Crystal structure and mechanism of (Z)-1-[2-(phenyl-bromide-chloride)vinyl]-1-cyclohexanol

The crystal structure and mechanism of the title molecule are described. This crystal is orthorhombic, belonging to space group PC21/B with a=1,002 1(2) nm, b=1.483 0(3) nm, c=2.173 6(4) nm, V=3.230 39(2) nm(3), Z=2, D-c=1.80 g/cm(3), R=0.069 3. The structure was solved by direct method. The tin atom of the title compound exists in two distorted-trigonal-bipyramidal geometry, defined by two carbon, one bromide, one chloride and one oxygen atoms leading to a five-membered chelate ring. In the structure, the five-membered ring containing the intermolecular O-->Sn has a half chair conformation.

The transfer of chloride ion across an anion exchange membrane

The transfer of chloride ions into a low resistance anion exchange membrane (AEM) was investigated by cyclic voltammetry (CV) and electrochemical impedance spectra. In all cases, concentration polarization of Cl- ions is exterior to the membrane. It controls the flux and produces the limiting currents: either steady state or transient (peak type) current. In CV experiments, when the size of the holes in the membrane was much smaller than the distance between membrane holes, the Cl- anion transfer showed steady state voltammetric behavior. Each hole in the membrane can be regarded as a microelectrode and the membrane was equivalent to a microelectrode array in this condition. When the hole in the membrane was large or the distance between membrane holes was small, the CV curve of the Cl- anion transfer across the membrane showed a peak shape, which was attributed to linear diffusion. In AC impedance measurement, the impedance spectrum of the membrane system was composed of two semicircles at low DC bias, corresponding to the bulk characteristics of the membrane and the kinetic process of ion transfer, respectively. The bulk membrane resistance increases with increasing DC bias and only one semicircle was observed at higher DC bias. The parameters related to kinetic and membrane properties were discussed.

The miscibility of homopolymer random copolymer blends .4. Poly(vinylidene chloride-co-acrylonitrile) poly(methyl methacrylate) blends

The miscibility of blends of poly(vinylidene chloride-co-acrylonitrile) (VDC-AN) and poly(methyl methacrylate) (PMMA) has been studied with DSC, FT-IR, and NMR methods. The results indicate that the VDC-AN/PMMA blends are miscibile on a molecular level, and the dipole-dipole interactions between C=O and C-Cl-2 and/or interpolymer hydrogen bondings between COOCH3 and CN and CCl groups play the role on the miscibility of the blends. It is found that the -CCl2- groups have two different chemical environments in the pure VDC-AN copolymer, which may result from the different configurations of the copolymer, such as -CCl2- groups in the ''alternating'' segments and -CCl2- groups in the ''blocky'' segments as proposed. It is the -CCl2- group in the ''alternating'' segment that takes part in the dipole-dipole interaction with C=O group in PMMA.

Structure and thermal properties of vinylidene chloride/acrylics copolymers

A series of vinylidene chloride (VDC) copolymers with methyl acrylate (MA) or butyl acrylate (BA) as comonomer (not more than 10%) was prepared by free-radical suspension copolymerization. The effects of comonomer structure, copolymer composition, and reaction condition (such as polymerization temperature on crystallinity) and thermal properties (such as melting temperature and decomposition temperature) were investigated. All VDC/acrylics copolymers studied here are semicrystalline and have more than one crystalline structure. The melting temperature of MA/VDC copolymers is decreased progressively with increase in MA content. The decomposition temperature of MA/VDC copolymers is slight increased gradually with increase in MA content. MA/VDC copolymers have lower melting temperature compared with BA/VDC copolymers with same VDC composition. The melting temperature of VDC copolymers increases with increase in polymerization temperature and decomposition temperature of those is almost independent of polymerization temperature. (C) 1996 John Wiley & Sons, Inc.

Barrier properties of vinylidene chloride copolymers

The permeability coefficients of a series of copolymers of vinylidene chloride (VDC) with methyl acrylate (MA), butyl acrylate (BA) or vinyl chloride (VC) (as comonomer) to oxygen and carbon dioxide have been measured at 1.0 MPa and 30 degrees C, while those to water vapor have been measured at 30 degrees C and 100% relative humidity. All the copolymers are semicrystalline. VDC/MA copolymers have lower melting temperature compared with VDC/BA copolymers, while that melting temperature of VDC/VC copolymer is higher than that of VDC/acrylate copolymers with the same VDC content. The barrier property of the copolymers is predominantly controlled by crystallite, free volume fraction, and cohesive energy. The permeability coefficients of VDC/MA copolymers to oxygen, carbon dioxide, and water vapor were successfully correlated with the ratio of free volume to cohesive energy.

Preparation of Pb-Ca-Na master alloy using molten chloride salt electrolysis

An electrolysis technique for co-deposition of Ca2+ and Na+ at the liquid lead cathode was put forward. The experiment was carried out at an electrolysis temperature below 650 degrees C and had a current efficiency of 98%, which are respectively 100 similar to 300 degrees C lower and 15% similar to 30% higher than those reported both at home and abroad.

Relationship between the dissolution behaviours and current efficiencies of La, Ce, Pr and Nd in their chloride molten salts

The dissolution behaviours of La and Nd in their chloride molten salts were studied by means of the see-through cell, electrochemical weak polarization and quantum chemistry (extended Huckel molecular orbital). The reasons for the low current efficiencies of rare earth metals and the difference between La and Nd in their own chloride electrolytes on the basis of the solubility, rate of dissolution, and existing state of the metals dissolved as well as the structure of the melts, are discussed.

ELECTROOXIDATION OF A CHLORIDE COMPLEX OF PLATINUM(II) AT A GLASSY-CARBON ELECTRODE

The electro-oxidation of PtCl42- was studied on a glassy carbon (GC) electrode. A Pt(IV) complex was formed on the electrode surface through coordination to the oxygen atom of an oxide functional group on the electrode, which results in its deactivation. The ferri/ferrocyanide redox couple was used as a probe to examine the activity of the GC electrode. X-ray photoelectron spectroscopy was employed to characterize the platinum on the electrode surface, and showed that the oxidation state of the Pt element changes depending on the electrochemical treatment of GC electrode. The platinum complex on the surface of the GC electrode can be transformed to Pt-0 by cycling the electrode between -0.25 and +1.65 V/SCE in 0.1 M H2SO4 solution. The above procedure can be used to disperse platinum ultramicroparticles on the surface of a GC electrode.

INHIBITION OF CORROSION BY HEXADECYL TRIMETHYL AMMONIUM BROMIDE LANGMUIR-BLODGETT MONOLAYERS ON CARBON-STEEL

Langmuir-Blodgett (LB) monolayers of hexadecyl trimethyl ammonium bromide (HTAB) were deposited onto a carbon steel surface to investigate the inhibition of corrosion by measurement of the polarization resistance and cyclic voltammetry. The corrosion proc

ELECTROCHEMICAL AND IN-SITU SPECTROELECTROCHEMICAL STUDY OF (TETRAPHENYLPORPHINATO)MANGANESE(III) PERCHLORATE IN THE PRESENCE OF CHLORIDE ANIONS .2. OXIDATION PROCESSES

An investigation of electrode oxidation processes of (tetra-phenylporphinato) manganese (III) Perchlorate, (TPS)Mn(III)ClO4, was carried out during the titration of chloride anions by conventional cyclic voltammetry, thin-layer cyclic voltammetry and spectroelectrochemistry. It was demonstrated that in the presence of one equivalent amount of Cl-, the first one electron oxidation reaction corresponds to the Mn(III)I cation radical oxidation, and the second one electron oxidation corresponds to the cation radical/dication generation followed by an iso-porphyrin formation reaction, however in the presence of two equivalent amount of Cl-, the first one electron oxidation of Mn(III) gives Mn(IV) porphyrin and the second one electron oxidation generates cation radicals of Mn(IV) followed by an iso-porphyrin formation reactions. Mechanisms of these redox processes are postulated.

ELECTROCHEMICAL FORMATION OF NI-Y INTERMETALLIC COMPOUND LAYER IN MOLTEN CHLORIDE

The reduction of Y(III) ions in molten chloride is known to be a one-step three electron reaction [1, 2, 3], but a voltammogram of YCl3 in molten LiCl-KCl-NaCl at a nickel electrode shows at least two reduction peaks of Y(III) ions, indicating the possibility of formation of Ni-Y intermetallic compounds. Using a galvanostatic electrolysis method, samples were prepared at several current densities at 450, 500, 600 and 700-degrees-C, respectively, and were identified with X-ray diffraction (XRD) and electron probe microanalysis (EPMA) methods. The results show that Ni2Y, Ni2Y3 and NiY can be produced by electrolysis and Ni2Y is found to be the predominant Ni-Y intermetallic compound under the experimental conditions. Nickel appears to diffuse in Ni2Y faster than yttrium, and the diffusion process is the rate determining step during Ni2Y formation.

AN INFRARED SPECTROSCOPIC STUDY ON THE STRUCTURAL PHASE-TRANSITIONS OF LAURYLAMMONIUM CHLORIDE

Infrared spectroscopy was used to study the structural phase, transitions of laurylammonium chloride in the temperature range from 290 to 365K. It was shown that there is a solid-solid phase transition at 339 K with a pre-transition at 327 K. The infrared spectra indicated that virgin crystals at room temperature form a well-ordered phase with all-trans hydrocarbon chains, and the lengths of N-H...Cl hydrogen bonds are different. The spectra suggested that the gauche conformers begin to appear at temperature above 327 K. The spectra at high temperature over 339 K demonstrated that the interaction between the chains decreases, the partial ''melting'' of the chains is obvious, and the hydrogen bonds (N-H...Cl) have the same lengths. The main transition and pre-transition are mainly assigned to the intramolecular and intermolecular order-disorder changes, respectively.

AN INFRARED SPECTROSCOPIC CHARACTERIZATION OF THE SOLID SOLID BEHAVIOR OF DODECYLAMMONIUM CHLORIDE

The infrared spectra of the bilayer system dodecylammonium chloride has been studied as a function of temperature. Unusual splitting of some vibrational modes helps us to characterize the structure of different solid states. This study provided the evidence for the occurrence of an order-disorder phase transition whose onset occurs at 327 K and its completion ends at 339 K. In the low temperature phase below 327 K, the virgin crystals form a well-ordered phase with all-transhydrocarbon chains. In the intermediate state between 327 and 339 K, the data demonstrate the introduction of intramolecular as well as intermolecular disorder. The coexistence of solid and liquid-crystal-like states is shown by the persistence of factor group splittings together with the existence of defect bands in the wide intermediate temperature range. In the high temperature phase over 339 K the crystals convert to a liquid-crystal-like system with extensive motional and conformational disorder, but still show characteristics in their infrared spectra which indicate the presence of ordered segments in the hexagonal solid phase.

THE COMPATIBILITY AND CRYSTALLIZATION OF THE MIXTURES OF POLY (TETRAHYDROFURAN-b-METHYL METHACRYLATE) DIBLOCK COPOLYMER WITH POLYVINYL CHLORIDE HOMOPOLYMER

The compatibility and crystallization behaviour of the mixtures of poly (tetrahydrofuran-methyl methacrylate) diblock copolymer (PTHF-b-PMMA) with polyvinyl chloride has been studied. We found that the compatibility of these blends, in which there is special interaction between the homopolymer and the PMMA block of the copolymer, is much better than that of the AB/A type blends; and that the crystallization rate and crystallinity of PTHF microdomain changed greatly due to the swollen by PVC homopolymer. In this paper, these changes in cryatallization are well explained according to the theories of block copolymer blends and the density gradient model presented by JIANG Ming.

SYNTHESES AND X-RAY STRUCTURES OF BIS(T-BUTYLCYCLOPENTADIENYL)LANTHANIDE CHLORIDE COMPLEXES [(BU(T)CP)2LNCL]2 (LN = PR, GD, ER)

Reaction of lanthanide trichlorides with two equivalents of sodium t-butylcyclopentadienide in THF gave rise to the bis(t-butylcyclopentadienyl)lanthanide chloride complexes [(Bu(t)Cp)2LnCl]2 (Ln = Pr, Gd, Er), which were characterized by elemental analysis, IR and H-1 NMR spectroscopy. In addition, the crystal structures of [(ButCp)2PrCl]2 (1) and [(ButCp)2GdCl]2 (2) were determined by single crystal X-ray diffraction at room temperature. The coordination number for Pr3+ and Gd3+ is 8 and the bond lengths Pr-Cl and Gd-Cl are 2.864(2) and 2.771(3) angstrom, respectively. The structural studies showed the complexes to have C2h symmetry.