Thermodynamic and quantum chemistry calculations of species in the molten AlCl3–MCl (M = Li, Na, K) system

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry Pub Date : 2025-07-08 DOI:10.1016/j.comptc.2025.115368

Ruidong Guo , Xianwei Hu , Liang Tian , Hongguang Kang , Ao Xu , Zhongning Shi , Zhaowen Wang

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Abstract

The Hall–Héroult process dominates aluminum production but suffers from high energy demands and pollution. This study investigates the aluminum chloride process as an alternative method by analyzing species behavior in AlCl₃–MCl (M = Li, Na, K) molten salts at 373–473 K and 933–1033 K through quantum calculations and mathematical modeling. When initial AlCl₃ < 50 mol%, Cl⁻ and AlCl₄⁻ dominate at 933–1033 K, with minor temperature effects. When initial AlCl₃ > 50 mol%, AlCl₄⁻, Al₂Cl₇⁻ and Al₂Cl₆ dominate at 373–473 K. Increasing AlCl₃ concentration decreases AlCl₄⁻ fraction; Al₂Cl₇⁻ fraction peaks at 66.7 mol% AlCl₃ then declines; Al₂Cl₆ fraction steadily increases. Higher temperatures promote Al₂Cl₇⁻ conversion to AlCl₄⁻ and Al₂Cl₆. Redox calculations show preferential Cl⁻ discharge at the anode when AlCl₃ < 50 mol%. At AlCl₃ > 50 mol%, Al³⁺ in Al₂Cl₆ discharges at the cathode and Cl⁻ in Al₂Cl₇⁻ discharges at the anode.

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熔融AlCl3-MCl （M = Li, Na， K）体系中物质的热力学和量子化学计算

霍尔-海姆法在铝生产中占主导地位，但能源需求高且污染严重。本研究通过量子计算和数学建模，分析了AlCl3-MCl （M = Li, Na， K）熔盐在373-473 K和933-1033 K下的物质行为，研究了氯化铝工艺作为一种替代方法。初始AlCl3 <；933 ~ 1033 K时，Cl−和AlCl4−占主导地位，温度影响较小。初始化AlCl3 >；在373 ~ 473 K时，AlCl4−、Al2Cl7−和Al2Cl6占主导地位。AlCl3浓度增加，AlCl4−分数降低；Al2Cl7−分数在66.7 mol% AlCl3时达到峰值，然后下降；Al2Cl6分数稳步增加。较高的温度促进Al2Cl7−转化为AlCl4−和Al2Cl6。氧化还原计算表明，当AlCl3 <；50摩尔%。At all >；50 mol%时，Al2Cl6中的Al3+在阴极放电，Al2Cl7−中的Cl−在阳极放电。

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来源期刊

Computational and Theoretical Chemistry CHEMISTRY, PHYSICAL-

CiteScore

4.20

自引率

10.70%

发文量

331

审稿时长

31 days

期刊介绍： Computational and Theoretical Chemistry publishes high quality, original reports of significance in computational and theoretical chemistry including those that deal with problems of structure, properties, energetics, weak interactions, reaction mechanisms, catalysis, and reaction rates involving atoms, molecules, clusters, surfaces, and bulk matter.