- Mass-spectrometric study of (indium + chlorine)(g). Enthalpies of formation of InCl(g), In2Cl2(g), In2Cl4(g), InCl3(g), and In2Cl6(g)
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The gaseous phase in equilibrium with InCl(s or l), InCl2(s or l), or InCl3(s) was analysed by the Knudsen-cell mass-spectrometric method.InCl3(g) and In2Cl6(g) are the main species vaporizing from InCl3(s); InCl(g), In2Cl2(g), In2Cl4(g), and InCl3(g) from InCl(s or l); and In2Cl4(g), InCl3(g), InCl(g), In2Cl6(g), and In2Cl2(g) from InCl2(s).The gas-phase analysis was performed by studying the ionization-efficiency curves and ionic-intensity ratios as a function of the temperature of vaporization and chemical composition in (indium + chlorine) for every InxCly+ ion (x = 1, 2 and y = 0 to 5).Enthalpies of formation were deduced from vaporization and gas-phase equilibria: ΔfH0m(InCl3, g, 298.15 K) = -(375.7 +/- 5.0) kJ * mol-1, ΔfH0m(In2Cl6, g, 298.15 K) = -(883.7 +/- 10.0) kJ * mol-1, ΔfH0m(InCl, g, 298.15 K) = -(68.2 +/- 4.6) kJ * mol-1, ΔfH0m(In2Cl4, g, 298.15 K) = -(573.2 +/- 12.6= kJ * mol-1.A lower bound was calculated for InCl2(g): ΔfH0m(InCl2, g, 298.15 K) >/= -201 kJ * mol-1.
- Defoort, F.,Chatillon, C.,Bernard, C.
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- Fourier-transform microwave spectroscopy of InF, InCl, and InBr, prepared using laser ablation
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High-resolution rotational spectra of InF, InCl, and InBr have been measured with a pulsed jet cavity Fourier-transform microwave spectrometer. Samples were prepared by vaporizing In with a pulsed Nd:YAG laser, and reacting the vapour with a precursor gas entrained in the Ne backing gas of the jet. Precise rotational and nuclear quadrupole coupling constants have been obtained for all these molecules, along with the first nuclear spin-rotation constants of InCl and InBr. The hyperfine coupling constants are discussed in terms of the electronic structures of the molecules.
- Hensel, Kristine D.,Gerry, Michael C. L.
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- Chemical vapor transport for the control of composition of low-volatile solids: II. the composition control of indium sulfides: Technique of the charge dilution
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Considering chalcogenide transport processes with a participation of indium and indium sulfides in the closed system it was found that non-isothermal conditions are insufficient for a noticeable reversible indium transfer. The main reason for this fact was considered as a deficiency of indium halides with a high oxidation degree of indium which are in the equilibrium in the vapor with condensed indium or its lower sulfides. To provide chemical transport that is impossible in the usual experimental conditions a new way was proposed and applied implying dilution of a charge (source or getter of indium) with inactive diluent. One of the probable diluents is gold. The probability of reversible and selective chemical transport was proved for indium in the system indium sulfides - vapor of In chlorides - (Au-In) charge . Conditions for performing the non-destructive composition control of indium sulfides in the non-destructive chemical transport were determined.
- Zavrazhnov,Naumov,Pervov,Riazhskikh
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- Detection and characterization of gas-phase InCl using resonance enhanced multiphoton ionization
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This paper presents an experimental observation of the Rydberg states of gaseous InCl, and hitherto unknown electronic states on the basis of resonance enhanced multiphoton ionization (REMPI) spectra between 330 and 490 nm. An adiabatic ionization potential is determined by extrapolating the Rydberg series for improved thermochemical calculations for InCl and InCl+. It is shown that REMPI spectroscopy is a sensitive technique (109 molecules cm-3 (laser pulse)-1 at 365.14 nm.
- Johnson III,Dearden,Hudgens
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- The preparation and vapour pressures of the indium(I) halides and the standard molar Gibbs free energy change for formation of InX from In(g) and X2(g), (X = Cl, Br, or I)
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The syntheses of high-purity InCl, InBr, and InI from the elements are outlined.The vapour pressures above the liquid indium(I) halides have been measured by the quasistatic method over the ranges: InCl, 528 to 914 K; InBr, 569 to 950 K; and InI, 646 to 9
- Brumleve, T. R.,Mucklejohn, S. A.,O'Brien, N. W.
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- Selective chemical vapor transport as a means of varying the composition of nonstoichiometric indium sulfides
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Investigation of halide vapor transport with the participation of indium and indium sulfides in a closed system indicates that applying a temperature gradient is insufficient for quantitative spontaneous indium transfer from the lower indium sulfides or for the transport of elemental indium. A major reason for this is that the vapor phase over indium and its lower sulfides is dominated by monohalides. Impossible under conventional experimental conditions, chemical vapor transport can be achieved by diluting indium with an inert substance, e.g., gold. Our results indicate that the vapor transport of indium is possible in systems of the form indium sulfide-indium chloride vapor-charge (Au-In) and that chloride vapor transport can be used to nondestructively control the composition of indium sulfides. The transport process is shown to be selective and reversible. Conditions are determined for nondestructive chemical transport control over the composition of indium sulfides.
- Zavrazhnov,Naumov,Sergeeva,Sidei
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- Recovery of indium from In2O3 and liquid crystal display powder via a chloride volatilization process using polyvinyl chloride
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Indium (In) was recovered from indium oxide (In2O3) and liquid crystal display (LCD) powder via a chloride volatilization process using polyvinyl chloride (PVC) as the chlorination agent. The recovery of In from In2O3
- Park, Kye-Sung,Sato, Wakao,Grause, Guido,Kameda, Tomohito,Yoshioka, Toshiaki
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p. 105 - 108
(2009/12/01)
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- Reaction of decamethylsilicocene with group 13 element halides: Insertions, rearrangements, and eliminations
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In the reaction of decamethylsilicocene (1; (Me5C5)2Si) with halides or organohalides of trivalent boron, aluminum, gallium, and indium, quite different and sometimes very complex pathways are observed which include adduct formation, 1,2-halide or -alkyl shifts, 1,2-dyotropic rearrangements, and reductive elimination and oxidative addition reactions. Cp*BCl2 (Cp* = pentamethylcyclopentadienyl), BCl3, and BBr3 reacted with 1 to form the pentacarba-nido-hexaboronium salts [Cp*SiCl2BCp*]+[Cp*BCl3]- (3a) and [Cp*SiX2BCp*]+-[BX4]- (3b, X = Cl; 4, X = Br). A second product (5b) of composition Cp*3Si2Br4B with an arachno-cluster framework was isolated from the reaction with BBr3. With AlCl3 and AlBr3 metathesis reactions gave the ionic compounds [Cp*2Al]-[AlX4]- (6a,b, X = Cl, Br), respectively. The formation of 6a,b is the result of a Lewis-base-catalyzed dismutation of Cp*AlX2 in which 1 is the base, as proved by separate experiments. The compound Cp*Al-(Me)Cl (7) was formed in the reaction of 1 with Me2AlCl. Silicocene 1 functioned as a dehalogenating agent in its reactions with GaCl3, GaBr3, Cp*GaBr2, InCl3, and InBr3, giving the corresponding monovalent, metastable ( GaCl , GaBr ) or stable (Cp*Ga, InCl, InBr) species. All new compounds were characterized by NMR (1H, 13C, 11B, 29Si) and mass spectrometry. The solid-state structures of 3a and 5b were determined by X-ray diffraction analysis.
- Holtmann, Udo,Jutzi, Peter,Kühler, Thorsten,Neumann, Beate,Stammler, Hans-Georg
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p. 5531 - 5538
(2008/10/08)
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- N,N′-Dialkyldithiocarbamate chelates of indium(III): Alternative synthetic routes and thermodynamics characterization
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Alternative synthetic routes to prepare N,N′-dialkyldithiocarbamate complexes of indium(III), In(S2CNR2)3 (R = CH3, C2H5, n-C3H7, i-C3H7, n-C4H9 and i-C4H9) from the metallic element and from indium monohalides, InX(X = Cl, Br and I) were established. The proposed mechanism of reaction involving InX considering a ligand redistribution reaction of XIn(S2C-NR2)2 initially produced, which could be derived from the insertion of InX into sulfur-sulfur bond of the tetralkylthiuram disulfide. The thermal decomposition of the In(S2CNR2)3 (R = CH3, C2H5, n-C3H7, i-C3H7, n-C4H9 and i-C4H9) compounds was investigated by the thermogravimetric technique, where two pathways were detected, depending on the dialkyldithiocarbamato ligand. The first step leads to indium metal, or alternatively In2S3, as the final residue for R = C2H5, n-C3H7, i-C4H9 and for R = CH3, i-C3H7, n-C4H9, respectively. The corresponding standard molar enthalpies of sublimation of all compounds were determined by means of differential scanning calorimetry and methods of estimation.
- Oliveira, Marcelo M.,Pessoa, Giuliana M.,Carvalho, Ludmilla C.,Peppe, Clovis,Souza, Antonio G.,Airoldi, Claudio
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p. 223 - 230
(2008/10/09)
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- Direct electrochemical synthesis of X2InCH2X compounds (X = Br, I) and a study of their coordination chemistry
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The electrochemical oxidation of indium in CH2X2/CH3CN media (X = Cl, Br, I) gives InX. Indium(I) chloride disproportionates, but InBr or InI react with CH2X2 to give X2InCH2X (X
- Annan, Theodore A.,Tuck, Dennis G.,Khan, Masood A.,Peppe, Clovis
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p. 2159 - 2166
(2008/10/08)
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- Emission spectra and electronic structure of group Illa monohalide cations
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Optical spectra of ten AX+ ions (A = B, Al, Ga, In; X = F, Cl, Br) have been observed in the visible and near UV; a total of 18 band systems were newly discovered.The emission was produced by chemiluminescent reactions A+ + X2 at low (2-10 eVCM ) kinetic energy in a beam-gas arrangement.A position-sensitive photon counting detector with large surface area and very low dark count rate was employed, the resolution was mostly 5-50 Angstroem FWHM.Three types of band systems were observed: ( 1 ) For all AX+ combinations except BCl+ and BBr+, a very broad quasicontinuum with undulatory structure appears.On the basis of electronic state correlation arguments, photoelectron data, some ab initio calculations and, in one case, a known emission spectrum (InCl+ ) these band systems were identified as B2Σ+-X2Σ+ transitions.It is concluded that the excited state potentials are considerably displaced against the ground state, and their energetics are given. (2) For six species AX+, narrow band systems were observed in the 2500 Angstroem region.They could be clearly identified as being due to C2Π- X2Σ+ transitions by means of comparison with the systematics of the analogous A2Π-X2Σ+ transitions of the isoelectronic alkaline earth halides, by the resolved fine structure, and, in the case of AlF+, by an ab initio calculation. (3) In the GaCl+, GaBr+, and InBr+ spectra, narrow features accompany the C-X transitions.They are attributed to D2Σ+-X2Σ+ transitions, analogous to the alkaline earth halide B2Σ+-X2Σ+ band systems.Qualitative electronic state correlations are discussed, and the expected dominant configurations in different regions of the AX+ ground and excited states are given.These are in accord with recent ab initio results on AlF+.
- Glenewinkel-Meyer, Th.,Kowalski, A.,Mueller, B.,Ottinger, Ch.,Breckenridge, W. H.
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p. 7112 - 7125
(2007/10/02)
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- Interaction in the In(met.)-InCl3-ZnCl2 system in aqueous solutions
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Kinetics of formation of monovalent indium in the InO-InCl3-ZnCl2 system were studied as a function of indium trichloride and zinc dichloride concentration. The relation between the equilibrium monovalent indium concentration and the structure of chloride solutions in the studied system was determined. As a result of the associative-dissociative processes ZnCl4(H2O)2-2, ZnCl4(H2O)2-, ZnClMIN3 ions, ZnCl2 molecules, polymeric associates (ZnCl2)n, In(I) ions, and unionized indium monochloride molecules, possibly dimeric, exist in the studied solutions as a function of the concentration of complexes.
- Kozin,Sheka
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- KINETICS OF FORMATION OF MONOVALENT INDIUM IONS AND EQUILIBRIUM IN THE In0-ZnCl2-NH4Cl SYSTEM.
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The kinetics of In(I) formation in molten electrolytes of the In**0-ZnCl//2-NH//4Cl system were investigated upon contact with metallic indium. The effect of temperature and composition of the medium on kinetics of the In(I) formation reaction in the melt was examined. Effective rate constants and activation energies of the In(I) formation reaction in the melt were determined.
- Kozin,Sheka
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- USE OF INDIUM MONOCHLORIDE FOR THE PURIFICATION OF INDIUM ELECTROLYTES.
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A new method is proposed for the purification of indium electrolytes with lower compounds of indium chlorides. It was established that purification of indium electrolytes from electropositive impurity metals by their reduction with monovalent indium is a simple and highly effective method.
- Kozin,Sheka
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- YIELD OF INDIUM AND TIN AS A FUNCTION OF CURRENT UPON ELECTROLYSIS OF CHLORIDE MELTS.
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The effects of cathodic and anodic current densities on the yield of indium and tin as a function of current during electrolysis of the sodium, potassium, and zinc eutectic, containing 40 mass% of the corresponding metal chlorides, was investigated. It was shown that cathodic and anodic yields as a function of current do not depend on current density and mainly monovalent indium and divalent tin compounds participate in electrode processes. The anodic yield as a function of current in all cases is higher than the cathodic yield, which is explained by a change in concentration of the electromotor material along the electrolyzer volumes. Electrolysis in a three-layer cell eliminates redistribution of electrolyte components.
- Omel'chuk,Gorbach,Zarubitskii
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- Kinetics of the Reaction Between Hydrogen Chloride and Indium in a Stream of Helium
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The kinetics of the reaction between hydrogen chloride and indium have been studied by thermogravimetric and mass-spectrometric methods at 630 - 820 K and 2 - 38 mmHg pressure of hydrogen chloride.The rate equation for the process has been obtained, and the heats of adsorption of the components and the activation energy of the reaction have been determined.
- Strel'chenko, S. S.,Molodyk, A. D.,Slonkova, V. I.
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p. 994 - 997
(2007/10/02)
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