Mechanism and kinetics of thermal decomposition of precipitates of the zinc oxide-aluminium oxide system from non-isothermal tg curves

Kinetics of decomposition of the precipitates of the ZnO&2sbndAl₂O₃ system, prepared by coprecipitation and mechanical mixing of the individual precipitates, have been studied. The decomposition of zinc basic carbonate is a first order rate process with an activation energy of 34.5 kcal/mole (Coats and Redfern equation). The decomposition of aluminium hydroxide is also best described as a first order rate process with one break in the Coats and Redfern plot corresponding to activation energies of 29.4 and 8.3 kcal/mole respectively. The entire course of decomposition of coprecipitated as well as mechanically mixed samples cannot be described by any one of the many rate equations available. Consequently, the Coats and Redfern equation has been employed. The plots indicate one or two breaks and thus two to three values of activation energy are reported. From the results it is to be concluded that decomposition of these precipitates is a heterogeneous process. The first step is definitely the decomposition of zinc basic carbonate followed by decomposition of aluminium hydroxide and/or interaction of the two precipitates resulting in the formation of “precursor” to spinel. The results of our earlier investigation on the same system (especially the formation of precursors) are well supported by the results reported in this investigation. p]A new equation (a modified form of the Elovich equation) has been proposed for such heterogeneous decomposition processes. The proposed equation also appears to be the general form of the equations where diffusion is the rate controlling process.     

On the optical properties of the imidazolium ionic liquids

Room-temperature ionic liquids, particularly those based on substituted imidazolium cations, are currently being extensively studied for a variety of applications. Herein, we explore the suitability of several imidazolium salts in optical applications by carefully examining the electronic absorption and fluorescence behavior of these substances, generally believed to be transparent in most of the UV region and fully transparent in the visible region. It is shown that all imidazolium ionic liquids are characterized by significant absorption in the entire UV region and a long absorption tail that extends into the visible region. These absorption characteristics are attributed to the imidazolium moiety and its various associated structures. When excited in the UV or early part of the visible region, these liquids exhibit fluorescence, which covers a large part of the visible region and shows dramatic excitation wavelength dependence. The excitation wavelength dependent shift of the fluorescence maximum has been rationalized taking into consideration the existence of the various associated structures of the ionic liquids and the inefficiency of the excitation energy-transfer process between them. The results imply that these liquids may have serious drawbacks in some of the optical studies.     

IR-Spektren einiger Doppeloxide des Typs Te3MIVO8

I.R. Spectra of Some Double Oxides of the Type Te₃M^IVO₈ The infrared spectra of the phases Te₃M^IVO₈ (M^IV = Ti, Zr, Hf, Sn), structurally related to fluorite, have been recorded and discussed. It is shown that all the observed have a complex origin, and it is not possible to assign them to definite vibrations of the metal-oxygen polyhedra present in the lattices.     

Magnesium perchlorate as an efficient catalyst for the synthesis of imines and phenylhydrazones

Magnesium perchlorate has been found to be an efficient catalyst for the synthesis of imines and phenylhydrazones by the reaction of carbonyl compounds with amines and phenylhydrazine in high yields at room temperatures and in short times. The condensation of less electrophilic carbonyl compounds with poorly nucleophilic amines affords the imines in excellent yields.     

ZrCl4 as a new and efficient catalyst for the opening of epoxide rings by amines

Zirconium(IV) chloride catalyses the nucleophilic opening of epoxide rings by amines leading to the efficient synthesis of β-amino alcohols. The reaction works well with aromatic and aliphatic amines in short times at room temperature in the absence of solvent. Exclusive trans stereoselectivity is observed for cyclic epoxides. Aromatic amines exhibit excellent regioselectivity for preferential nucleophilic attack at the sterically less hindered position during the reaction with unsymmetrical epoxides. However, in case of styrene oxide, selective formation of the benzylic amine was observed during the reactions with aromatic amines.     

Polarized infrared and Raman spectra of CsHSeO4 and CsDSeO4 single crystals

The polarized absorption infrared spectra of CsHSeO₄ and CsDSeO₄ single crystals and polarized Raman spectra of the CsHSeO₄ single crystal were measured at room temperature. The polarization features of the internal vibrations of the HSeO⁻₄ ions are predicted on the basis of the X-ray structure assuming strong couping between the vibrations of the two shortest Se---O bonds and an intermediate Se---O bond. The bending methods γOH and δOH of a hydrogen bond appear at 805 cm⁻ and 1258 cm⁻¹, respectively. The νOH absorption has the ABC structure due to Fermi resonance of νOH with the overtones of the δOH and γOH vibrations. A similar shape of the νOH band is observed in the Raman spectra. The νOD absorption has a different shape from that of νOH. Intra-chain coupling was observed for the νOH and νOD vibrations.     

Vinylation and polymerization with trivinylaluminum. I. Vinylation of organic halides as a model for termination in cationic polymerization leading to vinyl end groups

An improved synthesis of trivinylaluminum (V₃Al) is described. The proton magnetic resonance (PMR) spectrum of V₃Al was recorded and analyzed. A new vinylation method involving the use of V₃Al as the vinylating agent has been developed, and the vinylation of organic halides by V₃Al was studied at ?30, ?50 and ?70°C. Primary alkyl chlorides, such as methyl and methylene chloride, do not react with V₃Al and were used as solvents. Secondary chlorides such as 2-chloropropane also do not react. t-Butyl chloride gives rise to t-butylethylene (70–98%), depending on reaction conditions, and the allylic chlorides, 3-chloro-1-butene, and 3-chloro-3-methyl-1-butene, yield the expected vinylated products and their isomers (～90%). Allyl and benzyl chloride do not react under the conditions tried. The reaction between V₃Al and the ditertiary dichloride 2,6-dichloro-2,6-dimethylheptane yields several isomeric C₁₃H₂₄ and C₁₁H₂₀ hydrocarbons; however, surprisingly, C₉H₁₆ does not form. The C₁₃ hydrocarbons arise by divinylation at the termini of the dichloride, while the C₁₁ hydrocarbons are formed by vinylation at one and proton elimination at the other terminus of the dichloride. The presence of unsaturated C₁₃H₂₄ and C₁₁H₂₀ isomers is most likely due to proton induced isomerization. These results are explained by a proximity effect involving vinylation at one end of the dichloride by V₃Al followed by rapid reaction of the second chlorine (mostly) by V₂AlCl generated in situ during the first vinylation in the proximity of the chloride. At the other chlorine terminus V₂AlCl causes either a second vinylation (leading to C₁₃ hydrocarbons) or a proton elimination (leading to C₁₁ hydrocarbons). The absence of C₉H₁₆ among the reaction products indicates that V₃Al exclusively effects vinylation. The RCl + V₃Al ← RV + V₂AlCl reaction may be regarded as a model for initiation followed by immediate termination in cationic olefin polymerization, a process leading to vinyl-ended polymers.     

Das Schwingungsspektrum von Magnesium-orthovanadat

The infrared and laser-Raman spectra of crystalline Mg₃(VO₄)₂ are reported and a factor group analysis for the full lattice is presented to support the discussion. The 1,000 to 600 cm^?1 region of the spectrum is essentially related to internal (stretching) modes of the greatly distorted VO₄ tetrahedra, whereas the bands in the low frequency region must be assigned to complex vibrations originating in the interaction of the bending vibrations of the tetrahedral groups with the external modes.     

Speciation of arsenic in body fluids

Inorganic arsenic is metabolized by consecutive reduction and methylation reactions to dimethylated arsenic (DMA), and then excreted into the urine mostly in the form of DMA. Therefore, arsenic metabolites in the body fluids and organs/tissues are present in the form of inorganic (arsenite and arsenate) and methylated arsenics (MMA and DMA). Although pentavalent arsenics can be present mostly in the form of free ions, trivalent ones may be present more in the forms conjugated with thiol groups of glutathione (GSH) or proteins. Arsenic in the body fluids (plasma, bile and urine) is present in the soluble forms and can be speciated on ion exchange columns by HPLC with on-line detection by an inductively coupled argon plasma-mass spectrometer (ICP-MS). Free forms of arsenite, arsenate, and monomethylarsonous, monomethylarsonic, dimethylarsinous and dimethylarsinic acids in the body fluids have been demonstrated to be speciated simultaneously within 10 min or so on both anion and cation exchange columns together with arsenobetaine (AsB) and arsenocholine (AsC). Trivalent arsenics conjugated with GSH were eluted in intact forms on an anion exchange column but were liberated into free forms on a cation exchange column. Thus, free and GSH-conjugated arsenic metabolites in the bile and urine have been speciated simultaneously on ion exchange columns by HPLC-ICP-MS.     

Vibrational spectra of the adduct of 1,8-bis(dimethylamino)naphthalene with dichloromaleic acid (DMAN x DCM)

The infra-red (IR), Raman (R) and inelastic incoherent neutron scattering (IINS) spectra, particularly in low frequency region, of the title ionic adduct were studied. It is shown that all low frequency vibrations (below 200 cm(-1)) of (CH3)2N groups of protonated 1,8-bis(dimethylamino)naphthalene (DMAN)--clearly observed in IINS spectra--are sensitive to the environment, i.e. to the type of counterion forming short contacts with C-H bonds of methyl groups. The internal frequencies were also calculated by ab initio method. The results are consistent with numerous observations of the counteranion effect on the geometry of the protonated DMAN. The conclusions are compared with structural and NMR studies reported recently for the 1,8-bis(dimethylamino)naphthalene with dichloromaleic acid (DMAN x DCM) adduct. The single crystal R polarized spectra taken over the frequency range 20-3200 cm(-1) were analyzed in detail. We have shown that a substantial difference in the IR spectrum of the dichloromaleic acid (DCM) anion in the DMAN adduct and in the potassium salt results from different geometries of OHO hydrogen bonds. In the case of potassium salt the chains of longer intermolecular hydrogen bonds are formed described by means of a double minimum potential.