Mass Spectrometric Study of Stability, Thermochemistry and Structures of the Gaseous Oxyacid Salts

Лопатин, С. И.; Шугуров, С. М.

doi:10.2174/1874396x01307010035

Cited by 7 publications

(5 citation statements)

References 96 publications

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“…In the isocation series of gaseous oxy‐acid salts the atomization enthalpy of gaseous salts depends linearly on the atomization enthalpy of the gaseous anion‐forming oxide . This linear dependence can be represented by Equation :

Δ_{at} H^{0} ((),,, salt, gas, 298) = k Δ_{at} H^{0} ((),,, anion - forming oxide, gas, 298) + b

Prior to this work, data for at last 28 gaseous barium salts had been known, as shown in Figure .…”

Section: Resultsmentioning

confidence: 99%

“…In the isocation series of gaseous oxy-acid salts the atomization enthalpy of gaseous salts depends linearly on the atomization enthalpy of the gaseous anion-forming oxide. [1][2][3] This linear dependence can be represented by Equation (8):…”

Section: Methodsmentioning

confidence: 99%

“…The existence of a number of gaseous salts formed by oxides of the elements of the 14 th group of the periodic table is known, with the oxides possessing both basic and acidic properties. The thermal stability of a salt primarily depends on the acid–base properties of the oxides that form it .…”

Section: Introductionmentioning

confidence: 99%

“…Although SnO has rather pronounced basic properties, analogous to GeO, CrO, VO, NbO and MoO, it can also exhibit acidic properties, performing the function of an anion‐forming oxide, when alkaline oxides or barium oxide act as a cation‐forming oxide…”

Section: Introductionmentioning

confidence: 99%

“…18,19 PbO, due to its basic properties, is a typical cation-forming oxide in the synthesis of gaseous salts, and 13 gaseous lead salts are known. 20 Although SnO has rather pronounced basic properties, [1][2][3] analogous to GeO, CrO, VO, NbO and MoO, it can also exhibit acidic properties, performing the function of an anion-forming oxide, when alkaline oxides or barium oxide act as a cation-forming oxide. 21 The present work relates to an attempt to synthesize in a hightemperature vapor a gaseous salt which is the product of interaction between BaO and SnO, and also to determine the thermodynamic properties of BaSnO 2 .…”

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confidence: 99%

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Thermodynamic properties of gaseous BaSnO₂ and Ba₂O₂ studied by Knudsen effusion mass spectrometry

Emelyanova

Шугуров

Panin

et al. 2020

Rapid Comm Mass Spectrometry

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Rationale BaSnO3 is an interesting technical and industrial ceramic, with uses in many areas of electronic technology. Currently, there is great interest in this ceramic material because of its potential as a transparent conductive oxide. Due to its good chemical stability, it is also used as a surface processing material in the synthesis of electroluminophores. When heated, the stannates of alkaline earth metals can pass into the vapor phase with or without dissociation. Until the present investigation, gaseous salts where SnO plays the role of an anion‐forming oxide had been unknown. The formation enthalpy of gaseous Ba2O2 also needed to be determined. Methods Knudsen effusion mass spectrometry was used to determine the partial pressures of vapor species, equilibrium constants and enthalpies of the studied gas‐phase reactions, as well as the formation and atomization enthalpies of gaseous BaSnO2 and Ba2O2: a mixture of BaO and SnO2 was evaporated from a platinum effusion cell. For the evaporation of gold (pressure standard), a molybdenum effusion cell was used. A theoretical study of gaseous BaSnO2 and Ba2O2 was performed by several quantum chemistry methods. Results Ba, BaO, Ba2O2, SnO and BaSnO2 were found to be the main species in the vapor over the BaO–SnO2 mixture in the temperature range of 1680–1920 K. The standard formation enthalpies of gaseous BaSnO2 and Ba2O2 were determined on the basis of the equilibrium constants of the studied gas‐phase reactions. Energetically favorable structures of these gaseous species were found and vibrational frequencies were evaluated in the harmonic approximation. The formation enthalpy of gaseous Ba2O2 was clarified; in addition, the formation enthalpies of gaseous SrSnO3 and CaSnO3 were estimated. Conclusions The thermal stability of gaseous BaSnO2 was confirmed by Knudsen effusion mass spectrometry. The reaction enthalpies of gaseous BaSnO2 from gaseous barium and tin oxides were theoretically evaluated and the obtained values were found to be in reasonable agreement with the experimental ones.

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Δ_{at} H^{0} ((),,, salt, gas, 298) = k Δ_{at} H^{0} ((),,, anion - forming oxide, gas, 298) + b

Prior to this work, data for at last 28 gaseous barium salts had been known, as shown in Figure .…”

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Thermodynamic properties of gaseous BaSnO₂ and Ba₂O₂ studied by Knudsen effusion mass spectrometry

Emelyanova

Шугуров

Panin

et al. 2020

Rapid Comm Mass Spectrometry

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Thermodynamics of gaseous strontium and calcium cerates studied by Knudsen effusion mass spectrometry and estimation of relative electron ionization cross‐section for CeO₂(g)

Shugurov,

Lopatin,

Zhinkina

et al. 2024

Rapid Comm Mass Spectrometry

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RationaleCeria‐based systems are of great interest because of their unique properties. Such systems may be used as anode materials for SOFCs or in oxygen sensors. The exploitation of these materials often requires high temperatures. In such conditions, the partial or complete evaporation of materials is possible. Therefore, knowledge of the values of partial pressures and thermodynamic properties is essential to predict and/or prevent possible consequences and accidents.MethodsKnudsen effusion mass spectrometry was used to determine partial pressures of vapor species over the SrO–CeO2 and CaO‐CeO2 systems. Measurements of partial pressures were performed with a MS‐1301 mass spectrometer. Vaporization was carried out using molybdenum or tungsten effusion cells. A theoretical study of gaseous strontium and calcium cerates was performed by several quantum chemical methods: density functional theory (DFT) M06, DFT PBE0, and MP2.ResultsThe minimum value of relative electron ionization cross‐section for CeO2 was estimated. In the temperature range of 2218–2249 K above the SrO‐CeO2 system and of 2128–2208 K above the CaO‐CeO2 system, gaseous M, MO, MO, CeO2, O, O2 and MCeO3 (M = Sr, Ca) were found. Energetically favorable structures of gaseous SrCeO3 and CaCeO3 were found, and vibrational frequencies were evaluated in the “rigid rotor‐harmonic oscillator” approximation. On the basis of the equilibrium constants of gaseous reaction MO + CeO2 = MCeO3, the standard formation enthalpy of gaseous SrCeO3 (−913 ± 26 kJ/mol) and of gaseous CaCeO3 (−917 ± 26 kJ/mol) at 298 K were determined.ConclusionsThe estimated value of relative electron ionization cross‐section for CeO2 is in agreement with the general rule applicable for dioxides. The stability of SrCeO3 and CaCeO3 gaseous species was confirmed by KEMS. Gas‐phase reactions involving gaseous SrO (CaO) and CeO2 with gaseous SrCeO3(CaCeO3) were studied. Enthalpy of formation reaction of gaseous SrCeO3(CaCeO3) from gaseous SrO (CaO) were evaluated theoretically, and the obtained value is in agreement with the experimental one.

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High-Temperature Chemistry Applications of Mass Spectrometry

Sidorov¹,

Lopatin²

2013

Reference Module in Chemistry, Molecular Sciences and Chemical Engineering

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Mass Spectrometric Study of Stability, Thermochemistry and Structures of the Gaseous Oxyacid Salts

Cited by 7 publications

References 96 publications

Thermodynamic properties of gaseous BaSnO₂ and Ba₂O₂ studied by Knudsen effusion mass spectrometry

Thermodynamic properties of gaseous BaSnO₂ and Ba₂O₂ studied by Knudsen effusion mass spectrometry

Thermodynamics of gaseous strontium and calcium cerates studied by Knudsen effusion mass spectrometry and estimation of relative electron ionization cross‐section for CeO₂(g)

High-Temperature Chemistry Applications of Mass Spectrometry

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Mass Spectrometric Study of Stability, Thermochemistry and Structures of the Gaseous Oxyacid Salts

Cited by 7 publications

References 96 publications

Thermodynamic properties of gaseous BaSnO2 and Ba2O2 studied by Knudsen effusion mass spectrometry

Thermodynamic properties of gaseous BaSnO2 and Ba2O2 studied by Knudsen effusion mass spectrometry

Thermodynamics of gaseous strontium and calcium cerates studied by Knudsen effusion mass spectrometry and estimation of relative electron ionization cross‐section for CeO2(g)

High-Temperature Chemistry Applications of Mass Spectrometry

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Resources

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Thermodynamic properties of gaseous BaSnO₂ and Ba₂O₂ studied by Knudsen effusion mass spectrometry

Thermodynamic properties of gaseous BaSnO₂ and Ba₂O₂ studied by Knudsen effusion mass spectrometry

Thermodynamics of gaseous strontium and calcium cerates studied by Knudsen effusion mass spectrometry and estimation of relative electron ionization cross‐section for CeO₂(g)