Temperature dependence of apparent molar volumes and viscosity B-coefficients of amino acids in aqueous potassium thiocyanate solutions from 15 to 35°C

Precise density and viscosity data at 15, 25 and 35°C for solutions of glycine, DL-alanine, L-threonine, -alanine, -aminobutyric acid and -aminocaproic acid in water and in (1m, 3m, 5m) aqueous potassium thiocyanate were measured and the limiting apparent molar volumes V ^o and the B-coefficients calculated. The V ^o and B values were split into the contributions from the NH ₃ ⁺ ,COO^– and CH₂ groups. These data are rationalized on the basis of hydrophillic and hydrophobic interactions between the various groups present in these solutions.Abstracted from the Ph.D Thesis of R. K. Goyal, University of Delhi, 1990.     

Effects of some admixtures on the decomposition of calcium sulphate

The by-product phosphogypsum contains CaHPO₄, H₃PO₄, Ca₅(PO₄)₃F, Al₂O₃, Fe₂O₃, SiO₂ etc. besides the main product CaSO₄. By means of TG-DTA the thermochemical decomposition of pure phosphogypsum and phosphogypsum containing CaO, Al₂O₃, Fe₂O₃ and SiO₂ in a reductive atmosphere was studied. The solid phase was examined by high-temperature thermomicroscopy, scanning electronmicroscopy, X-ray diffraction and other methods. It could be confirmed, that most of the admixtures undergo secondary reactions with CaO and CaS, modifying the decomposition rate of CaSO₄.

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Zusammenfassung Das Abfallprodukt Phosphatgips enthält neben dem Hauptbestandteil CaSO₄ noch CaHPO₄, H₃PO₄, Ca₅(PO₄)₃F, Al₂O₃, Fe₂O₃, SiO₂ und anderes. Die thermochemische Zersetzung von Phosphatgips bzw. Phosphatgips mit Zusätzen von CaO, Al₂O₃, Fe₂O₃ und SiO₂ wurde in reduzierender Atmosphäre mittels TG-DTA untersucht. Die feste Phase wurde durch Hochtemperatur-Thermomikroskopie, Rasterelektronenmikroskopie, Röntgenbeugung und andere Methoden untersucht. Dabei wurde bestätigt, dass die meisten Beimengungen mit dem Calciumoxid bzw. -sulfid Sekundärreaktionen eingehen, wodurch auch die Zersetzungsgeschwindigkeit des CaSO₄ beeinflusst wird.

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, , ₄, Ca₅(PO₄)₃F, Al₂O₃, Fe₂O₃, SiO₂ . - , , , . , , . , , .

     

Hydrogenation of CO on thoria supported group VIII (Pd, Pt, Ir) metal catalysts

Comparative studies of the transformation of CO/H₂ mixtures on Pd supported (MgO, Al₂O₃, ThO₂) catalysts reveal the promoting effect of thoria, particularly towards hydrocarbon products.

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CO/H₂ Pd MgO, Al₂O₃ ThO₂ ThO₂, .

     

Hydrodewaxing studies over a pentasil ferrisilicate zeolite

The catalytic dewaxing of an atmospheric gas oil has been carried out over Pt-loaded catalysts containing a ferrisilicate zeolite of the ZSM-5 structure. It is observed that the mode of incorporation of the metallic function has a profound effect on the activity on the catalyst. Further, the use of alumina (instead of bentonite) as binder increases the activity of the catalyst.

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, ZSM-5. , . , ( ) .

     

Thermodynamics of 2,2′,2′'-terpyridinecopper(II) complexes in aqueous solution

Summary The thermodynamic quantities relative to the protonation and the complexation of 2,2,2'-terpyridine with copper(II) ion have been determined at 25° and I=0.1 mol dm^–3 (NaNO₃). The G data was obtained by potentiometric measurements; a copper selective electrode was employed for the study of the complexation equilibria. The H values have been determined by direct calorimetry.The hydrolytic species, existing at pH>6 and their relative G and H values have also been obtained.From the thermodynamic data the importance of enthalpy and entropy terms in stabilizing the complexes is assessed.Moreover some considerations on the chelating effect are reported.Presented in part at 2 Congresso Nazionale di Chimica Analitica, Catania (1977).     

Interactions of Some Amino Acids with Aqueous Tetraethylammonium Bromide at 298.15 K: A Volumetric Approach

The apparent molar volumes, V_,2, of glycine, L-alanine, DL--amino-n-butyric acid, L-valine, and L-leucine have been determined in aqueous 0.25, 0.75, 1.0, and 1.5 mol-dm^–3 tetraethylammonium bromide (TEAB) solutions by density measurements at 298.15 K. These data have been used to calculate the infinite dilution apparent molar volumes, V_2,m, for the amino acids in aqueous tetraethylammonium bromide and the standard partial molar volumes of transfer (_tr V_2,m) of the amino acids from water to the aqueous salt solutions. The linear correlation of V_2,m for a homologous series of amino acids has been utilized to calculate the contribution of the charged end groups (NH₃⁺, COO^–), CH₂ group, and other alkyl chains of the amino acids to V_2,m. The results of the standard partial molar volumes of transfer from water to aqueous tetraethylammonium bromide have been interpreted in terms of ion–ion, ion–polar, and hydrophobic–hydrophobic group interactions. The volume of transfer data suggest that ion–ion or ion–hydrophilic interactions are predominant in the case of glycine and alanine, and hydrophobic–hydrophobic group interactions are predominant in the case of DL--amino butyric acid, L-valine, and L-leucine.     

Reaction of triphenyl phosphite ozonide with thioacetals

Kinetic regularities in the reaction of triphenyl phosphite ozonide with several thioacetals in CH₂Cl₂ solution at –15°C have been studied. The consumption rate of ozonides is described by the kinetic equation W=k₀[(C₆H₅O)₃P·O₃]+k₁[(C₆H₅O)₃P·O₃][R₁R₂C(SR₃)₂] Rate constants k₀ and k₁ for the thioacetals: (CH₃H₇S)₂CH₂, (C₆H₅S)₂CH₂, (C₆H₅CH₂S)₂CH, (n=C₁₂H₂₅–S)₂CH₂, (C₃H₇S)₂C(H)CH₃, (C₃H₇S)₂C(H)C₆H₅, (C₃H₇S)₂C(CH₃)C₆H₅ and (C₃H₇S)₂C(H)C₁₀H₉, increases with increasing the electron-donating power of subtituents R_i.

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CH₂Cl₂ –15°C. : W=k₀[(C₆H₅O)₃P·O₃]+k₁[(C₆H₅O)₃P·O₃][R₁R₂C(SR₃)₂] k₀ k₁ (C₃H₇S)₂CH₂, (C₆H₅S)₂CH₂, (C₆H₅CH₂S)₂CH₂, (n-C₁₂H₂₅S)₂CH₂, (C₃H₇S)₂C(H)CH₃, (C₃H₇S)₂C(H)C₆H₅, (C₃H₇S)₂C(CH₃)C₆H₅, (C₃H₇S)₂C(H)C₁₀H₉. .

     

51V NMR studies of a system vanadium pentoxide-potassium pyrosulfate

Two states of pentavalent vanadium in the system K₂S₂O₇–V₂O₅ have been found by the⁵¹V NMR method. For state 1 a polynuclear structure with greater distorted local environment compared with V₂O₅ is retained. For state 2 the nearest environment of vanadium differs significantly from V₂O₅, and is probably characterized by the higher ionic nature of the vanadium-oxygen bond.

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⁵¹V K₂S₂O₇–V₂O₅ . V₂O₅. , V₂O₅ , , -.

     

Effect of the Reaction Products on the Rate of Oxidation of Crotonaldehyde

Study of the oxidation of crotonaldehyde revealed an appreciable inhibitory effect of the products on the process. Analysis of the kinetic data obtained over a wide range of reaction conditions (c ₀ 1.5-3.3 M, pO₂ 1-16 atm, T 293-309 K) showed that the overall oxidation process (with account taken of the inhibitory effect of the products) is described by the equation: W _CA = k*_ap c _CA (pO₂)^0.6 (1 + 0.17c _CA)^{- 1}, where k*_ap is the apparent rate constant, and c _CA is the decrease of the aldehyde concentration by a moment .     

The electronic structure of molecules by a many-body approach

The vertical valence ionization potentials of cyclopropane, ethylene oxide and ethylene imine are calculated by a many-body Green's function method. For C₃H₆ the ordering of the ionization potentials is 2e(), 1e(), 2a₁(), 1a₂(), 1e(). The assignment of the 2a₁ and the 1a₂ ionization potentials which has been controversial is thus clarified. The ordering is in agreement with the result obtained via Koopmans' theorem. For ethylene oxide and ethylene imine Koopmans' theorem fails in predicting the correct order of ionic states. For C₂H₄O the ordering of the ionization potentials is 2b ₁(), 4a ₁, 1a ₂(), 2b ₂,3a ₁, 1b ₁(), 1b ₂, 2a ₁ and for C₂H₅N 6a, 5a, 3a, 2a, 4a, 3a, 1a, 2a. The agreement of the computed ionization potentials with the experimental values is very satisfactory.     

Temperature dependence of CO insertion on S-, Ag-, and Cu-promoted Rh/SiO2 catalysts

The addition of sulfur and silver to Rh/SiO₂ inhibits hydrogenation of C₂H₄, but promotes CO insertion and extends the linearity of Arrhenius curves for CO insertion above 543 K.

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Rh/SiO₂ C₂H₄, CO CO 543 .

     

Synthesis of antigenic bacterial polysaccharides and their fragments

Conclusions The free trisaccharide-D-mannopyranosyl(1-4)--L-rhamnopyranosyl(1 3)-D-galactopyranose was obtained, which is the repeating unit of the backbone chain of the O-specific polysaccharides ofSalmonella of serological groups A, B, and D₁.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No.1, pp.165–167, January, 1976.     

Decomposition of N2O over CuxMg1?xAl2O4 catalysts

The results show that there is not difference between the catalytic activities of two series of Cu_xMg_1–xAl₂O₄ catalysts, despite a small but significant difference in cation distribution. The activity is mainly affected by the presence of CuO.

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, , , , - Cu_XMg_1–XAl₂O₄. CuO.

     

Thermal decomposition of the solvent-extracted chloro complexes of vanadium(IV) with trioctylamine and trioctylmethylammonium chloride

The complexes (R₃NHVO(OH)Cl₂)₂ and (R₃RNVO(OH)Cl₂)₂ prepared by drying in vacuo the organic solutions from the extraction into benzene of aqueous vanadyl chloride solution with trioctylamine (TOA, R₃N) and trioctylmethylammonium chloride (TOMAC, R₃RNCl), were studied by thermogravimetry and differential thermal analysis under an atmosphere of nitrogen, and the products of their thermal decomposition, such as volatile matter and residues, by gas chromatography. X-ray diffraction and infrared spectroscopy. It was found that the complexes with TOA and TOMAC thermally decompose to V₂O₃ at 200–300° by cracking of the compounds R₃NHVO(OH)Cl₂ and R₃RNVO(OH)Cl₂ formed via dissociation of the complexes at about 150°.

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Zusammenfassung Die Komplexe (R₃NHVO(OH)Cl₂)₂ und (R₃RNVO(OH)Cl₂)₂ wurden hergestellt, indem benzolische und wässrige Vanadylchlorid-Lösungen mit Trioctylamin (TOA, R₃N) und Trioctylmethylammoniumchlorid (TOMAC, R₃RNCl) extrahiert und die erhaltenen Lösungen im Vakuum eingedampft wurden. Die Komplexen wurden in Stickstoffatmosphäre mittels TG und DTA untersucht und die thermischen Zersetzungsprodukte, und zwar sowohl die flüchtigen Verbindungen als auch die Rückstände, gaschromatographisch bzw. röntgendiffraktometrisch und IR-spektroskopisch bestimmt. Es wurde festgestellt, daß die Komplexe mit TOA und TOMAC bei 150° in die Verbindungen R₃NHVO(OH)Cl₂ und R₃RNVO(OH)Cl₂ dissoziieren, die bei 200–300° thermisch zu V₂O₃ zersetzt werden.

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(R₃NHVO(OH)Cl₂)₂ (R₃RNVO(OH)Cl₂)₂ (R₃,) ( , R₃RNCl). , , . , 200–300° V₂₃ R₃NV()l₂ R₃RNVO(OH)Cl₂, 150°.

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We wish to thank the Koei Chemical Co. Ltd. for samples of TOA and TOMAC.     

A novel method for the preparation of extensively dealuminated faujasites

Open structure faujasites may be dealuminated with retention of crystallinity using phosgene (or similar reactants) provided the sample has been made ultrastable in a previous procedure.

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( ) . .

     

Zusammenhang zwischen den K α-Satelliten-Linien und den Röntgenübergängen vom Typ K 1 L 1→L 2 bei den Elementen Neon,Natrium, Magnesium,Aluminium und Silizium

Zusammenfassung Für die Elemente Neon, Natrium, Magnesium, Aluminium und Silizium werden mit einem quantenmechanischen Variationsverfahren unter Verwendung einer minimalen STF-Funktionenbasis Röntgenübergänge vom Typ K ¹L¹L² berechnet und den K -Satellit-Linien , , ₃, ₃ and ₄ zugeordnet.

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Relation between K -Satellits and X-ray-transitions of the type K ¹ L ¹L ² for Ne, Na, Mg, Al and Si

STF-Calculations are reported for X-ray-transitions of the type K ¹L¹L² for Ne, Na, Mg, Al and Si. It is shown that these transitions are correlated with the K -satellits , , ₃, ₃ and ₄.

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Die Wellenfunktionen können auf Anfrage zur Verfügung gestellt werden.     

Structure of vanadium phosphate anion in solutions from17O,51V and31P NMR data

¹⁷O,⁵¹V and³¹P NMR studies indicate that the anion structure of sodium vanadophosphate in an aqueous solution is close to that in crystals of the (CN₃H₆)₈HPV₁₄O₄₂ 7H₂O salt.

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¹⁷O,⁵¹V,³¹P , (CN₃H₆)₈HPV₁₄O₄₂ 7H₂O.

     

The Properties of Mixtures of Sodium Dodecylsulfate and Diethylsulfoxide in Water

The aqueous mixtures of sodium dodecylsulfate (SDS) and diethylsulfoxide (DESO) have been studied using conductivity, viscosity and surface tension techniques. The critical micellar concentration (cmc) was determined in the presence of DESO at 30, 40, and 50 C from conductance and surface tension measurements. The enthalpy ( G_m), entropy ( S_m) and Gibbs energy ( G_m) of micellization were determined from the temperature dependence of the cmc. The results obtained were compared with published results for aqueous solutions of SDS and dimethylsulfoxide (DMSO). The data demonstrate a more pronounced inhibitory effect of DESO on the micellization of SDS, in comparison with the effect of DMSO. On the basis of the dependences of the relative viscosities on concentration, as given by the Jones–Dole semi-empirical equation, the B-coefficients have been calculated for the post-micelle composition region.     

Kinetic study of the thermal dehydration of layered [Ni2Al(OH)6]2SO4.nH 2O

The kinetics of thermal dehydration of [Ni₂Al(OH)₆]₂SO₄.nH₂O has been studied through the analysis of isothermal weight loss data. The results obtained seem to indicate that the process is governed by a diffusion mechanism up to an value which is dependent on the temperature. An explanation is provided for this behaviour on the basis of the structural properties of the compound and the nature of the water loss.

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Zusammenfassung Die Kinetik der thermischen Dehydratisierung von [Ni₂Al(OH)₆]₂SO₄.nH₂O wurde mittels isothermer TG untersucht. Die Ergebnisse scheinen darauf hinzudeuten, daß der Prozeß bis zu einem von der Temperatur abhängigen -Wert von einem Diffusionsmechanismus bestimmt wird. Für dieses Verhalten wird basierend auf den strukturellen Eigenschaften der Verbindung und der Natur der Wasserabgabe eine Erklärung gegeben.

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, [Ni₂Al(OH)₆]₂SO₄.nH₂O. , , . , .