Institute of Chemistry, St Petersburg State University, 198504, St Petersburg, Russia.
Rapid Commun Mass Spectrom. 2019 Dec 15;33(23):1826-1833. doi: 10.1002/rcm.8544.
Sulfide systems are often used at high temperatures, when vaporization of the components is enabled. Sulfide ores are used as sources of various metals and nonmetals and gaseous sulfides, and sulfosalts may also play a role in the atmosphere chemistry of hot rocky exoplanets. To predict the existence and thermal stability of gaseous sulfides and sulfosalts it is important to know their thermodynamic characteristics. In this study the sulfosalt of indium and arsenic was obtained in the gaseous phase for the first time.
High-temperature Knudsen effusion mass spectrometry was used to determine the partial pressures of vapor species over indium and arsenic sulfides. A molybdenum double two-temperature cell was used to create the conditions of coexistence of indium and arsenic sulfides. A theoretical study of gaseous As S and In AsS was performed using both B3LYP, M06, PBE0 and TPSSh hybrid DFT functionals and an ab initio wave function-based MP2(Full) method.
Gaseous In AsS has been identified during vaporization of In S and As S from the molybdenum double two-temperature cell. The structure and molecular parameters of gaseous In AsS were determined using quantum chemical calculations. Energetically favorable structures of gaseous In S, AsS, As S and In AsS were found and vibrational frequencies were evaluated in the harmonic approximation. The formation enthalpy of gaseous In AsS (186 ± 37 kJ mol ) was derived as a result of measurements of the equilibrium constants of two independent gas-phase reactions.
The gaseous sulfosalt of indium and arsenic was obtained for the first time. The formation enthalpy of the In AsS (g) molecule at 298 K was evaluated both experimentally and theoretically. The thermal stability of the gaseous sulfosalt is less than that of the gaseous oxyacid salts.
当组分能够蒸发时，硫化物体系通常在高温下使用。硫化物矿石被用作各种金属和非金属以及气态硫化物的来源，而硫代硫酸盐也可能在热岩外行星的大气化学中发挥作用。为了预测气态硫化物和硫代硫酸盐的存在和热稳定性，了解它们的热力学特性非常重要。在这项研究中，首次在气相中获得了砷化铟和砷的硫代硫酸盐。
高温克努森扩散质谱法用于确定硫化铟和砷蒸气物种的分压。钼双双温度室用于创造共存铟和砷硫化物的条件。使用 B3LYP、M06、PBE0 和 TPSSh 杂化 DFT 函数以及从头算波函数的 MP2（全）方法对气态 AsS 和 InAsS 进行了理论研究。
在钼双双温度室中从 InS 和 AsS 蒸发时，已鉴定出气态 InAsS。使用量子化学计算确定了气态 InAsS 的结构和分子参数。找到了气态 InS、AsS、AsS 和 InAsS 的能量有利结构，并在谐波近似中评估了振动频率。气态 InAsS（186±37 kJ mol）形成焓是通过测量两个独立气相反应的平衡常数得出的。
首次获得了砷化铟和砷的气态硫代硫酸盐。通过实验和理论评估了 298 K 时 InAsS（g）分子的形成焓。气态硫代硫酸盐的热稳定性小于气态含氧酸盐。
