Estimation of thermodynamic and physicochemical properties of the alkali astatides: On the bond strength of molecular astatine (At2) and the hydration enthalpy of astatide (At−)

IF 1.9 3区 化学 Q3 BIOCHEMICAL RESEARCH METHODS
Peter C. Burgers, Lona Zeneyedpour, Theo M. Luider, John L. Holmes
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Abstract

The recent accurate and precise determination of the electron affinity (EA) of the astatine atom At0 warrants a re-investigation of the estimated thermodynamic properties of At0 and astatine containing molecules as this EA was found to be much lower (by 0.4 eV) than previous estimated values. In this contribution we estimate, from available data sources, the following thermodynamic and physicochemical properties of the alkali astatides (MAt, M = Li, Na, K, Rb, Cs): their solid and gaseous heats of formation, lattice and gas-phase binding enthalpies, sublimation energies and melting temperatures. Gas-phase charge-transfer dissociation energies for the alkali astatides (the energy requirement for M+At ➔ M0 + At0) have been obtained and are compared with those for the other alkali halides. Use of Born-Haber cycles together with the new AE (At0) value allows the re-evaluation of ΔHf (At0)g (=56 ± 5 kJ/mol); it is concluded that (At2)g is a weakly bonded species (bond strength <50 kJ/mol), significantly weaker bonded than previously estimated (116 kJ/mol) and much weaker bonded than I2 (148 kJ/mol), but in agreement with the finding from theory that spin-orbit coupling considerably reduces the bond strength in At2. The hydration enthalpy (ΔHaq) of At is estimated to be −230 ± 2 kJ/mol (using ΔHaq[H+] = −1150.1 kJ/mol), in good agreement with molecular dynamics calculations. Arguments are presented that the largest alkali halide, CsAt, like the smallest, LiF, will be only sparingly soluble in water, following the generalization from hard/soft acid/base principles that “small likes small” and “large likes large.”

Abstract Image

碱砹化物的热力学和物理化学性质的估计:关于分子砹(At2)的键强度和砹化物(At-)的水合焓。
最近对砹原子 At0 的电子亲和力(EA)进行了准确和精确的测定,因此有必要重新调查 At0 和含砹分子的估计热力学性质,因为发现该 EA 比以前的估计值要低得多(低 0.4 eV)。在这篇论文中,我们根据现有数据源估算了碱砹化物(MAt,M = Li、Na、K、Rb、Cs)的以下热力学和物理化学性质:它们的固态和气态形成热、晶格和气相结合焓、升华能和熔化温度。已获得碱砹化物的气相电荷转移解离能(M+ At- ➔ M0 + At0 的能量要求),并与其他碱卤化物的气相电荷转移解离能进行了比较。利用玻恩-哈伯循环和新的 AE (At0 ) 值,可以重新评估 ΔHf (At0 )g (=56 ± 5 kJ/mol);结论是 (At2 )g 是弱键物种(键强度 2 (148 kJ/mol),但与理论发现的自旋轨道耦合大大降低 At2 的键强度一致。At- 的水合焓(ΔHaq)估计为 -230 ± 2 kJ/mol(使用 ΔHaq [H+ ] = -1150.1 kJ/mol),与分子动力学计算结果十分吻合。根据 "小喜小 "和 "大喜大 "的硬/软酸/碱原理的概括,提出了最大的碱卤化物 CsAt 和最小的 LiF 一样只能少量溶于水的论点。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Journal of Mass Spectrometry
Journal of Mass Spectrometry 化学-光谱学
CiteScore
5.10
自引率
0.00%
发文量
84
审稿时长
1.5 months
期刊介绍: The Journal of Mass Spectrometry publishes papers on a broad range of topics of interest to scientists working in both fundamental and applied areas involving the study of gaseous ions. The aim of JMS is to serve the scientific community with information provided and arranged to help senior investigators to better stay abreast of new discoveries and studies in their own field, to make them aware of events and developments in associated fields, and to provide students and newcomers the basic tools with which to learn fundamental and applied aspects of mass spectrometry.
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