Determination of the thermodynamic activities of NaBr and DyBr3 in the phases of the NaBr–DyBr3 system at 863 K by Knudsen effusion mass spectrometry

Hilpert, K.; Miller, M.

doi:10.1016/j.jallcom.2004.02.026

Cited by 9 publications

(5 citation statements)

References 16 publications

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“…for ceramic solutions and metal alloys at high temperature) (Shilov et al, 1997;Hilpert and Miller, 2004;Hilpert, 2001Hilpert, , 1991Hastie, 1984). SOA components are likely to have vapour pressures around 10 −4 Pa (Camredon and Aumont, 2006;Seinfeld and Pankow, 2003), measurable at ambient temperature, well inside the range measurable by KEMS.…”

Section: Knudsen Effusion Mass Spectrometrymentioning

confidence: 99%

Design and construction of a simple Knudsen Effusion Mass Spectrometer (KEMS) system for vapour pressure measurements of low volatility organics

Markus²,

et al. 2009

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Abstract.A design of and initial results from a Knudsen Effusion Mass Spectrometer (KEMS) are presented. The design was adapted from high temperature alloy studies with a view to using it to measure vapour pressures for low volatility organics. The system uses a temperature controlled cell with an effusive orifice. This produces a molecular beam which is sampled by a quadropole mass spectrometer with electron impact ionization calibrated to a known vapour pressure. We have determined P (298 K) and H sub of the first 5 saturated straight chain dicarboxylic acids: 2.15±1.19×10 −2 Pa and 75±19 KJ mol −1 respectively for oxalic acid, 5.73±1.14×10 −4 Pa and 91±4 KJ mol −1 for Malonic acid, 1.13±0.47×10 −4 Pa and 93±6 KJ mol −1 for Succinic acid, 4.21±1.66×10 −4 Pa and 123±22 KJ mol −1 for Glutaric acid and 6.09±3.85×10 −6 Pa and 125±40 KJ mol −1 for Adipic acid.

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Section: Knudsen Effusion Mass Spectrometrymentioning

confidence: 99%

Design and construction of a simple Knudsen Effusion Mass Spectrometer (KEMS) system for vapour pressure measurements of low volatility organics

Markus²,

et al. 2009

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“…Knudsen Effusion Mass Spectrometry (KEMS) is an established vapour pressure measurement technique capable of measuring vapour pressures from 10 1 −10 −8 Pa (e.g. for ceramic solutions and metal alloys at high temperature) (Shilov et al, 1997;Hilpert and Miller, 2004;Hilpert, 2001Hilpert, , 1991Hastie, 1984). SOA components are likely to have vapour pressures around 10 −4 Pa (Camredon and Aumont, 2006;Seinfeld and Pankow, 2003), measurable at ambient temperature, well inside the range measurable by KEMS.…”

Section: Knudsen Effusion Mass Spectrometrymentioning

confidence: 99%

Design and construction of a simple Knudsen Effusion Mass Spectrometer (KEMS) system for vapour pressure measurements of low volatility organics

Booth¹,

Markus²,

McFiggans³

et al. 2009

Preprint

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Abstract. A design of and initial results from a Knudsen Effusion Mass Spectrometer (KEMS) are presented. The design was adapted from high temperature alloy studies with a view to using it to measure vapour pressures for low volatility organics. The system uses a temperature controlled cell with an effusive orifice. This produces a molecular beam which is sampled by a quadropole mass spectrometer with electron impact ionization calibrated to a known vapour pressure. We have determined P298 and ΔHsub of the first 5 unsaturated straight chain dicarboxylic acids: 2.15±1.19×10−2 Pa and 75±19 kJ mol−1 respectively for Oxalic acid, 5.15±0.76×10−4 Pa and 91±4 kJ mol−1 for Malonic acid, 9.19±2.26×10−5 Pa and 93±6 kJ mol−1 for Succinic acid, 4.21±1.66×10−4 Pa and 123±22 kJ mol−1 for Glutaric acid and 5.21±3.84×10−6 Pa and 125±40 kJ mol−1 for Adipic acid.

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“…Therefore, first we tested different computational methods; several density functional (B3LYP, , B3PW91, , and mPW1PW91) and the MP2 methods . After different trials, eventually we used the following basis sets: the dysprosium atom was described by a “large-core” (LC) ECP involving 55 electrons ([Kr]4d4f 9 ) and an associated basis set of the (7s6p5d)/[5s4p3d] type augmented with two f polarization functions from Dolg (α f = 1.158, α f = 0.416). − For the light atoms the cc-pVTZ-type all-electron bases (Li and F, Na, Cl) were used, and for the remaining atoms pseudopotentials from the Stuttgart group with associated basis sets: for Br and I SDB-cc-pVTZ-type , and for K, Rb, Cs small-core Stuttgart MDF type ECPs, in the case of Rb and Cs the g functions were removed from the basis.…”

Section: Computational and Experimental Detailsmentioning

confidence: 99%

“…Lanthanide halides (LnX 3 , Ln = lanthanide atom, X = halogen) and alkali halides (MX, M = alkali metal) are known to form MLnX 4 -type mixed complexes in the vapor phase. The existence of these complexes has been shown and thermodynamic characteristics of their dissociation to LnX 3 and MX have been determined by numerous experimental studies, mostly by Knudsen-effusion mass spectrometry. − Other techniques, such as gas-phase spectrophotometry, torsion-mass-effusion, chemical analysis of the condensed equilibrium vapors, vapor transpiration techniques and vapor pressure measurements have also been applied to a lesser extent (see ref and references therein).…”

Section: Introductionmentioning

confidence: 99%

Molecular Structure and Vibrational Spectra of Mixed MDyX₄ (M = Li, Na, K, Rb, Cs; X = F, Cl, Br, I) Vapor Complexes: A Computational and Matrix-Isolation Infrared Spectroscopic Study

et al. 2011

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The structures, energetic, and vibrational properties of MDyX(4) (M = Li, Na, K, Rb, Cs; X = F, Cl, Br, I) mixed alkali halide/dysprosium halide complexes have been investigated by a joint computational and experimental, matrix-isolation Fourier-transform infrared spectroscopic (MI-IR), study. According to our DFT computations for the complexes with heavier halides and alkali metals the ground-state structure is the tridentate isomer; while at high temperatures the bidentate structural isomer dominates. The survey of various dissociation processes revealed the preference of the dissociation to neutral MX and DyX(3) fragments over ionic and radical dissociation products. Cationic complexes are considerably less stable at 1000 K than the neutral complexes, and they prefer to dissociate to M(+) + DyX(4)(•) fragments. The vapor species of selected mixtures of NaBr and CsBr with DyBr(3) and of CsI with DyI(3) in the temperature range 900-1000 K have been isolated in krypton and xenon matrices and investigated by infrared spectroscopy. Besides the characteristic vibrational frequencies of the monomeric and dimeric alkali halide species and of the dysprosium trihalide molecules, certain signals indicated the formation of MDyX(4) (M = Na, Cs; X = Br, I) mixed complexes. Comparison with the computed vibrational and thermodynamic characteristics of the relevant species lead to the conclusion that these complexes appear in the vapor predominantly as the C(2v)-symmetry bidentate isomer. This is the first time that this structure was identified in an experimental vibrational spectroscopic study. The signals appearing upon performing a thermal anneal cycle were tentatively assigned to the double complex M(2)DyX(5) (M = Na, Cs; X = Br, I). A structure in which one alkali atom is bound to dysprosium by three and the other by two bridges is proposed for these double complexes.

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Determination of the thermodynamic activities of NaBr and DyBr3 in the phases of the NaBr–DyBr3 system at 863 K by Knudsen effusion mass spectrometry

Cited by 9 publications

References 16 publications

Design and construction of a simple Knudsen Effusion Mass Spectrometer (KEMS) system for vapour pressure measurements of low volatility organics

Design and construction of a simple Knudsen Effusion Mass Spectrometer (KEMS) system for vapour pressure measurements of low volatility organics

Design and construction of a simple Knudsen Effusion Mass Spectrometer (KEMS) system for vapour pressure measurements of low volatility organics

Molecular Structure and Vibrational Spectra of Mixed MDyX₄ (M = Li, Na, K, Rb, Cs; X = F, Cl, Br, I) Vapor Complexes: A Computational and Matrix-Isolation Infrared Spectroscopic Study

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Determination of the thermodynamic activities of NaBr and DyBr3 in the phases of the NaBr–DyBr3 system at 863 K by Knudsen effusion mass spectrometry

Cited by 9 publications

References 16 publications

Design and construction of a simple Knudsen Effusion Mass Spectrometer (KEMS) system for vapour pressure measurements of low volatility organics

Design and construction of a simple Knudsen Effusion Mass Spectrometer (KEMS) system for vapour pressure measurements of low volatility organics

Design and construction of a simple Knudsen Effusion Mass Spectrometer (KEMS) system for vapour pressure measurements of low volatility organics

Molecular Structure and Vibrational Spectra of Mixed MDyX4 (M = Li, Na, K, Rb, Cs; X = F, Cl, Br, I) Vapor Complexes: A Computational and Matrix-Isolation Infrared Spectroscopic Study

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Molecular Structure and Vibrational Spectra of Mixed MDyX₄ (M = Li, Na, K, Rb, Cs; X = F, Cl, Br, I) Vapor Complexes: A Computational and Matrix-Isolation Infrared Spectroscopic Study