The use of isotopic substitution and matrix isolation techniques in determining molecular constants for group IVA tetrahalides

Improved values of molecular constants of group IVA tetrahalides are reported. Accurate frequencies, including those of different isotopically substituted species, have been determined using matrix isolation spectroscopy in conjunction with isotope techniques (for SiF₄, GeF₄, SiCl₄, Si³⁵Cl₄, SiBr₄, GeBr₄, ⁷⁴GeBr₄, ^70/76GeBr₄, SnBr₄, ¹¹⁶SnBr₄ and ¹²⁴SnBr₄) and from vapour -phase IR spectra (for SiF₄, GeF₄, ⁷⁴GeF₄, SiCl₄, Si³⁵Cl₄ SiBr₄, GeBr₄, ⁷⁴GeBr₄, SnBr₄, ¹¹⁶SnBr₄ and ¹²⁴SnBr₄). Band contour analyses, often rendered difficult by isotopic effects and hot-band progressions, were simplified by measuring the spectra of isotopically pure compounds (e.g. ⁷⁴GeF₄, ¹¹⁶Sn³⁵Cl₄) and by measurements at lower temperatures (SiF)₄. The isotopic shifts, Coriolis coupling and force constant values determined in this study are more accurate than those previously reported for some of the molecules. In addition to the presentation of new data the known spectral information concerning the other tetrahalides of silicon, germanium and tin are reviewed.     

Zur gas-chromatographischen Untersuchung von Metallchloriden

Zusammenfassung Es wird über die Voraussetzungen und die Einhaltung gewisser Arbeitsbedingungen berichtet, die bei der Gas-Chromatographie anorganischer flüchtiger Metallchloride von ausschlaggebender Bedeutung sind.Folgende Verbindungen wurden gas-chromatographisch untersucht: SiCl₄, SnCl₄, GeCl₄, CCl₄, PCl₃, POCl₃, AsCl₃, TiCl₄, VCl₄, und SbCl₅.

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On the gas chromatographic investigation of metal chlorides

An account of the requirements is given and the necessary working conditions are stated which must be followed by using gas-liquid chromatography for the quantitative investigation of inorganic volatile chlorides.The following chlorides have been studied: SiCl₄, SnCl₄, GeCl₄, CCl₄, PCl₃, POCl₃, AsCl₃, TiCl₄ VCl₄, and SbCl₅.

     

Osmotic coefficients of aqueous rare-earth perchlorates and nitrates

Osmotic coefficients of aqueous solutions of La(ClO₄)₃, Pr(ClO₄)₃, Nd(ClO₄)₃, Sm(ClO₄)₃, Gd(ClO₄)₃, Dy(ClO₄)₃, Ho(ClO₄)₃, Er(ClO₄)₃, Tm(ClO₄)₃, Yb(ClO₄)₃, Lu(ClO₄)₃, Nd(NO₃)₃, Sm(NO₃)₃, and Gd(NO₃)₃ in the molality range from 0.1 mol kg^?1 nearly to saturation at 298.15 K have been determined by the isopiestic method. The results obtained agree very well with those of Rard et al. published recently. A distinct two-series effect has been observed for the constant-molality values of rare-earth perchlorates. The results are discussed in terms of hydration of the cations and ionic association.     

Synthesis of β-ketophosphonates with electron rich β-aryl groups as useful organophosphorus reagents in lignans synthesis

Investigation of the oxidation reaction of electron rich alkoxy substituted β-aryl β-hydroxyphosphonates to corresponding β-ketophosphonates, which may be utilized in syntheses of lignans with various oxidizing agents (PCC, PDC, SIBX, CAN, Oxone^®, KMNO₄/SiO₂, KMnO₄/MS 4 Å, KMnO₄/CuSO₄, KMnO₄/CuSO₄/Al₂O₃, MnO₂, CrO₃/SiO₂, H₂O₂/salen) is described. The effect of oxidants and reaction conditions on the reaction efficiency and yield was also investigated.     

Kryometrische Untersuchungen. IV. Lösungen von oxidischen Mo6+- und Cr6+-Verbindungen in geschmolzenem K2Cr2O7 und KNO3

The depression of freezing point of molten K₂Cr₂O₇ and KNO₃ as solvents was measured after addition of small concentrations of the following compounds: to K₂Cr₂O₇: MoO₃, CrO₃, (NH₄)₂CrO₄, K₂MoO₄, Na₂MoO₄, Li₂MoO₄, and Na₂Mo₂O₇, respectively; to KNO₃: CrO₃, (NH₄)₂Cr₂O₇ K₂Cr₂O₇, K₂CrO₄ and MoO₃, (NH₄)₆(Mo₇O₂₄) · 4 H₂O, K₂Mo₂O₇, K₂MoO₄, Na₂MoO₄ and Li₂MoO₄, respectively. It could be concluded from the measured values of the freezing point depression if a reaction between solvent and solute took place.     

A Nitron-Polyvinylbenzyl Chloride Polymer to Selectively Remove Oxidizing Anions from Non-Oxidizing Anions. Removal of NO3 − and NO2 − from Polluted Waters

Abstract

A nitron-polyvinylbenzyl chloride polymer was found to have a strong preference for oxidizing anions such as NO₃ ^?, NO₂ ^?, ReO₄ ^?, MnO₄ ^?, C1O₄ ^?, C1O₃ ^?, and Cr₂O₇ ⁼ but not for the non-oxidizing anions SO₄ ⁼, HSO₄ ^?, H₂PO₄ ⁼, HPO₄ ⁼, PO₄ ⁼, OH^?, CO₃ ⁼, HCO₃ ^?, F^?, C1^?, and Br^?.     

Representation of Electrical Conductances for Polyvalent Electrolytes by the Quint-Viallard Conductivity Equation. Part 1. Symmetrical 2:2 Type Electrolytes. Dilute Aqueous Solutions of Alkaline Earth Metal Sulfates and Transition Metal Sulfates

Literature values of the electrical conductivities of dilute aqueous solutions of alkaline metal sulfates (BeSO₄, MgSO₄, CaSO₄, SrSO₄) and of transition metal sulfates (MnSO₄, FeSO₄, CoSO₄, NiSO₄, CuSO₄, ZnSO₄, CdSO₄) were reexamined within the framework of the Quint-Viallard conductivity equations in order to obtain a uniform representation of conductivities. It was observed that the limiting conductances of electrolytes at infinite dilution are very similar irrespective of the applied conductivity equation, whereas the derived ion association equilibrium constants vary considerably. The ion association equilibrium constants are therefore of doubtful physical value and should be treated rather as just fitting parameters.     

Interaction of salts in ionic melts of the ternary reciprocal systems Na,K‖BO2,MoO4 and Na,K‖BO2,WO4

The phase diagrams of the ternary reciprocal systems Na,K‖BO₂,MoO₄ and Na,K‖BO₂,WO₄ were studied for the first time by a calculation-experimental method and differential thermal analysis. The coordinates were determined for binary eutectics of the diagonal stable sections NaBO₂-K₂MoO₄(K₂WO₄) and the ternary invariant points e(55 mol % NaBO₂, 45 mol % K₂MoO₄, 740°C), e(55 mol % NaBO₂, 45 mol % K₂WO₄, 730°C), E(4.5 mol % NaBO₂, 78 mol % Na₂MoO₄, 17.5 mol % K₂MoO₄, 652°C), E(4.5 mol % NaBO₂, 78 mol % Na₂WO₄, 17.5 mol % K₂WO₄, 643°C), P₂(5 mol % NaBO₂, 56 mol % Na₂MoO₄, 39 mol % K₂MoO₄, 673°C), P₂(5 mol % NaBO₂, 56 mol % Na₂WO₄, 39 mol % K₂WO₄, 671°C). Binary solid solutions based on sodium and potassium metaborates were shown to be stable. Analytical models of phase equilibrium states of the ternary reciprocal systems Na,K‖BO₂,MoO₄(WO₄) were obtained, which enable one to calculate melting (crystallization) points and construct isotherms at any given composition. The specific heats of melting of samples of invariant compositions were found by quantitative differential thermal analysis.     

Darstellung und Struktur von BaAl2Se4, BaGa2Se4, CaGa2Se4 und Caln2Te4

Preparation and Crystal Structure of BaAl₂Se₄, BaGa₂Se₄, CaGa₂Se₄, and CaIn₂Te₄ The new compounds BaAl₂Se₄, BaGa₂Se₄, CaGa₂Se₄ and CaIn₃Te₄ crystallize with constants see “Inhaltsübersicht”. The structures are strongly related to the TlSe structure.     

Solid phase reactivity of sodium oxosalts of manganese

The observed relationships are presented of the solid phase reactivity of the following salts: NaMnO₄, Na₂MnO₄, Na₃MnO₄, Na₄MnO₄, Na₂MnO₃, Na₂Mn₂O₅, Na₅MnO₄, Na₄Mn₂O₅, NaMnO₂, Na₄MnO₃, Na₂MnO₂ and Na₂Mn₂O₃.     

The analysis of the near IR of some organic and organometallic compounds by photoacoustic spectroscopy

The photoacoustic spectrum (PAS) was measured in the near IR region (1000 to 2600 nm) for organic compounds (C₆H₆, C₆D₆, C₇H₈, and C₆H₁₂) and organometallic compounds (Cp₂Fe, Cp₂Fe₂(CO)₄, Cp₄Fe₄(CO)₄, Cp₄Fe₄S₄, C₆H₆Cr(CO)₃, CpCo(C₄Ph₄) and CpCo(CO)₂). Band assignments were made by comparison to the infrared spectra. The bands were assigned as the CH overtone stretch and combinations of CH and other IR fundamentals. These bands provide fingerprint spectra for these compounds.     

Der chemische Transport von FeP2 und FeP4 mit lod

Chemical Transport of FeP₂ and FeP₄ with Iodine Experiments on the chemical transport of FeP₂ and FeP₄ with iodine are discussed, considering the gaseous molecules I₁, I₂, FeI₂, Fe₂I₄, FeI₃, Fe₂I₆, PI₃, P₂I₄, P₄, P₂, and P. Thermodynamic calculations give δH°(298) = 56.322 kcal and ΔS°(298) = 39.5 cal/K for the reaction FeP_2,f + I₂ = FeI₂ + 0.5 P₄ and δG°(923) = 35.8 kcal for the reaction FeP_4,f + I₂ = FeI₂ + P₄.     

The Oxidation of Heterogeneous Tl/Ni/P‐Alloys — Preparation and Crystal Structures of the Thallium Nickel Phosphates TlNi4(PO4)3, Tl4Ni7(PO4)6, and Tl2Ni4(P2O7)(PO4)2

Single crystals of the first anhydrous thallium nickel phosphates were prepared by reaction of heterogeneous Tl/Ni/P alloys with oxygen. TlNi₄(PO₄)₃ (pale‐yellow, orthorhombic, space group Cmc2₁, a = 6.441(2)Å, b = 16.410(4)Å, c = 9.624(2)Å, Z = 4) crystallizes with a structure closely related to that of NaNi₄(PO₄)₃. Tl₄Ni₇(PO₄)₆ (yellow‐brown, monoclinic, space group Cm, a = 10.711(1)Å, b = 14.275(2)Å, c = 6.688(2)Å, β = 103.50(2)°, Z = 8) is isotypic with Na₄Ni₇(PO₄)₆, and Tl₂Ni₄(P₂O₇)(PO₄)₂ (brown, monoclinic, space group C2/c, a = 10.389(2)Å, b = 13.888(16)Å, c = 18.198(3)Å, β = 103.1(2)°, Z = 8) adopts the K₂Ni₄(P₂O₇)(PO₄)₂ structure. Tl₂Ni₄(P₂O₇)(PO₄)₂ could also be prepared in nearly single phase form by reaction of Tl₂CO₃, NiO, and (NH₄)₂HPO₄.     

The electronic structures of tetrahedral oxo-complexes. The nature of the “charge transfer” transitions

The electronic structures of MnO^?₄, MnO^2?₄, MnO^3?₄, CrO^2?₄, CrO^3?₄, VO^3?₄, RuO₄, RuO^?₄, RuO^2?₄, TcO^?₄ and MoO^2?₄ have been investigated using the Hartree-Fock-Slater Discrete Variational Method. The calculated ordering of the valence orbitals of all the comlexes is: t₁, 4t₂, 3a₁, 1c, 3t₂, with t₁ the orbital of highest energy. The calculated single transition energies are in good agreement with experimental values and indicate the uniform assignment: t₁ → 2e(v₁), 4t₂ → 2e(v₂). t₁ → 5t₂(v₃), and 4t₂ → 5t₂(v₄). A/D values, calculated from the theory of magnetic circular dichroism (MDC) also support this assignment.Population analyses reveal that all complexes, whether d⁰, d¹ or d², have d-orbital populations close to those of the corresponding M²⁺ ions in which two electrons have been removed from the (n + 1)s orbital of M. This is also true of the excited states, such as t₁ → 2e and 4t₂ → 2e, where a transfer of charge from the ligands to the metal has previously been assumed. It is shown that, instead of a transfer of charge from ligands to metal, electronic excitation consists of a rearrangement of electron density both at the ligands and at the metal.     

On precipitation effects of aluminum,lanthanum, iron (III), and thorium phosphates

Summary Typical precipitation curves of various metal phosphates have been obtained using the turbidimetric technique. The following systems have been investigated: Al(NO₃)₃-K₃PO₄, Al(NO₃)₃-KH₂PO₄, Al(NO₃)₃NaH₂PO₄, FeCl₃-K₃PO₄, FeCl₃-(NH₄)₂HPO₄, FeCl₃K₂HPO₄, FeCl₃-KH₂PO₄, FeCl₃-NaH₂PO₄, La(NO₃)₃K₃PO₄,La(NO₃)₃-K₂HPO₄,La(NO₃)₃-KH₂PO₄,La(NO₃)₃NaH₂PO₄ and Th(NO₃)₄-K₂HPO₄. Typical precipitation curves indicated concentration ranges of phosphate precipitation and of complex solubility.

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Zusammenfassung Typische F?llungskurven verschiedener Metallphosphate, die mittels Trübungsmessungen erhalten wurden, wurden graphisch dargestellt. Die folgenden Systeme wurden untersucht: Al(NO₃)₃-K₃PO₄,Al(NO₃)₃KH₂PO₄, Al(NO₃)₃-NaH₂PO₄, FeCl₃-K₃PO₄, FeCl₃(NH₄)₂HPO₄, FeCl₃-K₂HPO₄, FeCl₃-KH₂PO₄, FeCl₃NaH₂PO₄, La(NO₃)₃-K₃PO₄, La(NO₃)₃-K₂HPO₄, La(NO₃)₃-KH₂PO₄, La(NO₃)₃-NaH₂PO₄ und Th(NO₃)₄K₂HPO₄. Typische F?llungskurven zeigten Konzentrationsgebiete, in welchen die Metallphosphate gef?llt werden, sowie Konzentrationen, die zur Komplexbildung führten.

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Supported in part by the U.S. Army Research Office, Contract No. DA-ORD-10.     

Darstellung von Schwermetallchalkogenid-Einkristallen durch chemischen Transport mit Aluminiumchlorid

Zusammenfassung Durch chemischen Transport mit wasseerfr. AlCl₃ als Transportmittel konnten folgende Schwermetallsulfide und-selenide in Form von Einkristallen erhalten werden: Cr₂S₃, Cr₃S₄, Cr₅S₆, Cr₇S₈, CrS, Cr₂Se₃, Cr₇Se₈, CoS₂, CoS, (Co), NiS₂, NiS, ZnCr₂S₄, CdCr₂S₄, MnCr₂S₄, ZnCr₂Se₄, CdCr₂Se₄, HgCr₂Se₄, CuCr₂Se₄, NiCr₂S₄, Ni_0,95Cr_0,05S, Ni_0,83Cr_0,17S, Ni_0,75Cr_0,25S. Der Mechanismus des Transports mit AlCl₃ und die Darstellung größerer Einkristalle werden diskutiert.

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Growing of chalcogenide single crystals by chemical transport with aluminium chloride

Single crystals of the following compounds have been grown by chemical transport with anhydrous aluminium chloride as transporting agent: Cr₂S₃, Cr₃S₄, Cr₅S₆, Cr₇S₈, CrS, Cr₂Se₃, Cr₇Se₈, CoS₂, CoS, (Co), NiS₂, NiS, ZnCr₂S₄, CdCr₂S₄, MnCr₂S₄, ZnCr₂Se₄, CdCr₂Se₄, HgCr₂Se₄, CuCr₂Se₄, NiCr₂S₄, Ni_0,95Cr_0,05S, Ni_0,83Cr_0,17S, Ni_0,75Cr_0,25S. The growing of larger crystals and the mechanism of the transport with AlCl₃ are discussed.

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Cs. Lovász, Teil der Dissertation, Universität Köln 1969.

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K.-H. Bertram, Teil der diplomarbeit, Universität Köln 1970.     

Influence of the Coordination of Donor Solvent Molecules to 1,4,7,10-Tetramethyl-1,4,7,10- tetraazacyclododecanenickel(II) and Analogous Nickel(II) Complexes on Their Steric Factors

Coordination equilibrium constants (K _NiS) of some donor solvent molecules to 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecanenickel(II) ([Ni(Me₄[12]aneN₄)]²⁺) were determined in nitrobenzene (a noncoordinating bulk solvent). The first (K _NiS1) and second stepwise coordination equilibrium constants (K _NiS2) for 1,4,7,10-tetraazacyclododecanenickel(II) ([Ni([12]aneN₄)]²⁺), 1,4,8,11-tetraazac yclotetradecane- nickel(II) ([Ni([14] aneN₄)]²⁺), 1,4,8,11-tetrathiacyclotetra-decanenickel(II) ([Ni([14]aneS₄)]²⁺) were also reinvestigated. The K _NiS values for [Ni(Me₄[12]aneN₄)]²⁺ were compared to those of [Ni([12]aneN₄)]²⁺, (1R,4S, 8R,11S)-1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecanenickel(II) (R,S,R,S-[Ni(Me₄[14]aneN₄)]²⁺), R,R,S,S-[Ni(Me₄[14]aneN₄)]²⁺, [Ni([14]aneN₄)]²⁺, and [Ni([14]aneS₄)]²⁺. Coordination of pyridine (Py), N,N,N′,N′-tetramethylurea (TMU), and N,N-dimethylacetamide (DMA) to [Ni(Me₄[12]aneN₄)]²⁺ was observed, although these donor solvent molecules did not coordinate to R,S,R,S-[Ni(Me₄[14]aneN₄)]²⁺. The K _NiS values for Py, TMU, and DMA are 7.9, 2.8, and 9.0 dm³⋅mol⁻¹, respectively. Some hydrogen-bonding waters were coordinated to R,S,R,S-[Ni(Me₄[14]aneN₄)]²⁺, but such waters did not coordinate to [Ni(Me₄[12] aneN₄)]²⁺. Also, the K _NiS2 values were larger than the corresponding K _NiS1 values for [Ni([14]aneS₄)]²⁺. Furthermore, the K _NiS1 values for [Ni([12]aneN₄)]²⁺ were the largest among these nickel(II) complex cations. The K _NiS, K _NiS1, and K _NiS2 values are discussed in terms of properties of the donor solvents and steric strains of these nickel(II) complex cations.     

Conductance of 1:1 electrolytes in methyl formate

The electrolytic conductivities of LiClO₄, LiAlCl₄, LiAsF₆, NaClO₄, NaBPh₄, and Bu₄NClO₄ have been measured in methyl formate at 25°C. Evidence is presented for strong association between the perchlorate ion and the formyl proton of the solvent. Ion association and triple ion formation constants suggest that LiClO₄, LiAlCl₄, and NaClO₄ form solvent separate ion pairs and triple ions. NaBPh₄ forms contact ion pairs and triple ions, and the remaining salts appear to form both types of ion pairs and triple ions.     

X-ray photoelectron spectroscopy of alkaline earth metal uranate complexes

Summary X-ray photoelectron spectra for MgUO_4–x, MgU₃O_8.9, CaUO_4–x, Ca₂UO₅, Ca₃UO₆, Ca₂U₃O₁₁, CaU₂O₇, CaU₄O₁₂, SrUO₄, SrUO_3.67, Sr₂U₃O₁₁, SrU₄O_12.8, Sr₂UO₅, Sr₃UO₆, BaUO₄, Ba₃UO₆, BaU₂O₇, Ba₂U₂O₇ and Ba₂U₃O₁₁ have been recorded.Recorded O(1s) peak positions range from 529.5 to 533.4 eV and certain trends can be related to data obtained from other studies. By contrast, the range of U(4f) peak positions is much smaller totalling 0.7 eV. All compounds show satellite structure to the high binding energy side of the U(4f) peaks. Satellites separated byca. 10 eV from the main peaks are assigned to a transition from the uranium-oxygen bonding band to the U(6d) conduction band.     

Photoinitiation by radical-cationic mechanism in the polymerization of isobutylene with lewis acids

ESR spectra of Lewis acids (VCl₄, TiCl₄, TiBr₄, SnCl₄, and AlBr₃) and their mixtures with isobutylene were investigated in a n-heptane solution in the dark and under irradiation at 400–480 nm at ?80 to ?150°C. A signal was observed only upon irradiating mixtures of VCl₄, TiCl₄, or TiBr₄ and isobutylene. The signal was identified as an isobutylene radical-cation by comparison with a simulated spectrum. A signal indicating the presence of peroxy radicals were recorded in measurements carried out in the presence of oxygen; these radicals originated from reaction of the isobutylene radical-cation with oxygen. Radical-cation initiation by visible light is indicated by the polymerization of isobutylene by VCl₄, TiCl₄, and TiBr₄ and by ESR spectra. The inhibiting effect of oxygen in photochemically initiated polymerization of isobutylene was also elucidated.