Thermodynamic properties of gaseous cerium molybdates and tungstates studied by Knudsen effusion mass spectrometry

Шугуров, С. М.; Panin, A. I.; Лопатин, С. И.

doi:10.1002/rcm.8210

Cited by 5 publications

(11 citation statements)

References 78 publications

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“…The value of reaction enthalpy, which was determined by Equation , is in a reasonable agreement with the values obtained earlier for gaseous cerium molybdates and tungstates . The values of reaction enthalpy determined by the second law procedure have more error value and decrease the correlation coefficient of Equation .…”

Section: Resultssupporting

confidence: 89%

“…The results obtained in this work together with the results obtained in our previous investigation of gaseous cerium oxyacid salts allow to obtain some regularities. In particular: The relative content of gaseous cerium oxyacid salt in high temperature vapor is low and does not exceed 1%. The main component of vapor over cerium dioxide is CeO 2 molecule.…”

Section: Resultssupporting

confidence: 70%

“…Beside of this, we have strong signal of O 2 + from the atmospheric background, which is very difficult to separate from the signal of the effusion cell. The WO 2 + and WO 3 + ions are the products of ionization of WO 2 and WO 3 , respectively . This species are produced as the result of interaction of the sample with the cell material.…”

Section: Resultsmentioning

confidence: 99%

“…It cannot therefore be excluded that the gas phase reaction (11) may occur and CePO 3 molecule may be formed as a result of this reaction. On other hand, the presence of gaseous CeO 2 and PO 2 species with high partial pressures leads to the assumption about possible formation of CePO 4 molecule (reaction ) by analogy with CeMoO 5 and CeWO 5 molecules

{CeO}_{2} + PO = {CePO}_{3},

{CeO}_{2} + {PO}_{2} = {CePO}_{4} .

Since the gaseous CePO 3 and CePO 4 species were not detected at our experimental conditions, we confined ourselves to study their equilibrium structures and molecular parameters by several quantum chemistry methods: DFT M06, DFT TPSSh, MP2(Full), and MP4(Full,SDQ).…”

Section: Resultsmentioning

confidence: 99%

“…

Δ_{at} H^{0} ((),,, M_{m} {XO}_{n}, gas, 298) = k Δ_{at} H^{0} ((),,, anion - forming oxide, gas, 298) + b .

In our case, M = Ce, m = 1 and anion‐forming oxides are PO, WO 2 , WO 3 , MoO 3 , and Mo 2 O 6 . Atomization enthalpies of the cerium molybdates and tungstates are taken from Shugurov et al This correlation for cerium salts is represented by the dependence displayed in Figure . The coefficients k and b of this regression are equal to 1.016 ± 0.019 and 1198.9 ± 42.7, respectively, and the correlation coefficient is 0.9995.…”

Section: Resultsmentioning

confidence: 99%

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Thermodynamic properties of gaseous cerium phosphate studied by Knudsen effusion mass spectrometry

2019

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Gaseous CePO2 has been identified by Knudsen effusion mass spectrometry during vaporization of CeO2 and magnesium diphosphate from tungsten double, two‐temperature effusion cell. Structure and molecular parameters of gaseous cerium phosphate under study were determined using quantum chemical calculations. On the basis of equilibrium constants measured for gas‐phase reaction, standard formation enthalpy of CePO2 was determined to be −508 ± 41 kJ ⋅ mol−1 at the temperature 298 K.

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Section: Resultssupporting

confidence: 89%

Section: Resultssupporting

confidence: 70%

Section: Resultsmentioning

confidence: 99%

{CeO}_{2} + PO = {CePO}_{3},

{CeO}_{2} + {PO}_{2} = {CePO}_{4} .

Section: Resultsmentioning

confidence: 99%

“…

Δ_{at} H^{0} ((),,, M_{m} {XO}_{n}, gas, 298) = k Δ_{at} H^{0} ((),,, anion - forming oxide, gas, 298) + b .

Section: Resultsmentioning

confidence: 99%

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Thermodynamic properties of gaseous cerium phosphate studied by Knudsen effusion mass spectrometry

2019

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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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Enhanced CeO2 evaporation from refractory crucibles (Mo, Ta, W)

Antonov,

Gavrikov,

Kuzmichev

et al. 2024

Heat Mass Transfer

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Thermodynamic properties of gaseous cerium molybdates and tungstates studied by Knudsen effusion mass spectrometry

Cited by 5 publications

References 78 publications

Thermodynamic properties of gaseous cerium phosphate studied by Knudsen effusion mass spectrometry

Thermodynamic properties of gaseous cerium phosphate 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)

Enhanced CeO2 evaporation from refractory crucibles (Mo, Ta, W)

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Thermodynamic properties of gaseous cerium molybdates and tungstates studied by Knudsen effusion mass spectrometry

Cited by 5 publications

References 78 publications

Thermodynamic properties of gaseous cerium phosphate studied by Knudsen effusion mass spectrometry

Thermodynamic properties of gaseous cerium phosphate 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)

Enhanced CeO2 evaporation from refractory crucibles (Mo, Ta, W)

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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)