Complexation and reduction-oxidation equilibriums of titanium chlorides in gaseous aluminum chloride

Soerlie, Morten; Oeye, H. A.

doi:10.1021/ic50187a028

Cited by 21 publications

(5 citation statements)

References 8 publications

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“…This structure would imply either C 2 v or D 2 h symmetry. Sørlie and Øye found the enthalpy of dimerization to be in the range of −32.7 to −34.2 kcal/mol . Previous experiments in other laboratories found the enthalpy of dimerization to be −31.9 kcal/mol 78 and −40.6 kcal/mol .…”

Section: Resultsmentioning

confidence: 94%

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Electronic Structure and Magnetic Properties of Y₂Ti(μ-X)₂TiY₂ (X, YH, F, Cl, Br) Isomers

Aikens

Gordon

2002

J. Phys. Chem. A

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The electronic structure and magnetic properties of homodinuclear titanium(III) molecules with halide and hydride ligands have been studied using single-and multireference methods. Natural orbital occupation numbers suggest that the singlet states are essentially diradical in character. Dynamic electron correlation is required for calculating quantitatively accurate energy gaps between the singlet and triplet states. Isotropic interaction parameters are calculated, and three of the compounds studied are predicted to be ferromagnetic at the MRMP2/TZV(p) level of theory. Zero-field splitting parameters are determined using CASSCF and MCQDPT spin−orbit coupling with three different electron operator methods. Timings for these methods are compared. Calculated dimerization energies suggest that all dimers studied are lower in energy than the corresponding monomers. Monomer structures and vibrational frequencies are reported. Disciplines Chemistry Comments Reprinted (adapted) with permission fromThe electronic structure and magnetic properties of homodinuclear titanium(III) molecules with halide and hydride ligands have been studied using single-and multireference methods. Natural orbital occupation numbers suggest that the singlet states are essentially diradical in character. Dynamic electron correlation is required for calculating quantitatively accurate energy gaps between the singlet and triplet states. Isotropic interaction parameters are calculated, and three of the compounds studied are predicted to be ferromagnetic at the MRMP2/ TZV(p) level of theory. Zero-field splitting parameters are determined using CASSCF and MCQDPT spinorbit coupling with three different electron operator methods. Timings for these methods are compared. Calculated dimerization energies suggest that all dimers studied are lower in energy than the corresponding monomers. Monomer structures and vibrational frequencies are reported.

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Section: Resultsmentioning

confidence: 94%

“…The calculated TiX 3 , TiX 2 H, and TiXH 2 dimerization energies are listed in Table . Sørlie and Øye report the presence of Ti 2 Cl 6 in high-temperature absorption spectroscopy . They suggest a distorted tetrahedral structure for Ti 2 Cl 6 in which two deformed tetrahedra share one edge.…”

Section: Resultsmentioning

confidence: 99%

Electronic Structure and Magnetic Properties of Y₂Ti(μ-X)₂TiY₂ (X, YH, F, Cl, Br) Isomers

Aikens

Gordon

2002

J. Phys. Chem. A

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“…In addition, reports were coming in of the transition metals, lanthanide metals, and actinide metal ions. 4,[13][14][15][16][17] Changing the electrolyte had achieved varying degrees of success in improving the efficiency. Considering this, a better understanding of the valence state of tungsten ions and dissolution of WC with the changes in solvent alkali ion radius in chloride molten salts is of great significance.…”

Section: Introductionmentioning

confidence: 99%

Valence and coordination form transition of tungsten ions in molten alkali chlorides

Feng

Zhang

et al. 2022

Phys. Chem. Chem. Phys.

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“…[11][12][13] It may be that Al lowers the barrier to phase transformation, but it is also possible that, in the industrial reactors, the phase is determined by the nucleation process. A small number of TiAl x Cl y species have been studied experimentally, 14,15 but the system with excess oxygen has not been investigated. Varga et al 16 provide thermochemical data for some of the aluminum oxyhalides from computational studies but a number of possible species, particularly dimers, are missing.…”

Section: Introductionmentioning

confidence: 99%

“…Some authors suggest that Al accelerates the anatase to rutile transformation, , but this is hard to reconcile with the theoretical studies showing that there is no significant thermodynamic bias between the doped phases. − It may be that Al lowers the barrier to phase transformation, but it is also possible that, in the industrial reactors, the phase is determined by the nucleation process. A small number of TiAl x Cl y species have been studied experimentally, , but the system with excess oxygen has not been investigated. Varga et al provide thermochemical data for some of the aluminum oxyhalides from computational studies but a number of possible species, particularly dimers, are missing.…”

Section: Introductionmentioning

confidence: 99%

First-Principles Thermochemistry for the Combustion of a TiCl₄ and AlCl₃ Mixture

et al. 2009

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AlCl(3) is added in small quantities to TiCl(4) fed to industrial reactors during the combustion synthesis of titanium dioxide nanoparticles in order to promote the rutile crystal phase. Despite the importance of this process, a detailed mechanism including AlCl(3) is still not available. This work presents the thermochemistry of many of the intermediates in the early stages of the mechanism, computed using quantum chemistry. The enthalpies of formation and thermochemical data for AlCl, AlO, AlOCl, AlOCl(2), AlO(2), AlO(2)Cl, AlOCl(3), AlO(2)Cl(2), AlO(3)ClTi, AlO(2)Cl(2)Ti, AlO(2)Cl(4)Ti, AlOCl(5)Ti, AlO(2)Cl(3)Tia (isomer-a), AlO(3)Cl(2)Ti, AlO(2)Cl(5)Ti, AlOCl(4)Ti, AlO(2)Cl(3)Tib (isomer-b), AlCl(7)Ti, AlCl(6)Ti, Al(2)Cl(6), Al(2)O(2)Cl, Al(2)O(2)Cl(3), Al(2)O(3)Cl(2), Al(2)O(2)Cl(2), Al(2)OCl(4), Al(2)O(3), and Al(2)OCl(3) were calculated using density functional theory (DFT). A full comparison between a number of methods is made for one of the important species, AlOCl, to validate the use of DFT and gauge the magnitude of errors involved with this method. Finally, equilibrium calculations are performed to try to identify which intermediates are likely to be most prevalent in the high temperature industrial process and as a first attempt to characterize the nucleation process.

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Complexation and reduction-oxidation equilibriums of titanium chlorides in gaseous aluminum chloride

Cited by 21 publications

References 8 publications

Electronic Structure and Magnetic Properties of Y₂Ti(μ-X)₂TiY₂ (X, YH, F, Cl, Br) Isomers

Electronic Structure and Magnetic Properties of Y₂Ti(μ-X)₂TiY₂ (X, YH, F, Cl, Br) Isomers

Valence and coordination form transition of tungsten ions in molten alkali chlorides

First-Principles Thermochemistry for the Combustion of a TiCl₄ and AlCl₃ Mixture

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Complexation and reduction-oxidation equilibriums of titanium chlorides in gaseous aluminum chloride

Cited by 21 publications

References 8 publications

Electronic Structure and Magnetic Properties of Y2Ti(μ-X)2TiY2 (X, YH, F, Cl, Br) Isomers

Electronic Structure and Magnetic Properties of Y2Ti(μ-X)2TiY2 (X, YH, F, Cl, Br) Isomers

Valence and coordination form transition of tungsten ions in molten alkali chlorides

First-Principles Thermochemistry for the Combustion of a TiCl4 and AlCl3 Mixture

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Electronic Structure and Magnetic Properties of Y₂Ti(μ-X)₂TiY₂ (X, YH, F, Cl, Br) Isomers

Electronic Structure and Magnetic Properties of Y₂Ti(μ-X)₂TiY₂ (X, YH, F, Cl, Br) Isomers

First-Principles Thermochemistry for the Combustion of a TiCl₄ and AlCl₃ Mixture