The application of the concept of reaction layer to the study of electrode processes coupled with the second-order chemical reactions at microelectrodes under steady-state conditions

Under steady-state conditions, the current equations of the second-order EC, ECE and DISPI reactions at microdisk, microspherical and microring electrodes are derived with the aid of the concept of the reaction layer. The conditions under which these equations would be valid are also discussed. Using these equations, methods to determine the kinetic parameters for the second-order EC, ECE and DISPI reactions are presented. The reduction of 2,6-diphenyl-pyrylium cation and oxidation of triphenylamine were investigated as examples of the second-order EC and ECE reactions.     

Ab initio calculation of 4-ClC6H4CH2Cl and peculiarities of electron density distribution in this molecule

Ab initio calculation of the 4-ClC₆H₄CH₂Cl molecule was performed by the restricted Hartree-Fock method in the split valence 6–31 G* basis set with complete optimization of its geometry. Populations of p-orbitals of atoms of this molecule were analyzed.³⁵Cl NQR frequencies and asymmetry parameters of the electric field gradient on³⁵Cl nuclei were estimated on the basis of the populations of valent p-orbitals of CI atoms and their components. Good conformity with the experimental values was obtained when only less diffuse components of p-orbitals were used in calculations of populations.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 823–826, April, 1996.     

Segregation of Sn in the binary CuSn and ternary CuSnSb alloy systems

Progression studies have been followed from Cu(111)‐ and Cu(100)Sn binaries to Cu(111)‐ and Cu(100)SnSb ternary‐alloy systems under the same experimental conditions. The segregation behaviour of Sn in the two orientations are explained. It is found that the kinetic segregation profiles of Sn in the ternary alloys shift to lower temperatures as compared to that in the binary. The Sn profile shift is mainly due to the decrease in the activation energy of Sn in the ternary systems. For a particular Cu orientation, the other segregation parameters that the Sn profiles depend on, like the pre‐exponential factor, segregation energy and the interaction coefficient, are found to be the same in the two systems. There is also a change in the equilibrium segregation profiles of Sn. In the ternary system, site competition between Sn and Sb causes the Sn to suffer exponential desegregation and eventual displacement from the surface. Copyright © 2006 John Wiley & Sons, Ltd.     

Investigation of solution and solid-state properties of poly(R,R,4,4-cyclohexylidene diphenylene diphenyl-4,4-disulfonate)

Solution and solid-state properties of poly(R,R^′,4,4^′-cyclohexylidene diphenylene diphenyl-4,4^′-disulfonate) (PS-6: R=R^′=H; PS-7: R=CH₃, R^′=H; PS-8: R=R^′=Cl; PS-9: R=CH₃, R^′=Cl and PS-10: R=R^′=Br) have been determined and discussed in terms of nature of the substituents. Ultrasonic velocity (2 MHz) and acoustical parameters of PS-7 and PS-9 solutions in chloroform, 1,2-dichloroethane and tetrahydrofuran (THF) at 30, 35 and 40 °C have been evaluated to understand the effect of methyl and chlorine groups, concentration, and temperature on molecular interactions. The data are interpreted in light of solvent-polymer and polymer-polymer interactions. Predominant solvation is observed in THF system and the least in chloroform system at all three temperatures. The structural change is observed above 2%. Both the polymers possess structure-forming tendency and it is supported by positive values of S_n.The densities of PS-7 and PS-9 determined by floatation method are in excellent agreement with calculated values but those determined by specific volume method differ remarkably from calculated values due to solvation effect. PS-7 and PS-9 possess respectively tensile strength of 38.4 and 1.1 N/mm²; electric strength of 16.2 and 25.0 kV/mm and volume resistivity of 5.7×10¹⁶ and 1.0×1017Ωcm. The low tensile strength of PS-9 is due to low molecular weight, rigid and brittle nature of the polymer chains. PS-6 to PS-9 are thermally stable up to about 349-379 °C while PS-10 up to about 279 °C and involved two-step degradation. DTA thermograms indicated T_g at about 204-226 °C. High activation energy indicated rigid nature of the polymer chains and the positive magnitudes of ΔS* indicated less ordered transition state. The nature of the substituents (CH₃, Cl and Br) affected thermal, mechanical and electrical properties.     

Molecular parameters and retention characteristics of unsubstituted polyaromatic hydrocarbons in HPLC

Summary The present research studies the possibility of using the correlation dependence between molecular parameters of unsubstituted polyaromatic hydrocarbons (PAH) and their retention in reversed-phase liquid chromatography to optimize the conditions for the separation and identification of unknown peaks on the chromatograms of multicomponent mixtures. A linear correlation equation, that takes the number and environment of the carbon atom in the PAH molecule into account as well as the differences in the specific interactions of isomeric molecules with polar eluent, has been proposed. The adequacy of the proposed PAH retention model was verified by comparing the calculated retention values with the experimental data. The possibility of identifying unsubstituted PAH according to the number of carbon atoms of various types and according to the values of the molecules lengths (calculated on the basis of the retention of these substances under different eluent compositions) was exemplified by various chromatographic systems (reversed phase-eluent-PAH molecules).     

Linear free energy relationship of the energy of the CTTS transition of Halide ions with the solvatochromic parameter α

A linear free energy relationship was found betweenv _max, the energy of the absorption maximum of chloride, bromide, or iodide ion in various solvents, and the solvatochromic parameter which is a measure of the hydrogen bond donor ability of the solvent. The relationships are: for chloride,v _max=6.99+50.16 kK; for bromide,v _max=5.52+45.20 kK; for iodide,v _max=5.02+40.33 kK. The correlation ofv _max for iodide ion with gave a larger correlation coefficient and smaller standard deviation than a correlation with the E _T (30) parameter of Dimroth. From the values ofv _max for iodide ion and the solvated electron in liquid ammonia at 25°C, these correlations indicate a preliminary value of 0.00 for the parameter of liquid ammonia. This had not been reported before and is lower than expected from a general knowledge of the physical and chemical properties of liquid ammonia but is consistent with a more detailed consideration and recent gas phase measurements of hydrogen bond donor strength.     

Thermal Degradation of Polychloroprene Rubber Under Isothermal and Non-Isothermal Conditions

The results of a kinetic investigation of the non-isothermal degradation and the isothermal degradation of the residual deformation under constant deflection for polychloroprene rubber are presented. A relationship was derived between the degree of non-isothermal conversion and the value of the investigated mechanical property. This revised version was published online in July 2006 with corrections to the Cover Date.     

聚合温度对聚甲基丙烯酸三丁基锡酯等规度的影响(Ⅰ)

本文测定了0—130℃温度范围内,由~(60)Co-γ射线和两种活性不同的引发剂引发聚合的聚甲基丙烯酸三丁基锡酯的等规度。利用~(13)C-NMR测定聚合物分子链的等规度,如预料的那样,以间同立构为主,并随着聚合温度的升高间同立构等规度降低。作者认为影响聚合物等规度的因素主要是取代基的极性效应。计算出的控制等规度的活化能参数与聚甲基丙烯酸甲酯和聚甲基丙烯酸三甲基锡酯的属同一数量级,可相互比较。     

A study of the thermal decarboxylation of three perfluoropolyether salts

The thermal decarboxylation of three dicarboxylic perfluoropolyether potassium salts of relatively short chain length has been investigated and the products and kinetics of the main reactions have been defined. From the rate constants and Arrhenius parameters data, the second decarboxylation appears to be quantitatively rather close to the first.     

Pressure and volume dependence of thelo-to phonons in InAs

The pressure dependence of thelo-to phonons in InAs has been investigated by Raman scattering using the diamond anvil cell. Indium arsenide transforms, presumably to the rock-salt structure at 70±1 kbar. The mode Grüneisen parameters for thelo-to phonons are γ _lo =0.99±0.03, γ _to =1.2±0.03 respectively. The effective charge,e* _T , for InAs decreases slightly with pressure and this trend is in accordance with the behaviour of other III–V zinc blende structured semiconductors: The structural phase transition is discussed in the light of theoretical calculations for phase stability of III–V compounds, as well as recent high pressure x-ray diffraction studies.