Quantitative Estimation of Ruthenium(III) Using Morpholine-4-Carbodithioate as a New Analytical Reagent

Ruthenium(III) has been precipitated gravimetrically in the pH range 7.0-8.5 with morpholine-4-carbodithioate and determined by weighing as a black complex (C₅H₆ONS₂)₃ Ru after drying at l00–110°C. The interference of the various metal ions has been avoided by using an ammonical mixture of EDTA and tartrate (1:1 molar ratio). The complex is thermally stable up to l60°C.     

Thermochemistry of C60 and C70 fullerene solvates

In an effort to improve understanding of dissolution behaviour of fullerenes and their simple chemical derivatives the binary systems of C₆₀, C₇₀ and the piperazine monoadduct of [60] fullerene C₆₀ N₂C₄H₈ with a series of aromatic solvents have been studied by means of DSC. In certain systems solid solvates have been found to be the thermodynamically stable phases relative to saturated solution at room temperature. Identified solid solvates were characterized by their compositions, temperatures and enthalpies of incongruent melting transitions. The regularities in thermodynamic stability of the solvated crystals have been discussed along with dissolution properties of fullerenes and the derivative. Certain correlations have been observed.     

Synthesis of di‐ and tetra‐adducts by addition of polystyrene macroradicals onto fullerene C60

Br‐terminated polystyrenes of controlled molar masses and low polydispersities prepared by atom transfer radical polymerization (ATRP) can be converted to macroradicals using an appropriate catalytic complex (CuBr/bipyridine/100 °C). The addition of this macroradicals PS° to 6–6 bonds of C₆₀ follows a specific atom transfer radical addition mechanism that favors the grafting of even number of chains onto the fullerene core. This peculiar mechanism, resulting from the properties of C₆₀, offers an easy synthetic route toward well‐defined di‐ and tetra‐adducts. In these adducts the disturbance of the electronic structure of the fullerene is kept at its minimum, as only one double bond needs to be opened on the C₆₀ to add two PS chains and only two double bonds are converted to single bonds in the tetra‐adduct. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3456–3463, 2004     

Crystal structures of chloroform solvates of fullerenes

The chloroform solvates of C₆₀ and C₇₀ fullerenes and of the C₆₀/C₇₀ mixture were synthesized and investigated by X-ray powder diffraction.     

Improvement of thermal and mechanical properties of poly(L‐lactic acid) with 4,4‐methylene diphenyl diisocyanate

In this study, the thermal and mechanical properties of biodegradable poly(L ‐lactic acid) (PLA) were improved by reacting with 4,4‐methylene diphenyl diisocyanate (MDI). The resulting PLA samples were characterized with Fourier transformation infrared spectrometer (FT‐IR). The glass transition (T_g) and decomposing (T_d) temperature of the resulting products were measured using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. The tensile properties were also measured with a tensile tester. The results show that when the molar ratio of ? NCO to ? OH was 2:1, the T_g value can be increased to 64°C from the original 55°C, and the tensile strength increased from 4.9 to 5.8 MPa. This demonstrated that by reacting PLA with MDI at an appropriate portion, both the thermal and mechanical performance of PLA can be increased. Copyright © 2006 John Wiley & Sons, Ltd.     

Separation and characterization of products from thermal cracking of individual and mixed polyalkenes

Low-density polyethylene (LDPE), polypropylene (PP), and their mixture in the mass ratio of 1: 1 (LDPE/PP) were thermally decomposed in a batch reactor at 450°C. The formed gaseous and oil/wax products were separated and analyzed by gas chromatography. The oils/waxes underwent both atmospheric and vacuum distillation. Densities, molar masses and bromine numbers of liquid distillates and distillation residues were determined. The first distillate fraction from the thermally decomposed LDPE contained mostly linear alkanes and alk-1-enes ranging from C₆ to C₁₃ (boiling point up to 180°C). The second distillate fraction was composed mostly of hydrocarbons C₁₁ to C₂₂ (boiling point up to 330°C). 2,4-Dimethylhept-1-ene was the major component of the first distillate fraction obtained from the product of PP decomposition, while in the 2nd distillate fraction it was 2,4,6,8-tetramethylundec-1-ene. The yields of some gaseous or liquid hydrocarbons obtained by distillation from thermally degraded LDPE/PP differed from the values corresponding to the decomposition of individual plastics due to the mutual influence of polyalkenes during their thermal cracking. Similarly, the yields of propene and methylpropene in the gaseous phase were higher in the case of mixture. Whereas the content of C₉ to C₁₇ alkanes and alkenes in the distillates separated from the liquid mixture obtained by the decomposition of LDPE/PP decreased, the formation of 2,4,6,8,10,12-hexamethylpentadec-1-ene remained unchanged. The corresponding mechanisms of thermal cracking were discussed.     

Simultaneous thermoanalytical investigations of (C6H5)4AsCl and (C6H5)4PCl under air and argon atmospheres

The thermoanalytical curves of (C₆H₅)₄AsCl (I) and (C₆H₅)₄PCl (II) were generated simultaneously by using a Netzsch simultaneous thermal analyser 409 under static air and dynamic argon atmospheres. The ranges of thermal stability of I and II were found to be 145–310°C and 137–365°C, respectively, and their melting points to be 261 and 278°C. The DTA profiles of I and II differ and can be used for their distinction.     

Characterization of layered double hydroxide Mg-Al-CO<Subscript>3</Subscript> prepared by re-hydration of Mg-Al mixed oxide

Emanation thermal analysis, differential thermal analysis, thermogravimetry, X-ray diffraction, scanning electron microscopy (SEM) and surface area and porosity determination from nitrogen adsorption/desorption measurements were used to characterize the Mg-Al-CO₃ LDH compound with the Mg:Al ratio 3:1 prepared by re-hydration of the Mg-Al mixed oxide. The mixed oxide was obtained after heating of the intial Mg-Al-CO₃ LDH compound in air at 500°C for 2 h. The samples were re-hydrated by two ways namely in a distilled water at 20°C for 5 days or by moistening at 60°C in air with RH 80% during 10 days, respectively. The characteristics of the re-hydrated LDH samples were compared with the initial Mg-Al-CO₃ compound. The influence of the re-hydration conditions on the microstructure, surface morphology and thermal stability of the regenerated Mg-Al-CO₃ LDHs samples is discussed. It was demonstrated that the re-generation of the layered structure by the hydration of the mixed oxide in water or in air, respectively, took place via the dissolution-crystallization mechanism and that the layered double hydroxide with different surface area and thermal behavior were formed after re-hydration in water or humid air, respectively. The emanation thermal analysis revealed differences in the microstructure changes of the re-hydrated sample during heating. XRD patterns and results of the methods used supported the ETA results.     

Highly active zirconium(IV) catalyst containing sterically hindered hydridotris(pyrazolyl)borate ligand for the polymerization of ethylene

The synthesis and characterization of the novel zirconium (IV) tris(pyrazolyl)borate compound {Tp^Ms*}ZrCl₃ ( 1 ) (Tp^Ms* = hydridobis(3‐mesitylpyrazol‐1‐yl)(5‐mesitylpyrazol‐1‐yl)), as well as its performance in polymerizing ethylene are described. The reaction of ZrCl₄ with 1 equivalent of TlTp^Ms* in toluene at room temperature affords 1 as a white solid in 62% yield. Compound 1 in the presence of MAO showed remarkable productivity using a low Al : Zr molar ratio (6.79×10⁴ kg of PE/(mol Zr·h·[C₂H₄]); toluene, 60°C, Al/Zr = 100). Under identical polymerization conditions, compound 1 and Cp₂ZrCl₂ showed comparable productivities. Compound 1 displayed similar productivities at temperatures in the range of 0–75°C and noticeable productivity at 105°C. The viscosity‐average molecular weight of the polyethylenes depends on the Al : Zr molar ratio and polymerization temperature and varied between 1.09 and 8.98×10⁵ g·mol^–1.     

Effect of synthesis temperature and molar ratio of organic lithium salts on the properties and electrochemical performance of LiFePO4/C composites

LiFePO₄/C cathode materials were synthesized through in situ solid-state reaction route using Fe₂O₃, NH₄H₂PO₄, Li₂C₂O₄, and lithium polyacrylate as raw materials. The precursor of LiFePO₄/C was investigated by thermogravimetric/differential thermal analysis. The effects of synthesis temperature and molar ratio of organic lithium salts on the performance of samples were characterized by X-ray diffraction, scanning electron microscopy, electrochemical impedance spectra, cyclic voltammogram, and constant current charge/discharge test. The sample prepared at optimized conditions of synthesis temperature at 700 °C and molar ratio with 1.17:1 exhibits excellent rate performance and cycling stability at room temperature.     

Thermal behaviour of synthetic pyroaurite-like anionic clay

Thermal behaviour of synthetic pyroaurite-like anionic clay with molar ratio Mg/Fe=2 was studied in the range of 60-1100°C during heating in air. TG/DTA coupled with evolved gas analysis, emanation thermal analysis (ETA), surface area measurements, XRD, IR and Mössbauer spectroscopy were used. Microstructure changes characterized by ETA were in a good agreement with the results of surface area measurements and other methods. After the thermal decomposition of the pyroaurite-like anionic clay, which took place mainly up to 400°C, a predominantly amorphous mixture of oxides is formed. A gradual crystallization of MgO (periclase) and Fe₂O₃ (maghemite) was observed at 400-700°C by XRD. The MgFe₂O₄ spinel and periclase were detected at 800-1100°C. The spinel formation was also confirmed by Mössbauer spectroscopy.     

EDTA assisted sol–gel synthesis of ZrW2O8

A novel sol–gel synthetic route using water-soluble precursor salts is presented as a synthetic path for a high-purity negative thermal expansion material, ZrW₂O₈. This synthetic route involves a sol–gel method with the use of EDTA as complexing agent. The aqueous solution is transformed into a ceramic material after a two-step heat treatment: gelation at 60 °C and reactive sintering at 1,180 °C. The decomposition of the gel is monitored with infrared spectroscopy and TGA. The high-temperature heat treatment results in ZrW₂O₈ with its characteristic negative thermal expansion behaviour α_{[75–130 °C]}: −9.8 ± 1.6 μm/m °C and α_{[175–300 °C]}: −1.2 ± 0.2 μm/m °C.     

A Thermochemical Study on the Formation of Oxalato-Titanium(III) Complex

The thermometric titration of titanium(III) chloride with oxalic acid was carried out at 25°C. The molar ratio of titanium (III): oxalate was found to be 1:2, which indicates the formation of Ti(C₂O₄)₂⁻ ion in acid media. The limiting value of the heat of reaction between Ti(III) ion and oxalic acid in hydrochloric acid solution was found to be −1.5 Kcal mole⁻¹ at 25°C.     

C60-C70-C6H5CH3 crystal solvates: Structure and thermal stability

Differential scanning calorimetry (DSC) and X-ray diffraction were used to study the thermal stability and structure of C₆₀-C₇₀-C₆H₅CH₃ crystal solvates synthesized at room temperature. The decomposition of the crystal solvates generates C₆₀-C₇₀ solid solutions with hexagonal close-packed (hcp) structure.     

A Thermal Decomposition Study of Individual and Co-Precipitated Y, Ba and Cu Oxalates

Y-Ba-Cu oxalate powder with a presumed Y:Ba:Cu molar ratio of 1:2:4 was prepared by a modified co-precipitation method and its solid-phase thermal decomposition was studied from 25 to 1000°C, the major evolved gases being H₂O and CO₂. The air-dried powder contained residual moisture. It required isothermal heat treatment for elimination of the evolved gases. The melting point of the co-precipitation Y-Ba-Cu oxalate powder, determined by DSC at a heating rate of 10°C min⁻¹ was approximately 882°C in N₂, 949°C in air and about 979°C in O₂. The dependence of the sintering properties of this material upon the atmosphere and the temperature is considered. This revised version was published online in August 2006 with corrections to the Cover Date.     

Controlled radical polymerization of styrene mediated by the C‐phenyl‐N‐tert‐butylnitrone/AIBN pair: Kinetics and electron spin resonance analysis

Kinetics of the free radical polymerization of styrene at 110 °C has been investigated in the presence of C‐phenyl‐N‐tert‐butylnitrone (PBN) and 2,2′‐azobis(isobutyronitrile) (AIBN) after prereaction in toluene at 85 °C. The effect of the prereaction time and the PBN/AIBN molar ratio on the in situ formation of nitroxides and alkoxyamines (at 85 °C), and ultimately on the control of the styrene polymerization at 110 °C, has been investigated. As a rule, the styrene radical polymerization is controlled, and the mechanism is one of the classical nitroxide‐mediated polymerization. Only one type of nitroxide (low‐molecular‐mass nitroxide) is formed whatever the prereaction conditions at 85 °C, and the equilibrium constant (K) between active and dormant species is 8.7 × 10^?10 mol L^?1 at 110 °C. At this temperature, the dissociation rate constant (k_d) is 3.7 × 10^?3 s^?1, the recombination rate constant (k_c) is 4.3 × 10⁶ L mol^?1 s^?1, whereas the activation energy (E_a,diss.), for the dissociation of the alkoxyamine at the chain‐end is ～125 kJ mol^?1. Importantly, the propagation rate at 110 °C, which does not change significantly with the prereaction time and the PBN/AIBN molar ratio at 85 °C, is higher than that for the thermal polymerization at 110 °C. This propagation rate directly depends on the equilibrium constant K and on the alkoxyamine and nitroxide concentrations, as well. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1219–1235, 2007     

Transformations of xylenes in trimethylammonium hydrochloride—Aluminum chloride ionic liquid

Isomerization of m-, o-and p-xylenes in the presence of trimethylammonium hydrochloride-AlCl₃ ionic liquid with different composition was studied. Ionic liquids with the following ammonium salt: AlCl₃ molar ratios were used: 1∶2, 1∶1.5 and 1∶1.25. It was shown that isomerization of xylenes proceeds under mild conditions at temperatures from 60°C to 110°C. It was found that the activity and selectivity of the ionic liquids depends on their composition. The most effective catalyst was the ionic liquid with the ammonium salt: AlCl₃ molar ratio equal to 1∶2.     

Polymerization of methyl methacrylate by a charge transfer mechanism with urea and iron (III) complex

Methyl methacrylate (MMA) can be polymerized by a charge transfer complex formed by the interaction of urea, methyl methacrylate, and carbon tetrachloride (CCl₄) in a nonaqueous solvent like dimethylsulfoxide (DMSO). The rate of polymerization can be accelerated by Lewis acids like Fe³⁺. This article reports the polymerization of MMA initiated by urea and CCl₄ and accelerated with hexakisdimethylsulfoxide iron (III) perchlorate, [Fe(DMSO)₆](ClO₄)₃, and A at 60°C. Definite induction periods were observed for the polymerization reaction initiated by urea and CCl₄ alone, but the induction period completely vanished when the molar ratio of urea to A reached 6:1. The molecular weights of the polymers with 6:1 molar ratio of urea to A were higher than with urea alone. The rate constant for the polymerization of MMA in the presence of [Fe(urea)₆]³⁺ was 1.03 × 10^?5 1 mol^?1 s^?1 at 60°C. The transfer constant for CCl₄ for polymerization with urea alone is 2.43 × 10^?3 at 60°C.     

Urease-Dextran complexes with enhanced enzymatic activity and stability

In this study, the urease-dextran non-covalent complexes in various molar ratios were synthesized and compared to the free enzyme in terms of pH, temperature, thermal and storage stabilities. Especially, the complex with a molar ratio of n_U/n_DA = 40/1 showed highest thermal stability and had ca. 1.4-fold at 25°C and 2.5-fold at 80°C higher activity than the free enzyme. The complex showed a high catalytic activity in organic solvent. In addition, the thermal and storage stabilities of urease were improved greatly as dextran complex, which has advantages for usage in practice.     

Synthesis of Gold Nanosheets through Thermolysis of Mixtures of Long Chain 1‐Alkylimidazole and Hydrogen Tetrachloroaurate(III)

Micron‐sized gold nanosheets were produced through thermolysis of a mixture composed of 1‐octa‐decanylimidazole (C₁₈‐im) and HAuCl₄ in a molar ratio of 4:1 at 200 °C for 1 h. Effects of the molar ratio of [₁₈‐im]/[HAuCl₄], the reaction temperature, and the N‐alkylimidazole chain length were studied. Adjusting the molar ratio of [C₁₈‐im]/[HAuCl₄] can tune the morphology and size of the nanostructures; the effect of reaction temperature is minimum; while using long chain imidazole tends to favor the formation of nanosheets, using 1‐methylimidazole (C₁‐im) produces micron‐sized polyhedra. The growth mechanism of these nanostructures was proposed. C₁₈‐im functions both as a templating and capping agent and favors the growth of nanosheets. On the other hand, C¹‐im functions only as a capping agent and thus favors the formation of polyhedra, especially octahedra.