Induced representations of point groups and symmetry of localized orbitals

Complete representation tables are constructed for crystallographic symmetry point-group representations induced by local subgroups. We discuss the applicability of induced representations of point groups to the analysis of symmetry and to the construction of orbitals localized on atoms and bonds in a molecule. As an example, canonical and localized orbitals in tetrahedral hydroxyanion MnO₄ ^– are considered.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 6, pp. 641–650, December, 1986.     

Activity coefficients of aqueous perchloric acid

Mean ionic activity coefficients for aqueous perchloric acid at 25°C were obtained from the emf of a HClO₄ concentration cell (m=1×10^–3–1.5) containing a ClO ₄ ^– ion solution electrode and a glass electrode. The results of an application of the Pitzer equations are compared with those previously reported from several different measuring methods. Perchloric acid activity coefficients have been calculated for the mixture HClO₄–NaClO₄. In both cases, good agreement has been obtained between our results and those derived from the isopiestic method.Deceased November 15, 1984.     

High-pressure phase equilibria for chlorosilane + carbon dioxide mixtures

Fluid-phase equilibria, including dew points, bubble points, and critical points were measured for four binary systems composed of a chlorosilane and carbon dioxide. The measurements were carried out in a constant-composition, variable-volume cell equipped with a sapphire window, which allowed visual observation of the phases in the cell. A syringe pump was used to inject the CO₂ into the cell and to control its pressure. Methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, and diethyldichlorosilane up to about 0.14 mol fraction were studied in this apparatus and a total of 243 phase-boundary points were obtained. Displacements in the critical point with respect to pure CO₂ of up to 11.81 MPa and 348.05 K were observed. Modeling of the fluid-phase equilibria for three of the four binary systems was done using the Peng–Robinson equation of state, standard van der Waals mixing rules with two binary interaction parameters, and a φ–φ formulation of the equilibrium. The binary interaction parameters were obtained by fitting the model to the experimental data. The model produced excellent agreement between computed and experimental data. Graphical representations of the modeling results are presented and compared to experimental results. The results indicate that the largest chlorosilane (diethyldichlorosilane) produced the largest shift in critical pressure and critical temperature with respect to pure CO₂.     

Determination of ratios of sulfate to bisulfate ions in aqueous solutions by Raman spectroscopy

Raman spectra are presented for aqueous ammonium bisulfate and zinc sulfate-sulfuric acid solutions over a wide range of concentration and from 20 to 85°C. The heights of the 980 cm ^–1 (primarily SO ₄ ^–2 ) and 1053 cm ^–1 (primarily HSO ₄ ^– ) bands are correlated with the pH of the solutions. The ratio of the species SO ₄ ^–2 and HSO ₄ ^– can be obtained from the ratio of scattering intensities at 980 and 1053 cm ^–1 . The H obtained from plots of the log of the concentration products versus 1/T is –37±5 kJ-mol ^–1 for ammonium bisulfate solutions and –48±4kJ-mol ^–1 for the ZnSO ₄ -H ₂ SO ₄ solutions. This compares to –22 kJ-mol ^–1 for the H of bisulfate ion dissociation as obtained from thermodynamic equilibrium constants.     

Solubility and Hydrolysis of La, Pr, Eu, Er, and Lu in 1 M NaCl Ionic Strength at 303 K

The pLn-pC _H diagrams obtained by a radiometric technique were used for the determination of the solubility and the first hydrolysis constants for La, Pr, Eu, Er, and Lu in 1 M NaCl ionic strength at 303 K. The saturation and unsaturation zones, and the borderline of precipitation were determined from these diagrams. The first hydrolysis constants were determined from pH titrations where no precipitation was found; these data were treated with the SUPERQUAD program. Fitting methods involving pLn versus pC _H and the average ligand number vs. pC _H were used to calculate both the first hydrolysis constants and the solubility products. The log K _sp values obtained for La, Pr, Eu, Er, and Lu were –19.53, –20.92, –22.24, –22.62, and –23.05 and the log* ₁ average values obtained were –8.87 ± 0.05, –8.54 ± 0.04, –8.34 ± 0.03, –8.16 ± 0.04, and –8.11 ± 0.03, respectively, under CO₂ free conditions. Finally, the results were compared with those found in the literature.     

Nucleation of Titania Nanocrystals in Silica Titania Waveguides

SiO_{2(1 – x)}-TiO_2(x) monomode waveguides at 632.8 nm, with x in the range 0.07–0.2 and thickness of about 0.4 m, were deposited on silica substrates by a dip-coating technique. Nucleation of TiO₂ nanocrystals and the growth of their size by thermal annealing up to 1300°C were studied by waveguided Raman scattering in the SiO_2(0.8)-TiO_2(0.2) composition. In the low frequency region (5–50 cm^–1) of the VV and HV polarized Raman spectra the symmetric and quadrupolar acoustic vibrations are observed. The mean size of the titania particles are obtained from the frequencies of the Raman peaks. The results are compared with those obtained from the measure of the linewidths in the X-ray diffraction spectra. Nanocrystals with a mean size in the range 4–20 nm are obtained by thermal annealing in a corresponding range of 700–1300°C.     

Osmotic coefficients of dilute aqueous solutions of unsymmetrical cobalt-amine type salts at 0°C

The osmotic coefficients of dilute aqueous solutions of [Co(pn)₃]X₃ [pn=1,2-diaminopropane and X=Cl^–, Br^– and (NO₃)^–] and [Co(tn)₃]X₃ (tn=1,3-diaminopropane and X=Cl^– and Br^–) have been measured from 0.00 to 0.02 mol-kg^–1 at 0°C by the freezing point method. The results have been compared with those obtained from the numerical integration of the Poisson-Boltzmann equation.     

Synthesis of pyridine and picolines over modified silica-alumina and ZSM-5 catalysts

In the reaction of acetaldehyde, formaldehyde and ammononia over HZSM-5 (Si/Al-280), PbZSM-5 and WZSM-5 catalysts at 420°C, 0.5 h^–1 weight hourly space velocity, the total yields of pyridine and 3-picoline obtained were 58.2, 42.8 and 78.3 wt.% based on aldehydes, respectively. In the reaction of acetaldehyde and ammonia over typical Pb–SiO₂–Al₂O₃ (20% PbO), W–SiO₂–Al₂O₃ (10% W), Pb–Cr–SiO₂–Al₂O₃ (F) and Pb–Cu–SiO₂–Al₂O₃ (E) catalysts at 420°C, 0.5 h^–1 W.H.S.V., the yields of 2- and 4-picolines obtained were 51.1, 66.1, 80.6 and 53.7 wt.%, respectively.IICT Communication No. 3421, — dedicated to Dr. A.V. Rama Rao on his 60th birthday.     

Characteristic features of decomposition of potassium pentacyano-cobaltates(III) on a bombardment with fast atoms

Mass spectra were obtained of cobalt(III) pentacyanide complexes of the K_n[Co(CN)₅X] type bombarded by fast atoms, where X = H₂O, NO₂ ^–, NO^–. The ligand elimination processes from the coordination sphere of the pentacyanides and the redox reactions of the complexes were studied.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 28, No. 2, pp. 173–176, March–April, 1992.     

Deposition behaviors and patterning of TiO2 thin films on different SAMs surfaces from titanium sulfate aqueous solution

Patterning of TiO₂ thin films was successfully obtained on different self-assembled monolayers (SAMs) in aqueous solution by micro-contact printing (μCP) method. The substrates were immersed in an aqueous solution containing titanium sulfate (Ti(SO₄)₂) and hydrogen peroxide for deposition at 80 °C. The growth rates on various surfaces were as follows: sulfonic (–SO₃H) > amino (–NH₂) > methyl (–CH₃) > hydroxyl (–OH). According to the XPS results, SAMs with the terminal groups of –SO₃H and –NH₂ were favorable for the deposition. The TiO₂ film deposited on the SAM with the terminal group of –CH₃ could be easily peeled off. Clearly, TiO₂ patterns were obtained on the prepatterned surfaces of –SO₃H/–CH₃ and –NH₂/–CH₃ SAMs. The deposition mechanism might be relevant to electrostatic interaction, Stern layer, lone pair electrons and Van der Vaals forces. The TiO₂ film was anatase after annealing at 500 °C and comprised particles with an average diameter of ca. 10 nm.     

Extraction of tungsten and rhenium by basic or neutral extractants in xylene from mineral acidic media

Extraction of WO ₄ ^2– and ReO ₄ ^– by Adogen-381, tricaprylmethylammonium chloride, Hyamine 10-X, trioctylphosphine oxide or dibenzylsulphoxide in xylene from HNO₃, HCl or H₂SO₄ acid medium was investigated. Based on the separation factors obtained, the separation of ReO ₄ ^– from WO ₄ ^2– was elucidated. ReO ₄ ^– was separated from WO ₄ ^2– in high radiochemical purity: >99.9% by three successive extractions and strippings using Adogen-381 from HCl or HNO₃ acid medium.     

Study of a bis-furaldehyde Schiff base copper(II) complex as carrier for preparation of highly selective thiocyanate electrodes

A new highly selective thiocyanate electrode based on N,N-bis-(furaldehyde)-1,2-phenylenediamine-dipicolyl copper(II) complex [Cu(II)-BFPD] as neutral carrier is described. The electrode has an anti-Hofmeister selectivity sequence: SCN^–>I^–>Sal^–>ClO₄ ^–>Br^–>NO₂ ^–>Cl^–>NO₃ ^–>SO₄ ^2–>SO₃ ^2–>H₂PO₄ ^– and a near-Nernstian potential linear range for thiocyanate from 1.0×10^–1 to 5.0×10^–6 mol L^–1 with a detection limit 2.0×10^–6 mol L^–1 and a slope of 57.5 mV decade^–1 in pH 5.0 of phosphate buffer solution at 20 °C. The response mechanism is discussed on the basis of results from A.C. impedance measurement and UV spectroscopy. The anti-Hofmeister behavior of the electrode results from a direct interaction between the central metal and the analyte ion and a steric effect associated with the structure of the carrier. The electrode has the advantages of simplicity, fast response, fair stability and reproducibility, and low detection limit. The selectivity of electrodes based on [Cu(II)-BFPD] exceeds that of classical anion-sensitive membrane electrodes based on ion exchangers such as lipophilic quaternary ammonium or phosphonium salts. Application of the electrode for determination of thiocyanate in waste water samples from a laboratory and a gas factory, and in human urine samples, is reported. The results obtained were fair agreement with the results obtained by HPLC.     

IR-Spektralanalyse von Gl?sern des Systems TeO2?V2O5

Studies of glasses and their crystalline products in the TeO₂–V₂O₅ system were made in the 1400–400 cm^–1 range. A continuous shift of the V=O-band from 1020 cm^–1 to 940 cm^–1 was found in the glasses with decreasing concentration of V₂O₅, as well as a sharp decrease in the intensity at 830 cm^–1. On the basis of the results obtained, it is concluded that with increasing TeO₂ content, the structure of the glasses is changed, caused by the breaking of the V–O–V bonds and the formation of Te–O–Te bridges.The IR-spectrum of the 2TeO₂·V₂O₅ compound in both crystalline and vitreous states was studied for the first time. The behaviour of the absorption bands is related to the structure of the glasses studied.     

Thermodynamics of formation of carnallite type double salts

The solubility of the systems RbCl–MgCl₂–H₂O, RbBr–MgBr₂–H₂O and CsBr–MgBr₂–H₂O have been investigated by the physicochemical analysis method at 25°C and formation of carnallite type double salts was established. The Pitzer model is used to calculate the thermodynamic functions needed to plot the solubility isotherms of the systems. The results obtained are in good agreement with the experimental data. The free energies of formation of carnallite and bromcarnallite type double salts from simple salts and the standard molar energies of formation are estimated.     

Reductive alkylation of p-phenylenediamine and its hydroquinone complex with ketones in presence of rhenium and palladium sulfides

Conclusions Conditions were found (150–200°, hydrogen pressure 110–150 atm, reaction time 3 h) for the reductive alkylation of p-phenylenediamine and its hydroquinone complex with acetone, butanone, and cyclohexanone in presence of Re₂S₇ or PdS as catalyst, and N,N'-diisopropyl-, N,N'-di-s-butyl-, and N,N'-dicyclohexyl-p-phenylenediamines and their hydroquinone complexes were obtained in 60–90% yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1601–1605, July, 1968.     

Synthesis and Structure of Organoantimony Peroxides

Organoantimony peroxides (Ar₂SbO)₄(O₂)₂ (Ar = Ph, p-Tol) were synthesized by oxidation of triarylantimony with hydrogen peroxide in the presence of nitrosophenol or 4-chlorophenol in an ether solution. X-ray diffraction analysis of peroxides obtained revealed that four antimony atoms have octahedral coordination and are connected via bridging oxygen atoms and two peroxide groups. The C–Sb, Sb–O_br, Sb–OO, and O–O distances are equal to 2.106–2.127, 1.958–1.974, 2.202–2.246, 1.471, 1.470 Å (Ar = Ph) and 2.086–2.139, 1.932–1.983, 2.215–2.289, 1.445–1.466 Å (Ar = p-Tol).     

Alkaloids of Stephania hernandifolia VIII. Methylhernandine

Summary A new hasubanan alkaloid with the composition C₂₀H₂₇O₆N, mp 152–153°C (ether-methanol) has been isolated from the herbStephania hernandifolia and has been called methylhernandine. The alkaloid has been shown to be identical with the methylamino alcohol obtained in the hydrolysis of hernandifoline.All-Union Scientific Research Institute of Medicinal Plants. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 455–457, July–August.     

Gas-phase combination reactions of SF4 and SF5 with F in plasmas of SF6

Reactions of both SF₄ and SF₅ with F have been studied at 295 K in a gas-flow reactor sampled by a mass spectrometer. The rate coefficient for the combination reaction of F with SF₄ to produce SF₅ was found to increase from (0.9 to 3.0)×10^–12 cm³ s^–1 when the helium bath gas number density was increased from (2 to 26)×10¹⁶ cm^–3. The values obtained here are three orders of magnitude higher than a recent estimate of the high-pressure value based on the modelling of photochemical studies. The experimental results have been compared with RRKM and master equation calculations in which a simplified Gorin model has been used to determine the structure of the transition state. These calculations show that reasonable agreement can be obtained between the experimental data and the calculation if a small (2 KJ/mol) activation energy is assumed. The rate coefficient for the reaction between SF₅ and F to produce SF₆ was found to be independent of helium bath gas number density within the range given above. The value obtained for the rate coefficient was 9×10^–12 cm³ s^–1 with an uncertainty of a factor of 2. This value is close to that of 1×10^–11 cm³ s^–1 computed from the simplified Gorin model and to the value of 1.7×10^–11 cm³ s^–1 deduced from modelling of photochemical experiments.     

On the role of solvent in complexation equilibiria. II. The acid-base chemistry of some sulfhydryl and ammonium-containing amino acids in water—acetonitrile mixed solvents

The macroscopic and microscopic acid-base chemistry of a series of sulfhydryl and ammonium-containing amino acids HS–R–NH₃ [R=–CH₂CH(COOH)–, cysteine (CYS); R=–C(CH₃)₂CH(COOH)–, penicillamine (PEN); R=–CH(COOH)CH₂CH₂CONHCH(–CH₂)CONHCH₂COOH, glutathione (GSH)] was characterized in water and its binary mixtures with acetonitrile (16.3, 34.2, and 53.9 mass % acetonitrile). Macroscopic acid dissociation constants were obtained by potentiometric titration using the glass-calomel electrode pair. Microscopic acid dissociation constants were calculated from ultraviolet absorption measurements at ca. 232 nm where the deprotonated sulfhydryl group absorbs. The macroscopic constants decrease uniformly as the solvent becomes enriched in acetonitrile. The microscopic constants, which characterize the relative concentrations of the two monoprotonated tautomers of the molecules (I and II) reveal that as the solvent becomes enriched in acetonitrile, the fraction of molecules existing as highly charged tautomer I decreases for CYS (0.68–0.40), PEN (0.85–0.34), and GSH (0.61–0.30). These results are related to the decreasing concentration of water as the solvent becomes enriched in acetonitrile.