Gamma radiolysis of toluene and deuterated toluenes—I. Isotopic exchange

The γ radiolysis of liquid toluene and toluene-d₈ was studied at 50°C. For toluene, product yields were 0.14 molecules of hydrogen, 0.006 of methane, 0.090 of biphenyl and 0.9 of “polymer” for each 100 eV absorbed. For toluene-d₈, these yields are lower by a factor of two to three. Radiolysis of mixtures of toluene and toluene-d₈ shows a disproportionately high decomposition of the light toluene, suggesting that energy initially absorbed in toluene-d₈ transfers to toluene before decomposition occurs.Deuterium tracer studies indicate that about 14% of the hydrogen arises from unimolecular processes, whereas none of the methane or bibenzyl arises in this way. Studies using an electron scavenger, ethyl bromide, and a proton scavenger, ethanol, showed that the hydrogen yield did not likely have long-lived electrons or ions as precursors. Thus the energy transfer from toluene-d₈ to toluene is probably by direct excitation transfer, and not by charge transfer.     

Association of stereoregular poly(methyl methacrylates) in dilute solution. Proton NMR study

By measurement of integrated intensities of high-resolution proton nuclear magnetic resonance (NMR) bands, associated structures of isotactic (i) and syndiotactic (s) poly(methyl methacrylate) (PMMA) in dilute toluene-d₈ and dimethylformamide-d₇ solutions were detected and characterized. In 1% (w/v) solutions of highly stereoregular s-PMMA in toluene-d₈ at 27°C, 76% of the monomer units are present in the form of compact aggregates. Consequences of this finding for the polymerization of methyl methacrylate in toluene in the presence of s-PMMA are discussed.     

Kinetics and mechanism of the oxidation of arenes in the presence of heteropoly acids and palladium(II) complexes supported on silica gel

Pd(II) complexes and twelfth-series heteropoly acids (HPA) H₉[PMo₆V₆O₄₀] and H₃[PMo₁₂O₄₀] supported on silica gel oxidize benzene and toluene at 95°C. The formation of methyldiphenylmethane in the oxidation of toluene on HPA/SiO₂ and (PdCl₂−HPA)/SiO₂ catalysts, KIE>1 for the toluene/toluene-d₈ pair, and greater rate for toluene than for benzene are in accord with a one-electron transfer mechanism. L. M. Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of Ukraine, 70 R. Lyuksemburg ul., Donetsk 340114, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 35, No. 4, pp. 249–252, July–August, 1999.     

Multiple quantum NMR spectra of toluene and p‐bromotoluene partially aligned in a nematic phase

¹H multiple quantum (MQ) NMR spectra of toluene and p‐bromotoluene, partially aligned in a liquid crystalline solvent, were acquired using gradient‐assisted methods. The MQ spectra were analysed to give the dipolar couplings (D_ij) and these were used to determine the molecular shape and average orientation of the of the spin systems. Copyright © 2003 John Wiley & Sons, Ltd.     

Factors affecting the sorption of Eu(III) on modified silica gel</p> </p>

Summary 8-Hydroxyquinoline in benzene, xylene, chloroform and toluene diluents was used to modify silica gel as a solid phase extractant (SPE) for the sorption of Eu(III) in batch extraction techniques. Influences of solid/liquid ratio, pH, metal ion concentration, particle size and temperature were studied. The optimum initial pH is 4.2, while the maximum sorption capacities for the prepared impregnated resins in benzene, xylene, chloroform and toluene diluents are 18.52, 14.98, 14.79 and 5.94 mg ^. g^-1, respectively. The sorption process is found to be affected by both metal ion concentration and particle size of the impregnated resin. Thermodynamic parameters for the sorption of Eu(III) were determined and the reaction is found to be exothermic and spontaneous with enthalpy-14.23 and-23.71 kJ ^. mol^-1 for benzene and xylene as diluents. Release of the element from the loaded solid particles into 0.01M HNO₃ is@85% and@53% from 8-HQ/benzene/silica gel and 8-HQ/xylene/silica gel.</p> </p>     

A new phosphor with flower-like structure and luminescent properties of Sr<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript>: Eu<Superscript>2+</Superscript>, Dy<Superscript>3+</Superscript> long afterglow materials by sol–gel method

The flower-like phosphors of Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ with high brightness and long afterglow were obtained by sol–gel method. X-ray diffraction pattern (XRD) shows that single-phased Sr₂MgSi₂O₇ phosphor is prepared by sol–gel method under 1250 °C. Scanning electron microscope (SEM) indicates that the phosphor consists of nano-sized whiskers which are detected for the first time in Eu²⁺ and Dy³⁺ co-doped long-lasting phosphorescence silicates. Furthermore, the investigation on the mechanism indicates that the internal structure and gas, liquid and solid phase effect play important roles in the formation of flower-like Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ nanostructure. Finally, the optical properties of flower-like Sr₂MgSi₂O₇ nanostructure have been characterized by photoluminescence (PL) spectra.     

Formation and properties of the Fe<Subscript>8</Subscript>V<Subscript>10</Subscript>W<Subscript>16–x</Subscript>Mo<Subscript>x</Subscript>O<Subscript>85</Subscript> type solid solution

Solid solution phases of a formula Fe₈V₁₀W_16–xMo_xO₈₅ where 0≤x≤4, have been obtained, possessing a structure of the compound Fe₈V₁₀W₁₆O₈₅. It was found on the base of XRD and DTA investigations that these solution phases melted incongruently, with increasing the value of x, in the temperature range from 1108 (x=0) to 1083 K (x=4) depositing Fe₂WO₆ and WO₃. The increase of the Mo⁶⁺ ions content in the crystal lattice of Fe₈V₁₀W₁₆O₈₅ causes the lattice parameters a=b contraction with cbeing almost constant. IR spectra of the Fe₈V₁₀W_16–xMo_xO₈₅ solid solution phases have been recorded.     

Heat capacity at constant pressure and thermodynamic properties of phase transitions in PbMO<Subscript>3</Subscript> (<Emphasis Type="Italic">M</Emphasis>=Ti,Zr and Hf)

The heat capacity of PbMO₃ (M=Ti, Zr and Hf) at constant pressure was measured using a differential scanning calorimeter (DSC) from room temperature up to 870 K. Large anomalies were found in the heat capacity curves, corresponding to the ferroelectricparaelectric phase transition in PbTiO₃ (PT), the antiferroelectric-paraelectric phase transitions in PbZrO₃ (PZ) and PbHfO₃ (PH). The transition entropies were estimated as 7.3 J K⁻¹ mol⁻¹ (PT), 9.9 J K⁻¹ mol⁻¹ (PZ) and 9.3 J K⁻¹ mol⁻¹ (PH). These values of transition entropies are much larger than that of a typical displacive-type phase transition.     

Studies on tetraborane(8) carbonyl, B4H8·CO: its isomeric composition in the gas phase and in solution, and its reactions with alkenes

¹¹B NMR spectra of tetraborane(8) carbonyl, B₄H₈·CO 1, reveal a changeover in the distribution of isomers in going from toluene solution to the gas phase. Fortuitously the distribution is 60:40 in each case, but comparison with published electron diffraction data and ab initio/IGLO computations indicates that the CO group is disposed endo with respect to the B₄ `butterfly' framework in the predominant isomer in the gas phase, and exo in solution. The results also allow conclusions to be drawn about the geometries of other B₄H₈·L isomers on the basis of their reported proton NMR chemical shifts. Reactions of B₄H₈·CO with ethene and propene at ca. 30 bar yield products, R₄B₄H₄·CO (R=Et 2 or Pr³ 3), in which all four wingtip hydrogen atoms of the tetraborane carbonyl have been replaced by alkyl groups. Variable-temperature ¹¹B and ¹H NMR spectra of 2 and 3 reveal interesting fluxional behaviour.     

Vibrational spectra of WO3·nH2O and WO3 polymorphs

Vibrational spectra of polycrystalline WO₃ hydrates and polymorphs were measured and analyzed. The effect of sampling techniques on IR spectra has been demonstrated. The phase transition into triclinic polymorph (C⁵_2 h → C¹_i) has been revealed for the sample of monoclinic WO₃ prepared as KBr pellet. Using the deuteration method in situ has shown that cubic WO₃ is non-stoichiometric oxide stabilized by residual OH groups of WO₃·H₂O precursor.     

Generation of fullerenyl radicals and chemiluminescence in the (C<Subscript>60</Subscript>—R<Subscript>3</Subscript>Al)—O<Subscript>2</Subscript> system

Fullerenyl radicals (FR) RC₆₀ ^· and chemiluminescence (CL) are generated in the presence of O₂ in C₆₀—R₃Al (R = Et, Buⁱ) solutions in toluene (T = 298 K). The FR are formed due to the addition of the R^· radical, which is an intermediate of R₃Al autooxidation, to C₆₀. Mass spectroscopy and HPLC were used to identify Et_nC₆₀H_m (n, m = 1–6), Et_pC₆₀ (p = 2–6), and dimer EtC₆₀C₆₀Et as stable products of FR transformations. As found by ESR, the EtC₆₀ ^· radical (g = 2.0037) is also generated by photolysis of solutions obtained after interaction in the (C₆₀— R₃Al)—O₂ system. In the presence of dioxygen, the FR is not oxidized but yields complexes with O₂, which appear as broadening of the ESR signals. Chemiluminescence arising in the (C₆₀—R₃Al)—O₂ system is much brighter (I _max = 1.86·10⁸ photon s⁻¹ mL⁻¹) than the known background CL (I _max = 6.0·10⁶ photon s⁻¹ mL⁻¹) for the autooxidation of R₃Al and is localized in a longer-wavelength spectral region (λ_max = 617 and 664 nm). This CL is generated as a result of energy transfer from the primary emitter ³CH₃CHO* to the products of FR transformation: R_nC₆₀H_m, R_pC₆₀, and EtC₆₀C₆₀Et. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 205–213, February, 2007.     

Infrared intensities of liquids XXII: Optical and dielectric constants, molar polarizabilities, and integrated intensities of liquid benzene-d6 at 25 °C between 5000 and 450 cm–1

This paper presents accurate infrared absorption intensities of liquid benzene-d₆ at 25?°C, between 5000 and 450 cm^–1. The results are presented as graphs and tables of the real, n, and imaginary, k, refractive index spectra, which are also called the optical constant spectra. The real refractive index is shown between 8000 and 450 cm^–1. The absolute errors in the k values are estimated to be ～3% below, and up to 60%, above, 4700 cm^–1, with those in the n values ～0.25% throughout. The Beer-Lambert molar absorption coefficient spectra, E _m(?ν), and the complex dielectric constant spectra, ?′(?ν) and ?″(?ν), were calculated from the optical constant spectra. To correct for macroscopic dielectric effects, the complex molar polarizability spectra, α′_m(?ν) and α″_m(?ν), were calculated from the dielectric constant spectra under the Lorentz local field. The properties of bands in these different spectra are compared. The imaginary molar polarizability spectra were fitted convincingly to 208 Classical Damped Harmonic Oscillator bands, and the areas under the corresponding ?να″_m bands gave the integrated intensities C _j . These were assigned as far as possible and are tabulated. The transition dipole moments of well assigned transitions, and for the infrared-active fundamentals, under the double harmonic approximation, the dipole moment derivatives with respect to the normal coordinates, were calculated from the values of C _j , and are presented. This appears to be the first extensive measurement of the infrared absorption intensities of liquid benzene-d₆. The results are compared with literature data for liquid and gaseous benzene-d₆.     

NMR relaxation study of the phase transitions and relaxation mechanisms of the alums MCr(SO4)2·12H2O (M=Rb and Cs) single crystals

The physical properties and phase transition mechanisms of MCr(SO₄)₂·12H₂O (M=Rb and Cs) single crystals have been investigated. The phase transition temperatures, NMR spectra, and the spin-lattice relaxation times T₁ of the ⁸⁷Rb and ¹³³Cs nuclei in the two crystals were determined using DSC and FT NMR spectroscopy. The resonance lines and relaxation times of the ⁸⁷Rb and ¹³³Cs nuclei undergo significant changes at the phase transition temperatures. The sudden changes in the splitting of the Rb and Cs resonance lines are attributed to changes in the local symmetry of their sites, and the changes in the temperature dependences of T₁ are related to variations in the symmetry of the octahedra of water molecules surrounding Rb⁺ and Cs⁺. We also compared these ⁸⁷Rb and ¹³³Cs NMR results with those obtained for the trivalent cations Cr and Al in MCr(SO₄)₂·12H₂O and MAl(SO₄)₂·12H₂O crystals.     

Synthesis and assembly of ultrathin film of Ni(OH)2 nanoparticles at gas/liquid interface, its high electrocatalytical oxidation toward bio-thiols and selective determination of cysteine

A facile strategy was reported to synthesize and assemble a stable ultrathin film of Ni(OH)₂ nanoparticles at gas/liquid interface where the aqueous phase contained Ni²⁺ and the organic phase was composed of triethylamine toluene solution. The ultrathin film of Ni(OH)₂ nanoparticles that precipitated at the interface was transferred onto the electrode surface for the electrocatalysis of bio-thiols and selective electroanalysis of cysteine. The preparation of Ni(OH)₂ ultrathin film and its transfer to an electrode substrate is very simple. The obtained Ni(OH)₂ ultrathin film modified electrodes are stable, showing high electrochemical oxidation toward bio-thiols and good selectivity toward cysteine in phosphate buffered solution of pH 7.5.     

Aqueous sol–gel processing of precursor oxides for ZrW<Subscript>2</Subscript>O<Subscript>8</Subscript> synthesis

This paper describes the synthesis of ZrW₂O₈ by the use of an aqueous citrate-gel method in order to prepare a fine, pure and homogeneous oxide mixture suitable for ceramic processing. The thermal expansion coefficient thus obtained for α-ZrW₂O₈ is −10.6 × 10⁻⁶ °C⁻¹ (50–125 °C) whereas for the β-ZrW₂O₈ a value of −3.2 × 10⁻⁶ °C⁻¹ (200–300 °C) is obtained. The advantages of the use of a sol–gel method is expressed in the very homogeneous end-products. The paper describes crystallographic data, morphological structure and the thermal expansion properties of the ZrW₂O₈ material. Moreover, photoluminescence and photochromic properties specific to the precursor gel are described and analyzed. These effects support our views that the precursors show homogeneity up to nanometer level.     

Effect of nanoscale CeO<Subscript>2</Subscript> on PVDF-HFP-based nanocomposite porous polymer electrolytes for Li-ion batteries

New poly (vinylidenefluoride-co-hexafluoro propylene) (PVDF-HFP)/CeO₂-based microcomposite porous polymer membranes (MCPPM) and nanocomposite porous polymer membranes (NCPPM) were prepared by phase inversion technique using N-methyl 2-pyrrolidone (NMP) as a solvent and deionized water as a nonsolvent. Phase inversion occurred on the MCPPM/NCPPM when it is treated by deionized water (nonsolvent). Microcomposite porous polymer electrolytes (MCPPE) and nanocomposite porous polymer electrolytes (NCPPE) were obtained from their composite porous polymer membranes when immersed in 1.0 M LiClO₄ in a mixture of ethylene carbonate/dimethyl carbonate (EC/DMC) (v/v = 1:1) electrolyte solution. The structure and porous morphology of both composite porous polymer membranes was examined by scanning electron microscope (SEM) analysis. Thermal behavior of both MCPPM/NCPPM was investigated from DSC analysis. Optimized filler (8 wt% CeO₂) added to the NCPPM increases the porosity (72%) than MCPPM (59%). The results showed that the NCPPE has high electrolyte solution uptake (150%) and maximum ionic conductivity value of 2.47 × 10⁻³ S cm⁻¹ at room temperature. The NCPPE (8 wt% CeO₂) between the lithium metal electrodes were found to have low interfacial resistance (760 Ω cm²) and wide electrochemical stability up to 4.7 V (vs Li/Li⁺) investigated by impedance spectra and linear sweep voltammetry (LSV), respectively. A prototype battery, which consists of NCPPE between the graphite anode and LiCoO₂ cathode, proves good cycling performance at a discharge rate of C/2 for Li-ion polymer batteries.     

Solubility of sulphur dioxide in aqueous electrolyte solutions at higher ionic strengths—Chloride and bromide containing systems

The absorption of sulphur dioxide in chloride and bromide containing electrolyte solutions was measured up to ionic strengths of 5 mol/dm³. The thermodynamic equilibrium of the gas phase and the liquid phase was characterized by UV spectroscopy. UV spectra analysis gave strong evidence for SO₂X⁻ complexes existing in the solutions. Consequently, these compounds were implemented in the reaction scheme for absorption.     

Kinetics of graft copolymerization of methyl methacrylate onto polychloroprene with tricaprylylmethylammonium chloride as a phase‐transfer catalyst

The phase‐transfer catalyzed graft copolymerization of methyl methacrylate onto polychloroprene was carried out using tricaprylylmethylammonium chloride as a phase‐transfer catalyst in a two‐phase system of an aqueous Na₂S₂O₈ solution and toluene at 55 °C under a nitrogen atmosphere. The initial rate of graft copolymerization was expressed as the combined terms of quaternary onium cation and peroxydisulfate anion in the aqueous phase rather than the fed concentrations of catalyst and Na₂S₂O₈. The observed initial rate of graft copolymerization was used to analyze the graft copolymerization mechanism with a cycle phase‐transfer initiation step in the heterogeneous liquid–liquid system. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3543–3549, 2000     

A Theoretical Study of the Interaction Between Cytosine and BX<Subscript>3</Subscript> (X = F,Cl) Systems

The B3LYP method of DFT and HF theories of ab initio with 6-311+G^** basis sets were used to predict the geometries of the cytosine-BX₃ (X,=F, Cl) complex systems. Four conformers were obtained with no imaginary frequencies, respectively. The binding energies, enthalpies and Gibbs energies of cytosine-BX₃ have been obtained. The analyses of the combinations between cytosine and BX₃ using the natural bond orbital (NBO) method and thermodynamics indicate that the complexes (a) and (e), which depend on the proton affinities of the oxygen on the cytosine and boron in BX₃, are the most stable ones with their combination energies of −234.21 and −228.23 kJ.mol⁻¹ (B3LYP method, BSSE corrected). Based on the calculation results, a reasonable method was employed to calculate the change in the enthalpies and Gibbs energies to form eight complexes in the gaseous state at 298.15K and 101.325 kPa. It can be shown that the conformers (a) and (e) are the most stable and form readily.