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Chr Balarew D. Trendafelov Dr. Draganova 《Monatshefte für Chemie / Chemical Monthly》1969,100(3):1115-1125
Zusammenfassung Untersucht wurde das System NH4Cl–CoCl2–H2O bei 25,0°C mit und ohne Überschuß an HCl in der Lösung. Bestimmt wurden die Kristallisationsbereiche der anomalen Mischkristalle auf der Basis von Ammoniumchlorid, der anomalen Mischkristalle auf der Basis des Doppelsalzes 2 NH4Cl·CoCl2·2H2O und der Kristallisationsbereich von CoCl2·6H2O. Die Gegenwart eines Säureüberschusses in der Lösung übt eine entsalzende Wirkung aus.Es wird gezeigt, daß die anomalen Mischkristalle Systeme darstellen, in denen mit der Zeit langsame Veränderungen eintreten. Die Einbaukomponente im Ammoniumchlorid ist das Doppelsalz 2 NH4Cl·CoCl2·2 H2O. Dieses liegt metastabil im Kristallisationsbereich des Ammoniumchlorids vor und zerfällt langsam in seine Bestandteile. Das dabei gebildete Kobalt(II)chlorid verbleibt adsorbiert im Kristallverband des Ammoniumchlorids und wird zusätzlich hydratisiert.
Mit 4 Abbildungen
Am Versuchsteil hatte auch FrauMargarita Sheleva-Vogel Anteil, wofür ihr die Autoren ihren Dank aussprechen. 相似文献
Anomalous mixed crystals of the ammonium chloride-cobalt(II) chloride-water type
The system NH4Cl–CoCl2–H2O is investigated at 25.0°C, with and without excess of HCl. The crystallization ranges of the anomalous mixed-crystals on the basis of ammonium chloride, of the anomalous mixed-crystals on the basis of the double-salt 2NH4Cl·CoCl2·2H2O and of CoCl2·6H2O were determined. The presence of HCl in the solution decreases the solubilities of the different phases occurring in the above system.It is shown that the anomalous mixed-crystals represent systems undergoing slow changes in time. The component which is built in ammonium chloride is the double-salt 2 NH4Cl·CoCl2·2 H2O. It is unstable in the crystallization range of ammonium chloride. This is why it decomposes slowly, into its components. The cobalt(II) chloride set free remains adsorbed in the ammonium chloride crystals and is hydrated additionally.
Mit 4 Abbildungen
Am Versuchsteil hatte auch FrauMargarita Sheleva-Vogel Anteil, wofür ihr die Autoren ihren Dank aussprechen. 相似文献
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H. J. Berthold D. Haas R. Tamme K. Brodersen K. P. Jensen D. Messer G. Thiele 《无机化学与普通化学杂志》1979,456(1):29-40
Crystal Structure of Thallium(I) Hexaiodomercurate(II), Tl4HgI6 In the structure of the tetragonal Tl4HgI6 (a = 944.6 pm, c = 926.0 pm, Z = 2, space group P 4/mnc) isolated, in c-direction compressed HgI6 octahedra are situated. The mercury atoms are disordered; they occupy statistically 4 positions in the equatorial plane of the octahedra in such a manner that strongly deformed HgI4 tetrahedra are produced. The thallium atoms are eightfold coordinated like a bicapped trigonal prism. The relationship between the Tl4HgI6 structure and the cubical K2PtCl6 type will be discussed. 相似文献
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H. G. Eulenhöfer 《Fresenius' Journal of Analytical Chemistry》1967,230(5):377
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《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》1989,45(2):129-137
The far infrared (FIR) spectra of [OsCl5I]2−, cis-[OsCl4I2]2−, fac-[OsCl3I3]2−, [OsCl5Br]2− and cis-[OsCl4Br2]2− (Cs-salts) have been recorded at temperatures down to 35 K. The measured band peaks are assigned to symmetry levels using group theory arguments and normal coordinate analyses starting from corresponding octahedral OsX2−6 compounds. In general, OsX bonding properties can be transferred from one compound to another except for XOsY axes where distinct trans-effects are operative. Normal coordinates are also able to explain weak oscillator strengths when predicting small changes of transition dipole moments. 相似文献
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Investigations on the Structure of Thallium(I) Halide Mercurates(II) Tl4HgBr6 crystallizes tetragonal with a = 8.978, c = 8.812 Å and Z = 2 in the space group P4/mnc. Singlecrystal methods revealed isolated HgBr6-octahedra, compressed alonged the [001] axis, with thallium atoms between them. The results have been extended to clarify the structures of the isomorphous compounds (NH4)4HgBr6 (a = 9.011, c = 8.660 Å), Tl4HgJ6 (a = 9.529, c = 9.387 Å) and Tl4HgCl2Br4 (a = 8.896, c = 8.735 Å). It was impossible to obtain Tl4HgCl6; all attempts resulted in the formation of Tl10Hg3Cl16, which crystallizes tetragonal (a = 8.477, c = 23.699 Å). 相似文献
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M. Leschke H. Lang M. Melter G. Rheinwald C. Weber H. A. Mayer H. Pritzkow L. Zsolnai A. Driess G. Huttner 《无机化学与普通化学杂志》2002,628(2):349-356
The title compounds 3‐5 are accessible by treatment of P(C6H4CH2NMe2)3( 1 ) with CuX ( 2a : X = Cl, 2b : X = Br, 2c : X = I) in the ratio of 1:1 or 1:2 in very good yields. Reaction of 1 with equimolar amounts of 2a affords the copper(I) chloride [P(C6H4CH2NMe2)3]CuCl ( 3 ). With a further equivalent of 2a homobimetallic [P(C6H4CH2NMe2)3]Cu2Cl2 ( 4 ) is formed, which also can be synthesized by the reaction of 1 with two equivalents of 2a. Complex 3 reacts with CuX (X = Br, I)to afford [P(C6H4CH2NMe2)3]Cu2ClX ( 5a : X = Br; 5b : X = I) in which mixed halides are present. The newly synthesized complexes 3‐5 were characterized by elemental analyses, by their IR‐, 1H‐, 13C{1H}‐ and 31P{1H}‐NMR spectra as well as by mass spectrometrical studies. The solid‐state structures of complexes 3 and 4 are reported. Mononuclear 3 crystallizes in the monoclinic space group P21/c with the cell parameters a = 14.285(2), b = 10.853(2), c = 17.425(2) Å , β = 103.310(10)?, V = 2628.9(7) Å 3 and Z = 4 with 4053 observed unique reflections; R1 = 0.0314. The crystal structure of 3 consists of monomeric molecules with planar coordinated copper(I) centres (CuClNP). Homobimetallic 4 crystallizes in the monoclinic space group P21/n with a = 23.905(4), b = 10.874(3), c = 25.314(5), β = 99.130(10)?, V = 6497(2) /Aring; 3 and Z = 4 with 9021 observed unique reflections; R1 = 0.0480. In 4 one of two copper(I) centres possesses a distorted trigonal‐pyramidal environment, while the other one is almost square‐pyramidal coordinated. The Cu2Cl2 segment resembles to a building block which is set up by a contact ion pair consisting of Cu+ and [CuCl2]‐ , respectively. 相似文献
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The solid state preparation, thermal and hydrolytic characteristics of thallium(I)—uranates(VI) are described. The phases identified were Tl2UO4, Tl2U2O7 and a range of solid solution (Tl2O. 2,33 UO3? Tl2O. 6 UO3). The thallium uranates are isostructural with the corresponding potassium uranates. Tl2U2O7 is the stable phase formed from the other uranates on hydrolytic treatment. The thallium uranates lose thallium(I) oxide on heating to temperatures above 750°C and the order of thermal stability is Tl2U6O19~Tl2U3O10~Tl2U2O7»Tl2UO4. 相似文献
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Dimitra Kovala-Demertzi 《Transition Metal Chemistry》1990,15(1):23-26
Summary Platinum(II) and platinum(IV) complexes of 2-amino-4, 6-dimethylpyrimidine, ADMPY, have been prepared. Solids of formula Pt(ADMPYH+)Cl3, Pt(ADMPY)2Cl4 and Pt(ADMPY)2Cl4·2HCl have been isolated and characterized by elemental analyses in conjuction with i.r. and n.m.r. spectra. A paramagnetic tan to reddishbrown complex has been reproducibly prepared from the direct reaction of K2PtCl4 and ADMPY at pH 6. 相似文献
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Novel Fast Ion Conductors of the Type M MIIICl6 (MI = Li, Na, Ag; MIII = In, Y) The ternary chlorides Li3InCl6, Na3InCl6, Ag3InCl6, and Li3YCl6 have been studied by difference scanning calorimetry, high-temperature X-ray, infrared, and high-temperature Raman methods. Impedance spectroscopic measurements exhibit fast ionic conductivity increasing in the sequence Na3InCl6 < Li3YCl6 < Ag3InCl6 < Li3InCl6. In the range of 300°C, Li3InCl6 is the best lithium ion conductor known so far (σ = 0,2 Ω?1 cm?1 at 300°C). With the exception of Na3InCl6, the chlorides exhibit complicated order-disorder phase transitions. 相似文献
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R. W. Dodson 《Journal of Radioanalytical and Nuclear Chemistry》1976,30(1):245-261
The rate of the electron exchange between thallium(I) and thallium(III) induced by iron(II) has been measured at various concentrations of Tl(I), Tl(III), and Fe(II).204Tl tracer, initially in the Tl(I) state, was used. Exchange induced by the separation method was less than 0.01%. The mechanism earlier discussed is $$\begin{gathered} Tl^{III} + Fe^{II} \rightleftharpoons Tl^{II} + Fe^{III} \left( {k_1 ,k_{ - 1} } \right) \hfill \\ Tl^{II} + Fe^{II} \rightharpoonup Tl^I + Fe^{III} \left( {k_2 } \right) \hfill \\ *Tl^I + Tl^{II} \rightleftharpoons *Tl^{II} + Tl^I \left( {k_I } \right) \hfill \\ *Tl^{II} + Tl^{III} \rightleftharpoons *Tl^{III} + Tl^{II} \left( {k_{III} } \right), \hfill \\ \end{gathered} $$ which provides an exchange path in addition to the two-electron reaction*TlI+TlIII?*TlIII+TlI (kex). The rate law deduced from this mechanism agrees with experiment over a limited range of conditions but fails to account for the observed effect at low concentrations of Tl(I). The additional rate can be represented by inclusion of a term in which the rate of the induced exchange is independent of the concentration of Tl(I). When treated according to the resulting complete rate law the data are consistent with earlier photochemical studies. The present results in combination with other data give k2=3·106 M?1·sec?1 in 1M perchloric acid at 25°C. This is in satisfactory agreement with a recent pulse radiolysis measurement as well as with independent flash photolysis studies. 相似文献
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Karl Wilhelm KlinkhammerSonja Henkel 《Journal of organometallic chemistry》1994,480(1-2):167-171
The reaction of LiN(SiMe3)2 With TlCl in toluene yields the bis(trimethylsilyl)amino derivative of thallium(I) (1). In the gaseous phase and in benzene solution the compound is mainly monomeric, whereas in the solid state the amide 1 consists of cyclic dimers, which are linked to infinite chains by intermolecular Tl Tl contacts. 相似文献
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Thallium(I), Silver(I), and Mixed Thallium(I)/Copper(I) Clusters with Bridging {Me2Si(N‐C6H4‐2‐SPh)2}2– Ligands
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The S‐functionalized aminosilane Me2Si(NH‐C6H4‐2‐SPh)2 (H2L) ( 1 ) was prepared from dichlorodimethylsilane and lithiated 2‐(phenylthio)aniline. Treatment of compound 1 with two equivalents of n‐butyllithium led to the dilithium derivative Li2L, which was used in subsequent reactions with MCl (M = Tl, Cu, Ag) to prepare the complexes [Tl2L] ( 2 ), [Cu2Tl2L2] · 2THF ( 3a ), [Cu2Tl2L2(THF)2] ( 3b ), and [Ag4L2(THT)2] ( 4 ) (THT = tetrahydrothiophene). Compound 2 consists of two thallium atoms, which are connected by a L2– ligand to give a puckered Tl2N2 ring with Tl–N distances of 255(1)–268(1) pm. Compounds 3a and 3b are heterobimetallic complexes, which are based on [Cu2L2]2– cores featuring a Cu2N4Si2 ring with linearly coordinated copper atoms [Cu–N: 190.7(3)–192.5(3) pm] and two peripherally attached Tl atoms [Tl–N: 272.7(3)–281.9(3) pm]. The molecular structure of the tetranuclear silver(I) complex 4 is closely related to the structure of compounds 3a and 3b by replacement of the Cu and Tl atoms with Ag atoms. The Ag–N distances are 217.5(3)–245.7(3) pm. 相似文献