Thermodynamic properties of neutral and charged species in high-temperature vapour over terbium and thulium trichlorides

Кудин, Л. С.; Pogrebnoi, Alexander; Khasanshin, I. V.; Моталов, В. Б.

doi:10.1068/htwu144

Cited by 20 publications

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“…A single focusing sector type magnet mass spectrometer MI-1201 modified for high temperature experiments was used [ 16 , 17 ]. Samples formed as disks were attached in molybdenum cylindrical holder at a depth of 2 mm from its surface.…”

Section: Methodsmentioning

confidence: 99%

Thermal Emission of Alkali Metal Ions from Al₃₀-Pillared Montmorillonite Studied by Mass Spectrometric Method

Моталов

Karasev

Ovchinnikov

et al. 2017

Journal of Analytical Methods in Chemistry

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The thermal emission of alkali metal ions from Al30-pillared montmorillonite in comparison with its natural form was studied by mass spectrometry in the temperature range 770–930 K. The measurements were carried out on a magnetic mass spectrometer MI-1201. For natural montmorillonite, the densities of the emission currents (j) decrease in the mass spectrum in the following sequence (T = 805 K, A/cm2): K+ (4.55 · 10−14), Cs+ (9.72 · 10−15), Rb+ (1.13 · 10−15), Na+ (1.75 · 10−16), Li+ (3.37 · 10−17). For Al30-pillared montmorillonite, thermionic emission undergoes temperature-time changes. In the low-temperature section of the investigated range (770–805 K), the value of j increases substantially for all ions in comparison with natural montmorillonite (T = 805 K, A/cm2): Cs+ (6.47 · 10−13), K+ (9.44 · 10−14), Na+ (3.34 · 10−15), Rb+ (1.77 · 10−15), and Li+ (4.59 · 10−16). A reversible anomaly is observed in the temperature range 805–832 K: with increasing temperature, the value of j of alkaline ions falls abruptly. This effect increases with increasing ionic radius of M+. After a long heating-up period, this anomaly disappears and the lnj − 1/T dependence acquires a classical linear form. The results are interpreted from the point of view of the dependence of the efficiency of thermionic emission on the phase transformations of pillars.

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Section: Methodsmentioning

confidence: 99%

Thermal Emission of Alkali Metal Ions from Al₃₀-Pillared Montmorillonite Studied by Mass Spectrometric Method

Моталов

Karasev

Ovchinnikov

et al. 2017

Journal of Analytical Methods in Chemistry

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“…This effect was due to the gradual blinding of the orifice in the extraction electrode (collimator) owing to LuCl 3 condensation on the relatively cold electrode surface. 2 The reduction in the effective diameter of the orifice improves the ion-beam collimation and reduces the probability of recording "surface" ions [11,12] (see below). In connection with this, the table gives the lower limit of the enthalpy of reaction (1), calculated from the data obtained at the end of the experiment.…”

Section: Lumentioning

confidence: 99%

“…Another possibility is an induction period in the initial stages of vaporization. In the range 1109-1386 K, ∆ r H 0 (298.15 K) is temperature-independent until complete evaporation of the 2 The blinding of the orifice in the extraction electrode was revealed by inspecting the evaporation source after the experiment. 3 LuCl 3 -EuCl 3 , and LuCl 3 -EuCl 3 -HoCl 3 -NdCl 3 samples were evaporated from a graphite insert.…”

Section: Lumentioning

confidence: 99%

“…Experimental studies of the thermodynamics of vaporization of lanthanide trichlorides (see, e.g., [1-3]) show that the saturated vapor over these trichlorides contains (LnCl 3 ) n molecular and Cl -· (LnCl 3 ) n ionic associates with n up to 8 [2]. Among ionic species, the Lu ions are the dominant components of the hightemperature vapor phase.…”

Section: Introductionmentioning

confidence: 99%

“…From the average enthalpy of reaction (8), ∆ r H 0 (298.15 K) = -27 ± 10 kJ/mol, and the enthalpy Enthalpy ∆ r H 0 (298.15 K) of reaction (2) as a function of temperature (high temperatures). Arrhenius plot of the equilibrium constant of reaction(2).…”

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confidence: 99%

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Stability of the LaCl 4 − and LuCl 4 − Ions Studied by Mass Spectrometry

2005

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Vapor species over cerium and samarium trichlorides, enthalpies of formation of (LnCl₃)_n molecules and Cl⁻(LnCl₃)_n ions

Pogrebnoi¹,

Кудин²,

Моталов³

et al. 2001

Rapid Comm Mass Spectrometry

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A Knudsen effusion cell mass spectrometric technique was used to study vapor species over CeCl(3) and SmCl(3). Monomer, dimer, and trimer (Sm(3)Cl(9)) molecules, and LnCl(4-), Ln(2)Cl(7-), Ln(3)Cl(10-) (Ln = Ce, Sm) negative ions, were observed in saturated vapor in the temperature range 958-1227 K. Partial vapor pressures of neutral constituents were determined and the enthalpies of sublimation (Delta(s)H, 298 K, kJ.mol(-1)) to monomers and associated molecules obtained: 328 +/- 6 (CeCl(3)), 306 +/- 6 (SmCl(3)), 453 +/- 16 (Ce(2)Cl(6)), 408 +/- 12 (Sm(2)Cl(6)), and 468 +/- 40 (Sm(3)Cl(9)). Equilibrium constants for various chemical reactions were measured and the enthalpies of reactions obtained using the second and third laws of thermodynamics. The enthalpies of formation (Delta(f)H, 298 K, kJ.mol(-1)) of molecules and ions have been calculated as follows: -730 +/- 6 (CeCl(3)), -722 +/- 6 (SmCl(3)), -1663 +/- 16 (Ce(2)Cl(6)), -1649 +/- 13 (Sm(2)Cl(6)), -2617 +/- 40 (Sm(3)Cl(9)), -1250 +/- 15 (CeCl(4)(-)), -1252 +/- 15 (SmCl(4-)), -2184 +/- 35(Ce(2)Cl(7-)), -2172 +/- 26 (Sm(2)Cl(7-)), -3183 +/- 43 (Ce(3)Cl(10-)), and -3147 +/- 43 (Sm(3)Cl(10-)).

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Thermodynamic properties of neutral and charged species in high-temperature vapour over terbium and thulium trichlorides

Cited by 20 publications

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Thermal Emission of Alkali Metal Ions from Al₃₀-Pillared Montmorillonite Studied by Mass Spectrometric Method

Thermal Emission of Alkali Metal Ions from Al₃₀-Pillared Montmorillonite Studied by Mass Spectrometric Method

Stability of the LaCl 4 − and LuCl 4 − Ions Studied by Mass Spectrometry

Vapor species over cerium and samarium trichlorides, enthalpies of formation of (LnCl₃)_n molecules and Cl⁻(LnCl₃)_n ions

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Thermodynamic properties of neutral and charged species in high-temperature vapour over terbium and thulium trichlorides

Cited by 20 publications

References 0 publications

Thermal Emission of Alkali Metal Ions from Al30-Pillared Montmorillonite Studied by Mass Spectrometric Method

Thermal Emission of Alkali Metal Ions from Al30-Pillared Montmorillonite Studied by Mass Spectrometric Method

Stability of the LaCl 4 − and LuCl 4 − Ions Studied by Mass Spectrometry

Vapor species over cerium and samarium trichlorides, enthalpies of formation of (LnCl3)n molecules and Cl−(LnCl3)n ions

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Thermal Emission of Alkali Metal Ions from Al₃₀-Pillared Montmorillonite Studied by Mass Spectrometric Method

Thermal Emission of Alkali Metal Ions from Al₃₀-Pillared Montmorillonite Studied by Mass Spectrometric Method

Vapor species over cerium and samarium trichlorides, enthalpies of formation of (LnCl₃)_n molecules and Cl⁻(LnCl₃)_n ions