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1.
Mass Spectroscopic Observations and Chemical Transport Experiments with the Systems VCl3/Al2Cl6 and VCl2/Al2Cl6 By mass spectrometry the equilibrium VCl3,s + 0.5 Al2Cl6,g ? VAlCl6,g has been determined: ΔH°(298) = 25.6(±0.5) kcal; ΔS°(298) = 23.0(±3) cal/K, ΔCp (assumed) = ?4 cal/K. This is approximately in agreement with results determined by ligand field spectroscopy by ANUNDSKÅS and ØYE (A. and Ø.). For the dimerization of VCl3,g values for ΔH and ΔS have been derived. The molecule VAl2Cl9 assumed by A. and Ø. could not been observed by mass spectrometry. For the VCl2/Al2Cl6 complex, observed by chemical transport, A. and Ø. give the formula VAl3Cl11. This molecule could not been observed by mass spectrometry. This suggests a smaller concentration, compared with the results of A. and Ø. Stabilization of VCl2,s (by metal-nietal-bonds) shifts the reaction to the left, whith explains the lower complex concentration as well as the larger molecular weight of the complex. With chlorides stabilized by stronger metal-metal bonds (MoCl3, MoCl2, Nb3Cl8) AlCl3 complexes are not formed in observable concentrations. The chemical transport of VCl2 with Al2Cl6 needs relatively high temperatures (973 → 873 K). In this case the addition of SiCl4 hinders the attack of the quartz ampoule by Al2Cl6. Using a VCl3 + VCl2 mixture, VCl3 is transported by Al2Cl6 (673 → 623 K) into the colder region. If afterwords the ampoule is reversed, VCl3 again moves into the colder region, but the thermal decomposition of VCl3 at the same time causes that a VCl2-residue remains in the hot region. 相似文献
2.
Equilibrium CuCl2,f + Al2Cl6,g = CuAl2Cl8,g and the Side Reactions Aim was the measurement of the equilibrium by the flow method. The following observations have been made:
- (a) The solid CuCl2 phase dissolves 1 mol% CuCl.
- (b) Measurements with CuAl2Cl8 as solid phase confirmed this formula for the gas molecule.
- (c) At constant temperature and by variation of P(Al2C16) the expression ΣP(Cu)/P(Al2Cl6) passes a flat minimum. This effect is caused by the fact that in the gas phase small concentrations of CuAlCl5 and CuAl3Cl11 are present besides the main complex CuAl2Cl8. For the formation equilibrium of these side complexes rough thermodynamic data have been given.
- (d) Taking into account the gas molecules Cl2…Cu3AlCl6 (see above) data for the equilibrium (12) have been ascertained, ΔS12°(590) = 8.64 kcal; ΔS12°(590) = 11.24 cal/K.
3.
The Chemical Transport of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir, Pt in the Presence of Al2Cl6, Fe2Cl6 or Al2I6, Causing Complex Formation Chemical transport experiments show, that the title elements (with exception of Os) in the presence of halide forming agents (HCl, Cl2 or I2 resp.) and of complex forming agents (Al2Cl6, Fe2Cl6 or Al2I6 resp.) give gaseous complex compounds with a remarkable stability. This leads to novel possibilities for the chemical transport of the elements and their compounds. The effect of complex formation can be predicted on the basis of qualitative thermodynamic considerations. The corrosion of the wall of the quartz ampoule at temperatures above 600°C by Al2Cl6/AlCl3 is avoidable by the usage of Fe2Cl6/FeCl3 instead of Al2Cl6/AlCl3. Experiments in the system Pd/I2, Al2I6 lead to the formation of crystals of Pd2Al. 相似文献
4.
Formation of CoAl3Cl11 at higher Al2Cl6 Pressures The reaction of CoCl2,f with Al2Cl6,g (≈ 3 atm) is investigated considering every component of the gas phase (Al2Cl6, AlCl3, Al3Cl9, CoAlCl5, CoAl2Cl8, CoAl3Cl11) and the deviation from the ideal behaviour. The conclusion is derived that at 600 K from CoCl2,s and larger pressures of Al2Cl6 besides CoAl2Cl8 a small amount of CoAl3Cl11 is formed. 相似文献
5.
Harald Schfer 《无机化学与普通化学杂志》1978,445(1):129-139
Reaction of Quartz Glass with Al2Cl6,g and with Al,f + Al2Cl6,g The attack of quartz glass by Al2Cl6,g at temperatures ≧ 300°C results in the formation of SiCl4,g. At low temperature the oxygen appears as gaseous oxide chloride (e. g. Al4OCl10…); above 300°C crystalline AlOCl is observed, whereas at more elevated temperatures Al2O3 is formed. With Al + Al2Cl6 (1 atm, 20°C) at 400/350°C thin silicon foils with metallic luster deposit on the quartz wall. Discussion of the experimental evidence leads to the suggestion that the reduction of SiCl4 — formed initially by attack of the quartz vessel — proceeds by reaction with Al2Cl4,g. 相似文献
6.
L. A. Curtiss 《International journal of quantum chemistry》1978,14(6):709-715
Ab initio minimal basis LCAO-SCF molecular orbital (MO ) calculations have been carried out on various structures of the AIF3 and AlCl3 dimers. A bridged D2h structure is found to be the most stable of the structures investigated for Al2F6. A similar structure was obtained for Al2Cl6 in agreement with the experimental evidence. 相似文献
7.
Equilibrium CrCl2,f + Al2Cl6,g ? CrAl2Cl8,g and Remarks on the System CrCl3/Al2Cl6,g For equation (1) spectralphotometric measurements lead to the data ΔH°(298) = 8.7 kcal; ΔS°(298) = 9.5 cal/K; (ΔCp ? ?1 cal/K). Measurements with CrCl3/Al2Cl6,g confirmed the absorption curve (and therefore the structure) of the complex (CrAl3Cl12) which we observed earlier. Side reactions (CrCl3-disproportionation) made the quantitative investigation of the equilibrium impossible. 相似文献
8.
CrCl3,g is chemically transported by means of Al2Cl6,g (~1 atm) in a temperature gradient (e. g. 500 → 400°C). Quantitative transport experiments have shown that the reaction goes via the gas molecule CrCl3 · 3 AlCl3. Its probable structural formula is CrCl6/2(AlCl2/2Cl2)3, containing Cr3+ in an octahedral and Al3+ in a tetrahedral Cl coordination1). 相似文献
9.
Chemically and isotopically pure Al35Cl3 and Al37Cl3 are synthesized from Al (s) and HCl (g). The yield is quantitative and no measurable decrease in isotopic content from HCl to AlCl3 takes place. 相似文献
10.
Gaseous BeCl2/AlCl3 complexes During the volatilization of the chlorides of beryllium and aluminium the complex molecules BeAlCl5, Be2AlCl7, BeAl2Cl8, Be2Al2Cl10, and (in a very small concentration) Be3Al2Cl12 have been observed by means of a mass spectrometer. The structure of the compounds is discussed. 相似文献
11.
Marcus R. Bond 《Acta Crystallographica. Section C, Structural Chemistry》2010,66(2):m17-m21
The title compound, {(C9H14N)2[Cu3Cl8]}n, consists of parallel chains of alternating quasiplanar Cu2Cl6 and planar CuCl4 complexes separated by trimethylphenylammonium cations. Both inorganic complexes possess inversion symmetry. Pairs of neighboring chloride ions of the CuCl4 complex each form a symmetric bridge and an asymmetric bridge to Cu2Cl6 complexes on either side. The Cu2Cl6 complex contains two symmetric chloride bridges between the copper cations with a terminal chloride bound to each five‐coordinated CuII ion. The CuCl4 complex completes its coordination environment by forming two long semicoordinate contacts to the bridging chloride ions of neighboring Cu2Cl6 complexes. The use of the bridging rather than the terminal chloride ions to form semicoordinate contacts generates a new zigzag chain structure that differs from the straight chain structures found for other A2Cu3Cl8 compounds. The zigzag chain structure is adopted so as to conform to the shorter repeat distance dictated by stacking of the organic cations. 相似文献
12.
SnAl2OCl6, a Quaternary Oxide‐Chloride with Edge‐Sharing [Al4O2Cl10] Tetramers and [(SnCl2/2Cl5)2] Dimers Single crystals of SnAl2OCl6 were obtained from the educts SnCl2 and AlCl3 (obviously containing an oxidic impurity) in silica ampoules with the aid of the Bridgman technique. According to single‐crystal structure analysis, SnAl2OCl6 crystallizes with the monoclinic system (P21/n, Z = 4, a = 942.3(2), b = 1225.8(2), c = 948.4(3) pm, β = 96.42(2)°). Characteristic structural features are centrosymmetric tetramers [Al4O2Cl10] and [(SnCl2/2Cl5)2] dimers which are connected via common edges, finally building up a three‐dimensional structure. 相似文献
13.
Syntheses and Crystal Structures of [Cu4(As4Ph4)2(PRR′2)4], [Cu14(AsPh)6(SCN)2(PEt2Ph)8], [Cu14(AsPh)6Cl2(PRR′2)8], [Cu12(AsPh)6(PPh3)6], [Cu10(AsPh)4Cl2(PMe3)8], [Cu12(AsSiMe3)6(PRR′2)6], and [Cu8(AsSiMe3)4(PtBu3)4] (R, R′ = Organic Groups) Through the reaction of CuSCN with AsPh(SiMe3)2 in the presence of tertiary phosphines the compounds [Cu4(As4Ph4)2(PRR′2)4] ( 1 – 3 ) ( 1 : R = R′ = nPr, 2 : R = R′ = Et; 3 : R = Me, R′ = nPr) and [Cu14(AsPh)6(SCN)2(PEt2Ph)8] ( 4 ) can be synthesised. Using CuCl instead of CuSCN results to the cluster complexes [Cu14(AsPh)6Cl2(PRR′2)8] ( 5–6 ) ( 5 : R = R′ = Et; 6 : R = Me, R′ = nPr), [Cu12(AsPh)6(PPh3)6] ( 7 ) and [Cu10(AsPh)4Cl2(PMe3)8] ( 8 ). Through reactions of CuOAc with As(SiMe3)3 in the presence of tertiary phosphines the compounds [Cu12(AsSiMe3)6(PRR′2)6] ( 9 – 11 ) ( 9 : R = R′ = Et; 10 : R = Ph, R′ = Et; 11 : R = Et, R′ = Ph) and [Cu8(AsSiMe3)4(PtBu3)4] ( 12 ) can be obtained. In each case the products were characterised by single‐crystal‐X‐ray‐structure‐analyses. As the main structure element 1 – 3 each have two As4Ph42–‐chains as ligands. In contrast 4 – 12 contain discrete AsR2–ligands. 相似文献
14.
A. B. Arbuzov E. N. Kudrya M. V. Trenikhin V. A. Drozdov 《Russian Journal of Applied Chemistry》2017,90(12):1926-1930
According to FT-IR and UV spectroscopic data, the interaction of the Al/Fe alloy with tert-butyl chloride results in that AlCl4–, Al2Cl7–, and FeCl2+ ion complexes, Fe3+ ions, and AlCl3 molecular form are produced in situ in the reaction medium. Ethylene was oligomerized in n-hexane on metal chloride complexes produced in situ from Al/Fe alloys and tert-butyl chloride. 相似文献
15.
Structure‐Behaviour‐Relation of Cu5Pb6O3Cl11, a Good Solid State Ionic Conductor for Cu+‐Ions A new compound within the group of coin metal lead(II) oxide halides is found and characterized by X‐ray single crystal structure determination in a temperature range from 120 K to 400 K. Cu5Pb6O3Cl11 shows a new crystal type structure with a = 21.098(4) Å, b = 10.233(2) Å, c = 12.224(2) Å, β = 124.08(3)°, Z = 4 and space group C 2/c (No. 15) at 120 K. There are found isolated oxidic chains built of OPb4 tetrahedra beside columnar areas consisting of CuCl. In this halidic partial structure are a lot of empty and partially occupied Cl4‐tetrahedra. This structural characteristic seems to be source of a very good conductivity of copper ions, like in microscopic and nanoscaled composites of Al2O3 and AgI. 相似文献
16.
Gas Molecules Pd2Al2Cl10 and PdAlCl5 as Accompanists of PdAl2Cl8 Mass spectrometric observations using a double cell showed that the reaction of gaseous Al2Cl6 with solid PdCl2 besides the known gaseous complex PdAl2Cl8 gives PdAlCl5 and the unexpected complex Pd2Al2Cl10. For the equilibrium (with ΔCp? ?1 cal/K) ΔH°(298) = 7.5 kcal/Mol and ΔS°(298) = 5.3 ± 2 cl have been obtained. 相似文献
17.
Harald Schfer 《无机化学与普通化学杂志》1981,479(8):105-112
Formation of Gaseous MCl2 Complexes. Comparative Study on the Suitability of Al2Cl6, Ga2Cl6, In2Cl6, Fe2Cl6, SiCl4, TiCl4, PCl5, TaCl5, and U2Cl10 as Complex Former The thermodynamic data for reactions of the type MCl2,s + L2Cl6,g = ML2Cl8,g are – as expected – nearly independent on L(Al, Ga, In, Fe). Transport rates e. g. of CoCl2 something smaller with L ? Ga may be traced back on uncertainties concerning the Ga2Cl6 dissociation, and with L ? Fe they may be traced back on the incorporation of FeCl2 into MCl2,s. SiCl4 and TiCl4 cause no noticable transport of CoCl2 or CuCl2 in a temperature gradient, which leads to a short bond consideration. PCl5 and TaCl5 cause the transport of small amounts of CoCl2. U2Cl10/UCl5 are able to transport a remarkable amount of CaCl2 and CoCl2, respectively. 相似文献
18.
Gaseous Complexes NiAl2Cl8 and NiAl3Cl11 Spectral photometric measurements of equilibria which are established by reaction of solid NiCl2 with gaseous Al2Cl6 have been made. Results see ?Inhaltsübersicht”?. 相似文献
19.
Metal Ampoules as Mini‐Autoclaves: Syntheses and Crystal Structures of [Al(NH3)4Cl2][Al(NH3)2Cl4] and (NH4)2[Al(NH3)4Cl2][Al(NH3)2Cl4]Cl2 The salts [Al(NH3)4Cl2]+[Al(NH3)2Cl4]–≡AlCl3 · 3 NH3 ( 1 ) and (NH4+)2[Al(NH3)4Cl2]+[Al(NH3)2Cl4]–(Cl–)2≡ AlCl3 · 3 NH3 · (NH4)Cl ( 2 ) have been obtained as single crystals during the reactions of aluminum and aluminum trichloride, respectively, with ammonium chloride in sealed Monel metal containers. The crystal structure of 1 was determined again [triclinic, P‐1; a = 574.16(10); b = 655.67(12); c = 954.80(16) pm; α = 86.41(2); β = 87.16(2); γ = 84.89(2)°], that of 2 for the first time [monoclinic, I2/m; a = 657.74(12); b = 1103.01(14); c = 1358.1(3) pm; β = 103.24(2)°]. 相似文献
20.
About Ternary Oxocuprates. X. On Ba2Cu3O4Cl2 The preparation of Ba2Cu3O4Cl2 and results by single crystal X-ray methods are described (a = 5.517, c = 13.808 Å; Space group D–I4/mmm). A so far unknown arrangement of square coordinated Cu2+ was detected. The Cu2+/O2?-squares are partly completed to a distorted octahedral coordination by two Cl?. 相似文献