Thermochemical study of gaseous indium–arsenic sulfosalt

Research output

Abstract

Rationale: 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. Methods: 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 As4S4 and In2AsS2 was performed using both B3LYP, M06, PBE0 and TPSSh hybrid DFT functionals and an ab initio wave function-based MP2(Full) method. Results: Gaseous In2AsS2 has been identified during vaporization of In6S7 and As2S3 from the molybdenum double two-temperature cell. The structure and molecular parameters of gaseous In2AsS2 were determined using quantum chemical calculations. Energetically favorable structures of gaseous In2S, AsS, As4S4 and In2AsS2 were found and vibrational frequencies were evaluated in the harmonic approximation. The formation enthalpy of gaseous In2AsS2 (186 ± 37 kJ mol−1) was derived as a result of measurements of the equilibrium constants of two independent gas-phase reactions. Conclusions: The gaseous sulfosalt of indium and arsenic was obtained for the first time. The formation enthalpy of the In2AsS2 (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.

Original languageEnglish
Pages (from-to)1826-1833
JournalRapid Communications in Mass Spectrometry
Volume33
Issue number23
Early online date1 Aug 2019
DOIs
Publication statusPublished - 15 Dec 2019

Fingerprint

Indium
Sulfides
Molybdenum
Arsenic
Vaporization
Enthalpy
Thermodynamic stability
Nonmetals
Temperature
Equilibrium constants
Vibrational spectra
Wave functions
Discrete Fourier transforms
Partial pressure
Ores
Mass spectrometry
Salts
Gases
Metals
Vapors

Scopus subject areas

  • Analytical Chemistry
  • Spectroscopy
  • Organic Chemistry

Cite this

@article{50b8ce9700734b9487ff0271f40842a9,
title = "Thermochemical study of gaseous indium–arsenic sulfosalt",
abstract = "Rationale: 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. Methods: 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 As4S4 and In2AsS2 was performed using both B3LYP, M06, PBE0 and TPSSh hybrid DFT functionals and an ab initio wave function-based MP2(Full) method. Results: Gaseous In2AsS2 has been identified during vaporization of In6S7 and As2S3 from the molybdenum double two-temperature cell. The structure and molecular parameters of gaseous In2AsS2 were determined using quantum chemical calculations. Energetically favorable structures of gaseous In2S, AsS, As4S4 and In2AsS2 were found and vibrational frequencies were evaluated in the harmonic approximation. The formation enthalpy of gaseous In2AsS2 (186 ± 37 kJ mol−1) was derived as a result of measurements of the equilibrium constants of two independent gas-phase reactions. Conclusions: The gaseous sulfosalt of indium and arsenic was obtained for the first time. The formation enthalpy of the In2AsS2 (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.",
author = "Shugurov, {Sergey M.} and Panin, {Andrej I.} and Lopatin, {Sergey I.} and Pulyalina, {Alexandra Yu}",
year = "2019",
month = "12",
day = "15",
doi = "10.1002/rcm.8544",
language = "English",
volume = "33",
pages = "1826--1833",
journal = "Rapid Communications in Mass Spectrometry",
issn = "0951-4198",
publisher = "Wiley-Blackwell",
number = "23",

}

TY - JOUR

T1 - Thermochemical study of gaseous indium–arsenic sulfosalt

AU - Shugurov, Sergey M.

AU - Panin, Andrej I.

AU - Lopatin, Sergey I.

AU - Pulyalina, Alexandra Yu

PY - 2019/12/15

Y1 - 2019/12/15

N2 - Rationale: 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. Methods: 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 As4S4 and In2AsS2 was performed using both B3LYP, M06, PBE0 and TPSSh hybrid DFT functionals and an ab initio wave function-based MP2(Full) method. Results: Gaseous In2AsS2 has been identified during vaporization of In6S7 and As2S3 from the molybdenum double two-temperature cell. The structure and molecular parameters of gaseous In2AsS2 were determined using quantum chemical calculations. Energetically favorable structures of gaseous In2S, AsS, As4S4 and In2AsS2 were found and vibrational frequencies were evaluated in the harmonic approximation. The formation enthalpy of gaseous In2AsS2 (186 ± 37 kJ mol−1) was derived as a result of measurements of the equilibrium constants of two independent gas-phase reactions. Conclusions: The gaseous sulfosalt of indium and arsenic was obtained for the first time. The formation enthalpy of the In2AsS2 (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.

AB - Rationale: 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. Methods: 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 As4S4 and In2AsS2 was performed using both B3LYP, M06, PBE0 and TPSSh hybrid DFT functionals and an ab initio wave function-based MP2(Full) method. Results: Gaseous In2AsS2 has been identified during vaporization of In6S7 and As2S3 from the molybdenum double two-temperature cell. The structure and molecular parameters of gaseous In2AsS2 were determined using quantum chemical calculations. Energetically favorable structures of gaseous In2S, AsS, As4S4 and In2AsS2 were found and vibrational frequencies were evaluated in the harmonic approximation. The formation enthalpy of gaseous In2AsS2 (186 ± 37 kJ mol−1) was derived as a result of measurements of the equilibrium constants of two independent gas-phase reactions. Conclusions: The gaseous sulfosalt of indium and arsenic was obtained for the first time. The formation enthalpy of the In2AsS2 (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.

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U2 - 10.1002/rcm.8544

DO - 10.1002/rcm.8544

M3 - Article

C2 - 31373065

AN - SCOPUS:85075093711

VL - 33

SP - 1826

EP - 1833

JO - Rapid Communications in Mass Spectrometry

JF - Rapid Communications in Mass Spectrometry

SN - 0951-4198

IS - 23

ER -