Integral isobaric heat of vaporization of benzene-1,2-dichloroethane system

Abstract is not available.

Thermodynamic properties of the system toluene-1,2-dichloroethane

Data on heats of mixing at 30 'C, vapor-liquid equilibrium, latent heats of vaporization at 686 mmHg, and vapor pressures for the system toluene-l,2-dichloroethane are presented.

Unimolecular HCl elimination from 1,2-dichloroethane: A single pulse shock tube and ab initio study

Thermal decomposition of 1,2-dichloroethane (1,2-DCE) has been studied in the temperature range of 10501175 K behind reflected shock waves in a single pulse shock tube. The unimolecular elimination of HCl is found to be the major channel through which 1,2-DCE decomposes under these conditions. The rate constant for the unimolecular elimination of HCl from 1,2-dichloroethane is found to be 10(13.98+/-0.80) exp(-57.8+/-2.0/RT) s(-1), where the activation energy is given in kcal mol(-1) and is very close to that value for CH3CH2Cl (EC). Ab initio (HF and MP2) and DFT calculations have been carried out to find the activation barrier and the structure of the transition state for this reaction channel from both EC and 1,2-DCE. The preexponential factors calculated at various levels of theory (BF/6-311++G**, MP2/6-311++G**, and B3LYP/6-311++G**) are (approximate to10(15) s(-1)) significantly larger than the experimental results. If the torsional mode in the ground state is treated as free internal rotation the preexponential factors reduce significantly, giving excellent agreement with experimental values. The DFT results are in excellent (fortuitous?) agreement with the experimental value for activation energy for 1,2-DCE while the MP2 and HF results seem to overestimate the barrier. However, DFT results for EC is 4.5 kcal mol(-1) less than the previously reported experimental values. At all levels, theory predicts an increase in HCI elimination barrier on beta-Cl substitution on EC.

The influence of trace impurities on the mechanical characteristics of a superplastic 2 mol% yttria stabilized zirconia

In contrast to metallic alloys, the mechanical characteristics of superplastic ceramics are very sensitive to minor changes in levels of trace impurities. In the present study, the mechanical behavior of a 2 mol% yttria stabilized tetragonal zirconia was studied in tension and compression in two batches of material, with small variations in levels of trace impurities, to examine the influence of stress axis and impurity content on the deformation behavior. The mechanical properties of the material were characterized in terms of the expression: (epsilon)over dot proportional to sigma(n) where (epsilon)over dot is the strain rate, sigma is the stress and n is termed the stress exponent. The mechanical behavior of the ceramic was identical in tension and compression, for a material with a given level of impurity. The high purity specimens exhibited a transition from a stress exponent of similar to 3 to similar to 2 with an increase in stress, whereas the low purity material displayed only n similar to 2 behavior over the entire stress range studied. Detailed high resolution and analytical electron microscopy studies revealed that there was no amorphous phase at interfaces in both batches of material; however, segregation of Al at interfaces was detected only in the low purity material. The observed transition in stress exponents can be rationalized in terms of two sequential mechanisms: grain boundary sliding with n similar to 2 and interface reaction controlled grain boundary sliding with n similar to 3. The transition from n similar to 3 to similar to 2 occurred at lower stresses with an increase in the grain size and a decrease in the purity level.

Helix-coil stability constants for amino acids in nonaqueous solvents. Studies of random poly(-benzyl-L-glutamate-co-L-alanine) and poly(-benzyl-L-glutamate-co-L-leucine) in a mixed solvent

The host-guest technique has been applied to the determination of the helix-coil stability constants of two naturally occurring amino acids, L-alanine and L-leucine, in a nonaqueous solvent system. Random copolymers containing L-alanine and L-leucine, respectively, as guest residues and -benzyl-L-glutamate as the host residue were synthesized. The polymers were fractionated and characterized for their amino acid content, molecular weight, and helix-coil transition behavior in a dichloroacetic acid (DCA)-1,2-dichloroethane (DCE) mixture. Two types of helix-coil transitions were carried out on the copolymers: solvent-induced transitions in DCA-DCE mixtures at 25°C and thermally induced transitions in a 82:18 (wt %) DCA-DCE mixture. The thermally induced transitions were analyzed by statistical mechanical methods to determine the Zimm-Bragg parameters, and s, of the guest residues. The experimental data indicate that, in the nonaqueous solvent, the L-alanine residue stabilizes the -helical conformation more than the L-leucine residue does. This is in contrast to their behavior in aqueous solution, where the reverse is true. The implications of this finding for the analysis of helical structures in globular proteins are discussed.

Thermodynamic properties of the systems benzene-chloroethanes

This paper presents the experimental data on vapor-liquid equilibrium and heats of mixing of mixtures of benzene with 1, e-dichloroethane, 1, l, 1 -trichloroethane, and lt1,2,2-tetrachloroethane.A literature survey revealed that the heats of mixing of benzene-l,2-dichloroethane have been studied and Table I shows the extent of study on this system.

Entropy and dynamics of water in hydration layers of a bilayer

We compute the entropy and transport properties of water in the hydration layer of dipalmitoylphosphatidylcholine bilayer by using a recently developed theoretical scheme two-phase thermodynamic model, termed as 2PT method; S.-T. Lin et al., J. Chem. Phys. 119, 11792 (2003)] based on the translational and rotational velocity autocorrelation functions and their power spectra. The weights of translational and rotational power spectra shift from higher to lower frequency as one goes from the bilayer interface to the bulk. Water molecules near the bilayer head groups have substantially lower entropy (48.36 J/mol/K) than water molecules in the intermediate region (51.36 J/mol/K), which have again lower entropy than the molecules (60.52 J/mol/K) in bulk. Thus, the entropic contribution to the free energy change (T Delta S) of transferring an interface water molecule to the bulk is 3.65 kJ/mol and of transferring intermediate water to the bulk is 2.75 kJ/mol at 300 K, which is to be compared with 6.03 kJ/mol for melting of ice at 273 K. The translational diffusion of water in the vicinity of the head groups is found to be in a subdiffusive regime and the rotational diffusion constant increases going away from the interface. This behavior is supported by the slower reorientational relaxation of the dipole vector and OH bond vector of interfacial water. The ratio of reorientational relaxation time for Legendre polynomials of order 1 and 2 is approximately 2 for interface, intermediate, and bulk water, indicating the presence of jump dynamics in these water molecules. (C) 2010 American Institute of Physics. doi:10.1063/1.3494115]

Novel Mn-doped chalcopyrites

Heavily Mn-doped II-VI-V-2 semiconductors, such as CdGeP2 and ZnGeP2 have been prepared by depositing Mn on single crystalline substrate at nearly 400 T in an ultra high vacuum chamber. Well-defined ferromagnetic hysteresis with a saturation behavior appears in the magnetization curve up to above room temperature. The chemical states of the ZDGeP(2):Mn interface has been clarified by a careful in situ photoemission spectroscopy. The as-prepared surface consists of Ge-rich, metallic Mn compound. In and below the sub-surface region, dilute divalent Mn species as precursors of the DMS phase exist. No MnP phase was observed at any stage of the depth profile. Theoretical band-calculation suggests that the system with vacancies (Cd, V-c, Mn)GeP2 or a non-stoichiometric (Cd, Ge, Mn)GeP2 are ferromagnetic and energetically stable although ferromagnetism is not stable in a stoichiometric compound (Cd, Mn)GeP2. (C) 2003 Elsevier Ltd. All rights reserved.

Growth of TiO2 Films by RF Magnetron Sputtering for MOS Gate Dielectrics: Influence of Substrate Temperature

Titanium dioxide thin films were deposited by RF reactive magnetron sputtering technique on p-type silicon(100) substrates held at temperatures in the range 303-673 K. The influence of substrate temperature on the core level binding energies, chemical bonding configuration, crystallographic structure and dielectric properties was investigated. X-ray photoelectron spectroscopy studies and Fourier transform infrared transmittance data confirmed the formation of stoichiometric films with anatase phase at a substrate temperature of 673 K. The films formed at 303 K were nanocrystalline with amorphous matrix while those deposited at 673 K were transformed in to crystalline phase and growth of grains in pyramidal like structure as confirmed by X-ray diffraction and atomic force microscopy respectively. Metal-oxide-semiconductor capacitors were fabricated with the configuration of Al/TiO2/Si structures. The current voltage, capacitance voltage and conductance voltage characteristics were studied to understand the electrical conduction and dielectric properties of the MOS devices. The leakage current density (at gate voltage of 2 V) decreased from 2.2 x 10(-6) to 1.7 x 10(-7) A/cm(2), the interface trap density decreased from 1.2 x 10(13) to 2.1 x 10(12) cm(-2) eV(-1) and the dielectric constant increased from 14 to 36 with increase of substrate temperature from 303 to 673 K.

Interface between 2 dissimilar fluids beneath a sheetpile cofferdam

A closed form solution is presented for determining the shape and location of the interface between two dissimilar fluids (having different densities) when steady flow takes place through a homogeneous and isotropic porous medium, into a sheetpile cofferdam; the interface is assumed to be sharp and the lower fluid stationary. The solution is obtained using the inverse hodograph. Numerical results are presented in nondimensional form for various parametric conditions in the physical plane; the interface pattern, as also the seepage discharge and exit gradient distribution are shown. The critical conditions of the interface are studied.

Reduction of oxygen impurity at GaN/beta-Si(3)N(4)/Si interface via SiO(2) to Ga(2)O conversion by exposing of Si surface under Ga flux

The removal of native oxide from Si (1 1 1) surfaces was investigated by X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectra (SIMS) depth profiles. Two different oxide removal methods, performed under ultrahigh-vacuum (UHV) conditions, were carried out and compared. The first cleaning method is thermal desorption of oxide at 900 degrees C. The second method is the deposition of metallic gallium followed by redesorption. A significant decrease in oxygen was achieved by thermal desorption at 900 degrees C under UHV conditions. By applying a subsequent Ga deposition/redesorption, a further reduction in oxygen could be achieved. We examine the merits of an alternative oxide desorption method via conversion of the stable SiO(2) surface oxide into a volatile Ca(2)O oxide by a supply of Ga metals. Furthermore, ultra thin films of pure silicon nitride buffer layer were grown on a Si (1 1 1) surface by exposing the surface to radio-frequency (RF) nitrogen plasma followed by GaN growth. The SIMS depth profile shows that the oxygen impurity can be reduced at GaN/beta-Si(3)N(4)/Si interfaces by applying a subsequent Ga deposition/redesorption. (C) 2011 Elsevier B.V. All rights reserved.

Supramolecular control of the magnetic anisotropy in two-dimensional high-spin Fe arrays at a metal interface

Magnetic atoms at surfaces are a rich model system for solid-state magnetic bits exhibiting either classical(1,2) or quantum(3,4) behaviour. Individual atoms, however, are difficult to arrange in regular patterns(1-5). Moreover, their magnetic properties are dominated by interaction with the substrate, which, as in the case of Kondo systems, often leads to a decrease or quench of their local magnetic moment(6,7). Here, we show that the supramolecular assembly of Fe and 1,4-benzenedicarboxylic acid molecules on a Cu surface results in ordered arrays of high-spin mononuclear Fe centres on a 1.5nm square grid. Lateral coordination with the molecular ligands yields unsaturated yet stable coordination bonds, which enable chemical modification of the electronic and magnetic properties of the Fe atoms independently from the substrate. The easy magnetization direction of the Fe centres can be switched by oxygen adsorption, thus opening a way to control the magnetic anisotropy in supramolecular layers akin to that used in metallic thin films.

Functional correlation of bacterial LuxS with their quaternary associations: interface analysis of the structure networks

Background The genome of a wide variety of prokaryotes contains the luxS gene homologue, which encodes for the protein S-ribosylhomocysteinelyase (LuxS). This protein is responsible for the production of the quorum sensing molecule, AI-2 and has been implicated in a variety of functions such as flagellar motility, metabolic regulation, toxin production and even in pathogenicity. A high structural similarity is present in the LuxS structures determined from a few species. In this study, we have modelled the structures from several other species and have investigated their dimer interfaces. We have attempted to correlate the interface features of LuxS with the phenotypic nature of the organisms. Results The protein structure networks (PSN) are constructed and graph theoretical analysis is performed on the structures obtained from X-ray crystallography and on the modelled ones. The interfaces, which are known to contain the active site, are characterized from the PSNs of these homodimeric proteins. The key features presented by the protein interfaces are investigated for the classification of the proteins in relation to their function. From our analysis, structural interface motifs are identified for each class in our dataset, which showed distinctly different pattern at the interface of LuxS for the probiotics and some extremophiles. Our analysis also reveals potential sites of mutation and geometric patterns at the interface that was not evident from conventional sequence alignment studies. Conclusion The structure network approach employed in this study for the analysis of dimeric interfaces in LuxS has brought out certain structural details at the side-chain interaction level, which were elusive from the conventional structure comparison methods. The results from this study provide a better understanding of the relation between the luxS gene and its functional role in the prokaryotes. This study also makes it possible to explore the potential direction towards the design of inhibitors of LuxS and thus towards a wide range of antimicrobials.

Kinetics of Extraction of Iron(II1) by Bis(2-ethylhexyl Phosphate in a Laminar Liquid-Liquid Jet Reactor

The kinetics of iron(II1) extraction by bis(Zethylhexy1) phosphate (HDEHP, HA) in kerosene from sulfuric acid solutions has been studied in a liquid-liquid laminar jet reactor. The contact time of the interface in this reacting device is of the same order of magnitude as the surface renewal time in dispersion mixing and much less than that obtained in the relatively quiescent condition of the Lewis cell. Yet the analysis of the data in this study suggested a rate-controlling step involving surface saturation quite in conformity with that obtained in the Lewis cell and not with that in dispersion mixing as reported in the literature. Further, the mechanism suggested a weaker dependence of the rate on hydrogen ion concentration which was reported by other workers.