Der chemische Transport von Ni3Ge,Ni5Ge3, Ni(Ge)-Mischkristall,CoSn, Co3Sn2, Cu41Sn11 (δ-Phase), Cu10Sn3 (ζ-Phase) und Cu(Sn)-Mischkristall

Chemical Vapour Transport of Intermetallic Systems. 7. Chemical Transport of Ni₃Ge, Ni₅Ge₃, Ni(Ge)-mixed Crystal, CoSn, Co₃Sn₂, Cu₄₁Sn₁₁ (δ-phase), Cu₁₀Sn₃ (ζ-phase), and Cu(Sn)-mixed Crystals By means of GaI₃ as transport agent some intermetallics in the Ni/Ge- and Co/Sn-system can be prepared by CVT-methods. Using Iodine Cu–Sn-compounds can be deposited in a similiar way.     

Chemischer Transport intermetallischer Phasen Der chemische Transport von Mischkristallen im System Cu/Ag

Chemical Vapor Transport of Intermetallic Systems Chemical Transport of Cu/Ag-mixed Crystals By means of chemical transport reaction it is possible to prepare Cu-rich and Ag-rich mixed crystals in the Cu/Ag system. The composition of individual deposited crystals was different. Mass-spectrometric analysis of the gas-phase above CuI/AgI has shown the formation of CuAg₂I_3,g und Cu₂AgI_3,g. Thermodynamic computations explain the formation of crystals as well as the reaction conditions.     

Der chemische Transport von Titangermaniden

Chemical Vapor Transport of Intermetallic Systems. 8. Chemical Transport of Titaniumgermanides By means of chemical vapor transport using iodine as transport agent in the System Ti/Ge the compounds TiGe₂ and Ti₅Ge₃ have been prepared in form of single crystals. Unexpectedly the phase Ti₆Ge₅ could not be deposited from the vapor phase. The experiments show in contrast to the literature that Ti₆Ge₅ is at 700 °C thermodynamic unstable. Chemical vapor transport is a suitable method to determine coexistence conditions of intermetallic compounds.     

Der Chemische Transport von Cr(Ge) (Mischkristall), Cr3Ge,Cr5Ge3, Cr11Ge8, CrGe,Cr11Ge19 und Ge(Cr) (Mischkristall)

Chemical Vapor Transport of Intermetallic Systems. Chemical Transport of Cr(Ge) (Mixed Crystal) Cr₃Ge, Cr₅Ge₃, Cr₁₁Ge₈, CrGe, Cr₁₁Ge₁₉ and Ge(Cr) (Mixed Crystal) All intermetallics in the Cr/Ge-system can be prepared by CVT-methods. The composition of the deposited crystals is influenced first and foremost by the composition of the starting material. Thermodynamic calculations allow to understand the process qualitatively.     

Chemischer Transport von Mischkristallen im System CuMoO4/ZnMoO4

Chemical Vapour Transport of Solid Solutions in the CuMoO₄/ZnMoO₄ System Two solid solutions exist in the system CuMoO₄/ZnMoO₄: Cu_1‐xZn_xMoO₄ with x=0 to x=0.15 and x=0.20 bis x=1, respectively. Single crystals of Cu_1‐xZn_xMoO₄ were obtained by chemical vapor transport in the temperature gradient 973K→873K using Cl₂, Br₂ or NH₄Cl as transport agents. No difference of the Cu/Zn ratio between source and sink was observed for the transport agents Cl₂ and NH₄Cl. A slight shift to higher Zn amounts was observed for single crystals of Cu_1‐xZn_xMoO₄ grown using Br₂ as transport agent. The experimental results were compared with results of model calculations.     

Chemischer Transport intermetallischer Phasen. 3 [1]. Der chemische Transport von Mischkristallen im System Mo/W

Chemical Vapor Transport of Intermetallic Systems. 3. Chemical Transport of Mo/W-mixed Crystals Mo/W-mixed crystals can be prepared by means of chemical vapor transport with HgBr₂ (1000°C→900°C). It is known [2] that the transport reaction of tungsten begins hours or even days after starting the experiment. This is the reason for the unusual composition of deposited crystals: EDX-analysis show them to have a Mo-rich nucleus and a W-rich shell.     

Synthese und Kristallstruktur des Aminoimino‐Phosphinat–Kupfer(I)‐Komplexes [Cu(Me3SiNP(Ph)2NSiMe3)]2

Synthesis and Crystal Structure of the Aminoiminophosphinate Copper(I) Complex [Cu(Me₃SiNP(Ph)₂NSiMe₃)]₂ The title compound 1 was prepared by the reaction of Me₃SiNP(Ph)₂N(SiMe₃)₂ with copper(I) chloride at 120 °C to give colourless crystals which were characterized by a crystal structure determination. Space group C2/c, Z = 4, lattice dimensions at 193 K: a = 1854.0(3), b = 1256.2(3), c = 1969.9(3) pm, β = 106.30(2)°; R₁ = 0.063. 1 forms dimeric molecules with a nonplanar Cu₂N₄P₂ eight‐membered ring of symmetry C₂ and a rather long Cu…Cu distance of 262.1(1) pm.     

Der Chemische Transport von Kupfer/Gallium‐ und Silber/Gallium‐Phasen

Chemical Vapor Transport of Intermetallic Systems. 10. Chemical Transport of Copper/Gallium and Silver/Gallium Phases The solid solution of gallium in copper and the ζ‐ and the γ‐phase can be prepared by CVT‐methods using iodine as transport agent. The solid solution of gallium in silver and the ζ‐phase and the ζ′‐phase can also prepared by CVT‐methods. Thermodynamic calculations allow to understand why these phases can be prepared by this manner.     

Beiträge zum thermischen Verhalten von Sulfaten. VI. Zum chemischen Transport von CuSO4, Cu2OSO4 und CuO

Contributions on the Thermal Behaviour of Sulfates. VI. On the Chemical Transport of CuSO₄, Cu₂OSO₄, and CuO A powder of anhydrous CuSO₄ can be prepared by heating CuSO₄ · 5 H₂O in air or in an argon atmosphere. In the same way it is possible to get a powder of Cu₂OSO₄. But up to now, it was difficult to get crystals of CuSO₄ and there was no method known to synthesize crystals of Cu₂OSO₄. Investigations concerning chemical transport reactions of anhydrous heavy metal sulfates showed, that it is possible to get well formed crystals of CuSO₄ and Cu₂OSO₄ by deposition from a vapour phase. As transport agents for CuSO₄, Cl₂ and HgCl₂ are especially suitable. Less appropriate are HCl, NH₄Cl, and I₂. The chemical vapor deposition of Cu₂OSO₄ proceeds well with HgCl₂. In course of these investigations we recognized, that for CuO in addition to the well approved transport agents also Cl₂, HgCl₂ or I₂ (NH₄Cl less suitable) can successfully be used.     

CuInOVO4 – Einkristalle eines Kupfer(II)‐indiumoxidvanadats durch Oxidation von Cu/In/V‐Legierungen

CuInOVO₄ – Single Crystals of a Copper(II) Indium Oxide Vanadate by Oxidation of Cu/In/V Alloys Red‐brown crystals of the new compound CuInOVO₄ (monoclinic, P2₁/c, a = 879.3(2) pm, b = 615.42(6) pm, c = 1526.2(2) pm, β = 106.69(2)?, Z = 4) were prepared by the reaction of Cu/In/V alloys with oxygen. The investigated crystals were twins by pseudo‐merohedry with a (001) twinning plane. The structure contains isolated Cu₄O₁₈‐groups consisting of trans edge sharing CuO₆‐octahedra. Interconnection of the groups by [In₄O₁₆]‐ribbons running along [010] which are built of edge‐ and corner‐sharing InO₆‐octahedra results in the formation of slabs perpendicular to the c‐axis. The slabs are linked to a threedimensional framework by VO₄^3– groups. The structure may be derived from a cubic closest packing of the oxygen atoms with copper and indium atoms in the octahedral and vanadium atoms in the tetrahedral vacancies.     

Der Chemische Transport ternärer intermetallischer Phasen in den Systemen Cr/Co/Ge und Co/Ta/Ge

Chemical Vapor Transport of Intermetallic Systems. 11 Chemical Vapor Transport of Ternary Intermetallic Phases in the Systems Cr/Co/Ge and Co/Ta/Ge By means of chemical vapor transport using iodine as transport agent it is possible to prepare a number of ternary intermetallic compounds in the system Co/Cr/Ge as single crystals. The transport behaviour in this ternary system is related to that in the binary systems. Some informations are given about transport phenomena in the systems Co/Cr and Co/Ta/Ge.     

COPPER(II) COMPLEXES OF 1-[O-ALLYLPHENOXY]-3-[ISOPROPYLAMINO]-2-PROPANOL (ALPRENOLOL)

Abstract

Complexation of Cu(II) with the antihypertension drug Alprenolol (HAlp) under different conditions (metal/ligand ratios and solvents) results in the formation of two complexes - a binuclear green one, Cu₂Alp₂Cl₂ (1), and a mononuclear violet species CuAlp₂·2H₂O (2). Single crystals of (1) were isolated and its structure determined by X-ray diffraction. In the complex Alprenolol molecules are bidentately coordinated and each Cu atom is bound with NH, and bridged by the deprotonated OH group of the ligand to the second Cu centre. The chloride ions are coordinated to copper as terminal ligands. The mononuclear complex (2) was characterized using electronic and IR spectra, EPR, magnetochemical, calorimetric, thermogravimetric methods and elemental analysis. Copper is coordinated through O^? and N of OH and NH groups of the ligands in a distorted tetrahedral structure. The structure includes also two solvent molecules per CuAlp₂ unit.     

Koexistenzbeziehungen,Darstellung und Eigenschaften ternärer Phasen im System Cu/Mo/O

Coexistence Relations, Preparation and Properties of Ternary Compounds in the System Cu/Mo/O The phase diagram of the ternary system Cu/Mo/O is presented at 773 K. The compounds CuMoO₄, Cu₃Mo₂O₉, Cu₄Mo₅O₁₇, Cu₆Mo₅O₁₈, Cu_4–xMo₃O₁₂, and Cu_xMoO₃ are found to be thermodynamical stable. The homogeneity range of Cu_4–xMo₃O₁₂ runs to x = 0.1–0.2. Single crystals of CuMoO₄ and Cu₃Mo₂O₉ were grown by chemical transport reactions with TeCl₄, Cl₂, HCl, and Br₂ as transport agent. The results were compared with thermochemical calculations. The decomposition of CuMoO₄ and Cu₃Mo₂O₉ was investigated with thermal analysis and decompositon pressure measurements.     

Chemischer Transport intermetallischer Phasen. 4. Der chemische Transport von Co5Ge3 und CoGe

Chemical Vapor Transport of Intermetallic Systems. Chemical Transport of Co₅Ge₃ and CoGe By means of transport reaction (900 → 700°C, Iodine as transport agent) pure Co₅Ge₃ or Co₅Ge₃ with CoGe as a by-product can be prepared. Thermodynamic calculations allow to understand the reaction semiquantitatively.     

Chemischer Transport fester Lösungen. 22 [1] Beschreibung des Chemischen Transports im System ZnS/ZnSe

Studies on the Chemical Vapor Transport in the System ZnS/ZnSe By means of chemical transport reactions homogeneous ionic mixed crystals with well defined compositions can be prepared in a simple way. This is shown at the example of ZnS/ZnSe‐mixed crystals. ZnS_1?xSe_x‐mixed crystals can be prepared by chemical vapour transport in the temperature gradient 1000 → 900 °C using iodine as transport agent. A thermodynamic model is presented to calculate the thermodynamic stability of ionic mixed phases and possible enrichment effects during the vapor transport. The results are compared with experimental fundings and well known transport models.     

Neues zum chemischen Transport von CuO und Cu2O

New Results on the Chemical Transport of CuO and Cu₂O The preparation of CuO crystals by chemical transport reactions with HCl is already well known, a comparison with other transport agents based on the principal of thermodynamic equilibrium and also the rate of transport was missing up to now. We report about experiments with the transport agents HgCl₂, Cl₂, I₂, Nh₄Cl, or CuCl; the quantitative evaluation was made by means of the cooperative transport model on the basis of the free energy function. By this way it is possible to find favourable experimental conditions for the suitable transport agents at the outset. It turned out that HgCl₂ is an appropriate transport agent which can easily be weighed. Also I₂ is useful, whereas the effect fo transport with Cl₂ (1 atm/298 K), CuCl, or NH₄Cl is very small. We investigated the chemical transport of Cu₂o and the conditions for the change of its direction of transport.     

Darstellung,Kristallstruktur und Eigenschaften des Kupfer(II)‐Indium(III)‐Orthophosphats Cu3In2[PO4]4

Contributions on Crystal Chemistry and Thermal Behaviour of Anhydrous Phosphates. XXIV. Preparation, Crystal Structure, and Properties of Copper(II) Indium(III) Orthophosphate Cu₃In₂[PO₄]₄ Crystals of Cu₃In₂[PO₄]₄ were grown by chemical vapour transport (temperature gradient 1273 K → 1173 K) using chlorine as transport agent. The mixed metal phosphate forms a new structure type (P2₁/c, Z = 2, a = 8.9067(6), b = 8.8271(5), c = 7.8815(5) Å, β = 108.393(5)°, 13 atoms in asymmetric unit, 2549 unique reflections with F_o > 4σ, 116 variables, R(F²) = 0.065). The crystal structure shows a hexagonal closest packing of [PO₄]^3– tetrahedra. Close‐packed layers parallel (1 0 –1) are stacked according to the sequence A, B, A′, B′, A. The octahedral interstices in this packing are completely occupied by two In³⁺, one (Cu1)²⁺ and a “dumb bell” (Cu2)₂⁴⁺. In the latter case four of the six phosphate groups that belong to this octahedral void act as bi‐dentate ligands, thus forming dimers [(Cu2)₂O₁₀] with d_Cu–Cu = 3.032 Å. Cu₃In₂[PO₄]₄ is paramagnetic (μ_eff = 1.89 μ_B, θ_P = –16.9 K). The infrared and UV/Vis reflectance spectra are reported. The observed d‐electron levels of the Cu²⁺ cations agree well with those obtained from angular overlap calculations.     

Chemischer Transport von Eisensulfid. III. Der Transport von Bodenkörpern der Zusammensetzung FeS1,00

Chemical Transport of Iron Sulphide. III. The Transport of Solids of the Composition FeS_1,00 It is possible to transport FeS_1,0 using such transport systems, in which S₂ and other sulphur-consisting gaseous species exist, for instance H₂S or some metal sulphides. The systems Fe/S/H/halogene and Fe/S/Ge (Sn)/halogene are studied experimentally and theoretically. The role of the influence of the solid composition upon the gas phase equilibria and the transport behaviour is discussed concerning a solid of the type AB_x.     

Mischkristallbildung im System CuMoO4/ZnMoO4

Mixed Crystals in the System CuMoO₄/ZnMoO₄ The existence of a complet solid solution serie Cu_1–xZn_xMoO₄ (0 ≤ x ≤ 1) is confirmed. Single crystals were obtained by chemical transport with different transport agents. The compositions and structures were characterized by EDX analysis, photometic analysis, and X‐ray investigations on polycrystallin powders and single crystals. The substitution behaviour of (Cu_1–xZn_x)O₆‐ and (Cu_1–xZn_x)O₅‐polyhedra is different and the reason for deviations from the Vegards rule are near x = 0.25.     

Bildung von HfSiO4-Einkristallen durch chemische Transportreaktion

On the Formation of HfSiO₄ Single Crystals by Chemical Transport Reactions The formation of synthetic hafnon single crystals, HfSiO₄, during chemical transport reactions in order to prepare CuCrHfSe₄ was observed. Characterization of the crystals was by electron microprobe analysis and X-ray methods. The crystals are tetragonal, a = 658.0(2), c = 598.0(6) pm, the space group is I4₁/amd (zircon structure). Refined atom parameters and details of preparation of these crystals by chemical transport reactions starting from mixtures of HfO₂ and SiO₂ are reported.