生的电子还原了包含二价碱土或过渡金属离子的气态纳米滴。反应能量1）M-（H2O）（24）（2 +）（g）+ e（-）（g）-> M（H2O）（24）（+）（g）和2）M（H2O ）（24）（2 +）（g）+ e（-）（g）-> MOH-（H2O）（23）（+）（g）+ H（g）和MOH（H2O）的氢原子亲和力（23）（+）（g）是从通过每个途径损失的水分子数量中获得的。通过对包含九种不同金属离子和已知热化学值（包括溶液水解能）的簇的测量，平均绝对SHE电位+ 4.29V vs. e（-）（g）（标准偏差0.02V）和真实的质子溶剂化获得-265 kcal mol（-1）的自由能。通过这种方法，可以从含有二价离子的纳米滴的单电子还原中获得绝对的SHE电位，这些二价离子在水溶液中未经历单电子还原。

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