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61.
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. 相似文献
62.
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. 相似文献
63.
《Surface and interface analysis : SIA》2006,38(9):1249-1251
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. 相似文献
64.
Y.V. PatelP.H. Parsania 《European Polymer Journal》2002,38(9):1827-1835
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 Sn.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 Tg 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. 相似文献
65.
Molecular parameters and retention characteristics of unsubstituted polyaromatic hydrocarbons in HPLC 总被引:1,自引:0,他引:1
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). 相似文献
66.
Dean C. Luehrs Richard E. Brown Kalpana A. Godbole 《Journal of solution chemistry》1989,18(5):463-469
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. 相似文献
67.
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. 相似文献
68.
69.
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. 相似文献
70.
M. Yakup Arca Meltem Ylmaz Emine Yaln Gülay Bayramo
lu 《Journal of membrane science》2004,240(1-2):167-178
Poly(hydroxyethyl methacrylate), pHEMA, and a composite pHEMA/chitosan networks were synthesized in the membrane form via UV initiated photo-polymerisation in the presence of an initiator ,′-azoisobutyronitrile. Reactive Yellow 2 (RY-2) was covalently immobilised as a dye–ligand onto both membranes. The polarity and surface energy of the investigated membranes were determined by contact angle measurement. The incorporation of chitosan in the pHEMA networks produced more hydrophilic surface, as indicated by contact angle analysis. The binding characteristics of lysozyme, γ-globulins, human serum albumin (HSA) and bovine serum albumin (BSA) to pHEMA-RY-2 and pHEMA/chitosan-RY-2 affinity membranes have been investigated from aqueous solution and their dye–ligand free forms were used as control systems. When chitosan was incorporated in the pHEMA network as a cationic polymer led to higher adsorption capacity for the lysozyme. Selective adsorption behaviour was also observed in the case of pHEMA/chitosan-RY-2 membrane for the lysozyme. The non-specific adsorptions of the lysozyme on the pHEMA and pHEMA/chitosan membranes were about 1.9 and 7.2 mg/ml, respectively. These were negligible for all others investigated proteins. The lysozyme adsorption data was analysed using the first-order and the second-order models. The first-order equation in both affinity membrane systems is the most appropriate equation to predict the adsorption capacities of the adsorbents. The adsorption isotherms well fitted the combined Langmuir–Freundlich model. A theoretical analysis has been conducted to estimate the thermodynamic contributions (changes in enthalpy, entropy and Gibbs free energy) for the adsorption of lysozyme to both dye–ligand immobilised membranes. The adsorption capacities of both dye–ligand immobilised membranes increased with increasing the temperature while decreased with increasing the NaCl concentration. Both affinity membranes are stable when subjected to sanitization with sodium hydroxide after repeated separation–elution cycles. 相似文献