Radiochemical measurement of solubility product and thermodynamic functions for erbium trifluoride-water system

The solubility and solubility product of erbium trifluoride in aqueous solution were measured using three different techniques. The more acceptable radiometric values for the solubility and solubility product are 1.98×10^–5M and 3.5×10^–18, respectively. The values for the thermodynamic functions, H ₂₉₈ ^o , G ₂₉₈ ^o and S ₂₉₈ ^o for the dissolution of ErF₃ and the stability constant for ErF²⁺ have also been measured.     

Role of Tin Difluoride and Gallium Trifluoride in Glass Formation in SnF2–GaF3–BaF2

The structure of glasses in SnF₂–GaF₃ and SnF₂–GaF₃–BaF₂ systems was investigated by IR spectroscopy. It is shown that the glass structure in systems of this type is formed by two glass-forming agents: gallium trifluoride and tin difluoride. The introduction of 5 mole % barium difluoride shifts the edge of the absorption band to the low-frequency region.     

Crystal and molecular structure of the simple cation-radical salt ethylenedithiopropylenedithiotetrathiafulvalene trichloromercurate (EPT)HgCl3

The new cation-radical salt (EPT)HgCl₃ is prepared. Its structure and electrical conductivity are studied. The crystal structure of (EPT)HgCl₃ contains (EPT)⁺ in the chair conformation and trigonal planar HgCl₃ ^– packed into organic and inorganic layers alternating along thea axis. Shortened intermolecular contacts join HgCl₃ ^– into infinite chains along the c axis (Hg...Cl, 3.289 and 3.387 Å), form stacks (S...S, 3.536 and 3.597 Å) and layers (S...S, 3.427–3.498 Å) of EPT⁺ cation-radicals, and create cation-anion interactions between neighboring layers in the crystal (Cl...S, 3.396–3.521 Å, Cl...C, 3.360 Å). The configuration of the bonds around Hg in HgCl₃ ^– is distorted trigonal planar: Hg-Cl, 2.342(3)–2.449(3) Å, Cl-Hg-Cl, 110.7(1)–137.4(1). The Hg atom lies out of the plane of the Cl atoms by 0.015 Å. The conductivity of (EPT)HgCl₃ at 20°C is ₃₀₀ 5·10^–2 (·cm)^–1. The dependence of conductivity on temperature is semiconducting in nature.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2055–2061, September, 1991.     

Oxidative ammonolysis of 3-picoline on mixed oxide catalysts

The oxidative ammonolysis of 3-picoline has been studied on the following catalysts: V₂O₅ on corundum, V₂O₅ with the addition of 1% of H₂WO₄ on corundum, V₂O₅ + MoO₃ + P₂O₅ (10.350.35) on silica gel, V₂O₅ + Al₂O₃, and a melt of V₂O₅ + TiO₂ (10.22). Mixed catalysts of vanadium and titanium oxides exhibited the highest activity and selectivity. With the passage of 25–45 moles of oxygen (in the form of air), 5–10 moles of ammonia, and 50–70 moles of water per mole of 3-picoline at a temperature of 390–410° C, the amount of nicotinonitrile formed on these catalysts amounted to 85–90% of the theoretically possible amount.Part LXIII of the series Oxidation of organic compounds; for part LXII, see [1].     

3, 3, 3-Trifluoropropyl(methyl)cyclosiloxanes

The influence of the number of 3, 3, 3-trifluoropropyl(methyl)siloxane links (/) in the cyclotetrasiloxanes _mD_4-m, where D represents the dimethylsiloxane link and m=0–4, on the rearrangement of these compounds in acetone solution under the action of sodium siloxanolate has been studied. The rearrangement takes place with the formation of a linear polysiloxane the degradation of which yields, in addition to the initial ring, cyclosiloxanes with a different structure. The rate of rearrangement of _mD_4-m and of the formation of a linear polysiloxane rises with an increase in m from 0 to 3. The equilibrium concentration of the linear polysiloxane formed from _mD_4-m is inversely proportional to m. Results have been obtained on the kinetics of the formation of the cyclosiloxanes _mD_n, where m=0–5, n=0–5, and m+n=3–6, in the rearrangement of the rings D₃, ₂D₂, ₃D, and ₄. The reactivity of the siloxane links rises in the sequence (CH₃)₂Si-O-Si(CH₃)₂ < (CF₃CH₂CH₂)-(CH₃) Si-O-Si(CH₃)₂ <(CF₃CH₂CH₂) (CH₃)Si-O-Si(CH₃) (CH₂CH₂CF₃) . Because of the negative inductive effect transferred through the siloxane links, the 3, 3, 3-trifluoropropyl groups strongly activate the siloxane ring with respect to nucleophiiic reagents.For part I, see [3].     

Conservatism of the KTi2(PO4)3 : Al3+ Phosphate Crystal Lattice

We have studied phosphate crystals with low dopant content using X-ray photoelectron spectroscopy (XPS), X-ray fluorescence analysis (XFA), and electron paramagnetic resonance (EPR). We have observed a new stage in the process of doping KTi₂(PO₄)₃ with aluminum: for low aluminum content (n 0.7 at.%), the aluminum forms a new Al sublattice in the channels of the matrix and essentially does not replace titanium in the main Ti sublattice. It is shown that the anomalous physical and chemical properties of the phosphates are due to a change in the mechanism of dopant distribution in the crystal for small n. We have observed selectivity in the way aluminum occupies different types of voids. The mechanism proposed for the appearance of anomalous properties in the system KTi₂(PO₄)₃–Al₂O₃–KPO₃ can be used in practice for a wide range of oxide framework matrices.     

Proanthocyanidins ofPolygonum coriarium. IV. Structures of proanthocyanidins T3 and T4

Two oligomeric proanthocyanidins have been isolated from the roots ofPolygonum coriarium. By a study of their physical properties and spectral characteristics and analysis of the results of chemical transformations, the chemical structures of these compounds have been established as: (–)-epicatechin-77[O--D-glucopyranosyl]₃ O-⊃-D-glucopyranosyl (m-trigallolyl)-[(4-6)-(–)-epigallocatechin]₂-(4-6)-(–)-epigallocatechin—T3; and (–)-epicatechin-3-O-galloyl-7-[O--D-glucopyranosyl]₃O--D-glucopyranosyl galloyl-[(4-6)-(–)-epicatechin]₄-(4-6)-(–)-epigallocatechin — T4.The materials of this paper were presented at the IInd International Symposium on the Chemistry of Natural Compounds (SCNC), Eskiehir, Turkey, October 22–24, 1966).Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 707–713, September–October, 1997.     

Viskosimetrische Untersuchung des Systems LiNO3−H2O

Zusammenfassung Die Temperaturabhängigkeit der Viskosität im System LiNO₃–H₂O und im Temperaturbereich 20–70°C wird in der Gleichung =A expB/T=T ₀ zusammengefaßt; aus der so erhaltenen Beziehung werden Rückschlüsse auf die Struktur der Lösungen gezogen.

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Temperature dependence of the viscosity in the system LiNO₃–H₂O is expressed by =A expB/T-T ₀ in the temperature range 20–70°C. Possible relations to structural changes in the solutions are considered.

     

Kinetics and mechanism in the decomposition of NH3 in a radio-frequency pulse discharge

Studies of time-resolved absorption spectra of transient species in the decomposition of NH₃ by an r.f. pulse discharge together with product analysis showed that the major radical formed was NH at concentrations of the order of 10^–6 mol dm^–3 (10⁵ molec. cm^–3). Possible mechanisms for the formation of the radical during the discharge and its decay following pulse cut-off were tested by computer simulation of the kinetic data. Following zero-order formation with rate coefficient 0.19±0.03 mol dm^–3 s^–1, the decay was second order in NH with rate coefficient 2.1±0.5×10⁹ mol^–1 dm³ s^–1 both for pure NH₃ and where NH₃/rare gas mixtures were investigated. The kinetic data are consistent with NH removal in a nonassociative radical-radical reaction proceeding via a short-lived collision complex, probably 2NH N₂H₂ N₂ + H₂.     

Integral heats of solution and enthalpies of ionization of 100% nitric acid at 298 K 3. Aqueous solutions of sulfuric acid containing 70–90% H2SO4 and ionization of HNO3 as a base

The integral heats of solution of 100% HNO₃ at =0.1mole/liter in aqueous solutions of H₂SO₄ of <90% by wt. were measured. A scheme was proposed and proved for ionization of HNO₃ as a base in 82–90% aqueous solutions of H₂SO₄, according to which un-ionized HNO₃ exists in the form of an aqueous solvate H₂O-HNO₃ and the ionized form as the ion pair NO₂ ⁺·HSO₄ ^–. The value of the enthalpy of ionization of nitric acid H(NO₂ ⁺ HSO₄ ^–)=H(NO₂ ⁺·HSO₄ ^–) drops from 2.05 at 89.99% H₂SO₄ to 0.18 kcal/mole in 84.07% H₂SO₄.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 306–310, February, 1990.     

Fuel Combustion Reactions and Catalysts: XXI. Synthesis and Characterization of Modified Mn–Al–O Catalysts for High-Temperature Oxidation

The phase composition of supported Mn–Al–O catalysts and their activity in the reaction of methane oxidation were studied depending on the composition of aluminum oxide supports (-Al₂O₃ with different -Al₂O₃ contents modified with individual Mg, La, and Ce oxides or Mg + La and Mg + Ce oxide mixtures) and calcination temperatures (500, 900, and 1300°C). It was found that the Mn–Al–O catalysts based on -alumina containing -Al₂O₃ and modified with Mg, La, or Ce additives are more active and thermally stable (up to 1300°C) than the samples based on pure -Al₂O₃. A conclusion was drawn that a higher degree of disorder of the structure of -Al₂O₃, compared to that of -Al₂O₃, is favorable for a deeper interaction of manganese and modifying additives with the support at the early stages of the synthesis and for the formation of Mn–Al compounds with complex composition (solid solutions and/or hexaaluminates) at 1300°C. These compounds are responsible for the stability and high activity of the catalysts in methane oxidation.     

Synthesis of an intercalated compound of montmorillonite and 6-polyamide

Natural montmorillonite, fractionated from bentonite produced in Yamagata, Japan, was ion-exchanged for NH ₃ ⁺ –(CH₂)₁₁–COOH, NH ₃ ⁺ –(CH₂)₅–COOH, Al³⁺, Cu²⁺, Mg²⁺, Co²⁺, Li⁺, K⁺ and H⁺. The mixtures of the ion-exchanged montmorillonite and -caprolactam were heated at 263°C in glass ampoules for various periods. The intercalated compounds before and after the heating were examined by X-ray powder diffraction, DSC and GPC. Although -caprolactam was not polymerized without montmorillonite, it was polymerized at 263°C in the presence of montmorillonite. The polymerization rate varied with the interlayer cations in the order of NH ₃ ⁺ –(CH₂)₁₁–COOH>Al³⁺>NH ₃ ⁺ –(CH₂)₅–COOH>H⁺>Cu²⁺>Mg²⁺>Co²⁺>Li⁺>K⁺. After heating at 263°C for 5 h, the mean number-average molecular weight was about 1.5×10⁴. Although the interlayer distance of NH ₃ ⁺ –(CH₂)₁₁–COOH type montmorillonite/-caprolactam compound increased from 2.85 nm to 4.90 nm by heating at temperatures above the melting point of -caprolactam, those of other compounds were not changed. After heating at 263°C, an intercalated compound of montmorillonite and 6-polyamide, whose interlayer distance was more than 10 nm, was obtained. It is concluded that montmorillonite acts as a Brönsted acid and initiates the open ring polymerization of -caprolactam and that the driving force of swelling is the polymerization energy.Presented at the Fourth International Symposium on Inclusion Phenomena and the Third International Symposium on Cyclodextrins, Lancaster, U.K., 20–25 July 1986.     

Reaction of Ru(PPh3)3Cl2 with arylazoimidazoles: spectral characterisation and redox studies of [bis-{N(1)-alkyl-2-(arylazo)imidazole}-bis-(triphenylphosphine)]-ruthenium(II) perchlorate

Ru(PPh₃)₃Cl₂ reacts with N(1)-alkyl-2-(arylazo)imidazoles, p-RC₆H₄N=NC₃H₂N₂X, [RaaiX, R = H(a), Me(b), Cl(c); X = Me(1), Et(2), Bz(3)] under refluxing conditions in EtOH to give [Ru(RaaiX)₂(PPh₃)₂](ClO₄)₂ · H₂O complexes (4–6). RaaiX is a bidentate chelator (N, N) with N(imidazole), N and N(azo), N donor centres. Three isomers are present in the mixture in which the pairs of PPh₃, N and N occupy cis–cis–trans, cis–trans–cis and cis–cis–cis, positions respectively. The isomers were identified by ¹H-n.m.r. spectra. Four signals are observed in the aliphatic zone for N(1)-X; two are of equal intensity at higher and the other two signals at lower in the ratio 1:0.3:0.2 suggesting the presence of cis–cis–cis, cis–trans–cis and cis–cis–trans-geometry. The complexes display the allowed t ₂(Ru) ^*(RaaiX) transition. Cyclic voltammetry indicates two consecutive Ru^III/II couples along with azo reductions.     

Textured PbTiO3, Pb(Ca)TiO3-Al2O3 Composite Films Prepared by Chemical Solution Deposition Method

Chemical solution deposition method (CSD) method was used to prepare PbTiO₃ (PT), Pb_{1– x} Ca _x TiO₃ (PCT), PbTiO₃-Al₂O₃ (PT-AL) and Pb_{1 – x} Ca _x TiO₃-Al₂O₃ (PCT-AL) thin films on amorphous (soda-lime glass, SiO₂ glass) substrates. The films were examined by XRD methods to describe the phase composition, cell parameters, type and degree of texture. In dependence on the molar ratio of Ti:Al, the different extent of crystallographic ordering was observed ranging from randomly oriented to strongly textured crystallites of PT. (100)uvw preferred orientation growth of PT grains was identified.     

Molecular Structures and Vibrational Spectra of ScF3, YF3, and LaF3 as Calculated by the CISD+Q Method

Molecular structures and vibrational spectra of ScF₃, YF₃, and LaF₃ were studied by the Hartree–Fock– Roothaan method in terms of second-order Möller–Plesset perturbation theory and by the configuration interaction method including all singly and doubly excited configurations and Davidson's correction for quartic excitations (CISD+Q). The atomic core orbitals are defined in terms of the effective relativistic potentials suggested by Stevens et al. The equilibrium nuclear configuration is shown to be planar (D _3h symmetry) for ScF₃ and YF₃ and pyramidal (C _3v ) for LaF₃ with a bond angle . The inversion barrier of LaF₃ is very low: h = E(D _3h )- E(C _3v ) = 38 cm ^–1 (CISD+Q). The vibrational spectra were calculated by the variational method using the vibrational Hamiltonian describing the nonrigidity of a molecule with respect to out-of-plane deformation. The calculation results are compared with the previously published experimental data. The IR band assignments for matrix-isolated molecular conformations in a vapor over yttrium trifluoride were corrected.     

Effect of alumina concentration on thermal and structural properties of mas glass and glass-ceramics

Magnesium aluminum silicate (MAS) glass samples with different concentrations of alumina (7.58 to 14.71 mol%) were prepared by melt and quench-technique. Total Mg content in the form of MgF₂+MgO was kept constant at 25 mol%. MAS glass was converted into glass-ceramics by controlled heat treatment at around 950°C. Crystalline phases present in different samples were identified by powder X-ray diffraction technique. Dilatometry technique was used to measure the thermal expansion coefficient and glass transition temperature. Scanning electron microscopy (SEM) was employed to study the microstructure of the glass-ceramic sample. It is seen from X-ray diffraction studies that at low Al₂O₃ concentrations (up to 10.5 mol%) both MgSiO₃ and fluorophlogopite phases are present and at higher Al₂O₃ concentrations of 12.3 and 14.7 mol%, fluorophlogopite and magnesium silicate (Mg₂SiO₄), respectively are found as major crystalline phases. The average thermal expansion co-efficient (_avg) of the glass samples decreases systematically from 9.8 to 5.5·10^–6 °C^–1 and the glass transition temperature (T g) increases from 610.1 to 675°C with increase in alumina content. However, in glass-ceramic samples the _avg varies in somewhat complex manner from 6.8 to 7.9·10^–6 °C^–1 with variation of Al₂O₃ content. This was thought to be due to the presence of different crystalline phases, their relative concentration and microstructure.Authors wish to thank Dr V. C. Sahni, Director Physics Group and Dr J. V. Yakhmi, Head TPPED, BARC for encouragement and support to the work. They would like to thank Dr S. K. Kulshreshtha for many useful discussions. Technical assistance from Shri B. B. Sawant, Mrs Shobha Manikandan, Mr Rakesh Kumar and Shri P. A. Wagh is gratefully acknowledged. One of authors (BIS) would like to thank BRNS-DAE for awarding him KSKRA fellowship.     

Homogeneous pyrolysis kinetics of ethyl 3-hydroxy-3-methylbutanoate in the gas phase

The pyrolysis kinetics of ethyl 3-hydroxy-3-methylbutanoate have been examined over the temperature range of 286–330°C and pressure range of 29–108 Torr. In a seasoned vessel and in the presence of the free radical inhibitor cyclohexene or toluene the reaction is homogeneous, unimolecular and obeys a first-order rate law. The elimination products are mainly acetone and ethyl acetate, and very small amounts of ethyl 3-butenoate, acetic acid, ethylene and H₂O. The rate coefficient is expressed by the following equation: log k₁(s^–1)=(12.39±0.46)–(174.5±5.2) kJ mol^–1 (2.303RT)^–1. The mechanism appears to proceed via a six-membered cyclic transition state, where polarization of the (CH₃)C(OH)^+...-CH₂COOCH₂CH₃ bond is rate determining.     

Metal ion catalysed aquation of carboxylatoamine cobalt(III) complexes. Kinetics of copper(II) catalysed aquation ofcis(diformato)bis(ethylenediamine)cobalt(III) ion

Summary The aquation ofcis-[(en)₂Co(CO₂H)₂]⁺ tocis-[(en)₂Co(OH₂)(CO₂H)]²⁺ is catalysed by Cu²⁺ and the rate equation, –d[complex]_t/dt=(k_Cu[Cu²⁺]+k_H [H⁺]) [complex)_T is valid at [Cu²⁺]_T=0.01–0.1, I=0.5 and [HClO₄]=0.005 mol dm^–3. The rate measurements are reported at 30, 35, 40 and 45°C and the rate and activation parameters for the Cu²⁺ and H⁺-catalysed paths are: k_H(35°C)=(2.44±0.09)×10^–2 dm³ mol^–1 s^–1, H=83±13 kJ mol^–1, S=–8±42 JK^–1 mol^–1, k _Cu (35°C)=(3.30±0.09)×10^–3 dm³ mol^–1 s^–1, H=73.2±6.1 kJ mol^–1, S=–55±20 JK^–1 mol^–1. The formate-bridged innersphere binuclear complex,cis-[(en)₂Co{(O₂CH)₂Cu}]³⁺ may be involved as the catalytically active intermediate in the copper(II)-catalysed path, just as the corresponding H⁺-bridged species presumed to be present in the acidcatalysed path.     

Study of complex formation between aluminum bromide and benzene by 27Al NMR spectroscopy

The reaction of aluminum bromide with benzene in n-hexane was studied by ²⁷Al NMR spectroscopy in the temperature range from –80 to +20 °C. The formation of C₆H₆·Al₂Br₆ (1 : 2) complexes is accompanied by broadening of the resonance line with 178. No peak splitting following a decrease in the temperature was observed but the temperature dependence of the line width passed through a maximum near –60 °C. A procedure for determination of the constant K for the formation of 1 : 2 complexes at –20, 0, and +20 °C based on the line broadening with an increase in the C₆H₆ : Al₂Br₆ molar ratio was proposed. The thermodynamic parameters of complex formation, G, H, and S, were calculated.     

Electronic structure of XYZ−trihalide anions (X,Y, Z = Cl,Br, I)

The electronic structures of the Cl₃ ^–, Br₃ ^–, I₃ ^–, BrCl₂ ^–, BrI₂ ^–, BrICl^–, and BrII^– anions were calculated using the discrete variational X method. These calculations showed that the adiabatic electron affinity (EA) of the corresponding trihalogen molecules is close to the vertical EA and first vertical ionization potential (IP) of the corresponding singly charged anions. The calculated first IP of all these anions are rather similar (3.3–3.8 eV). Thus, these trihalides may be considered weak superhalogens.Branch of the Institute of Chemical Physics, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 5, pp. 41–47, September–October, 1989.