Critical test of first-order theories for electron transfer in collisions between multicharged ions and atomic hydrogen: The boundary condition problem

1987 ◽  
Vol 36 (4) ◽  
pp. 1601-1617 ◽  
Author(s):  
Dzevad Belkić ◽  
Subhash Saini ◽  
Howard S. Taylor
Keyword(s):  
Boundary Condition ◽  
Electron Transfer ◽  
Atomic Hydrogen ◽  
Critical Test ◽  
First Order ◽  
Condition Problem

Interpretation of Electron Transfer Spectra of Iridium (IV) and Osmium(IV) Mixed Chloro-Bromo Complexes

1967 ◽  
Vol 22 (6) ◽  
pp. 945-954 ◽  
Author(s):  
Chr. Klixbüll Jørgensen ◽  
W. Preetz
Keyword(s):  
Electron Transfer ◽  
Faraday Effect ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
University Of Virginia ◽  
First Order ◽  
Order Of Magnitude ◽  
Moderate Difference ◽  
The University ◽  
As If

The previous M.O. treatment of unsubstituted hexahalides has been modified, taking the results on Faraday effect obtained at the University of Virginia into account. The absorption spectra previously measured of the complexes (M=Os, Ir) trans-MCl4Br2— and trans-MCl2 Br4— are interpreted by a M.O. treatment for the symmetry D4h as electron transfer transitions, including a first-order relativistic (spin-orbit coupling) correction. The concept of holohedrized symmetry is sufficiently valid to allow a description of MCl5Br— and MClBr5— as if they were tetragonal with centre of inversion and ƒac-(or cis-)MCl3Br3— as if they were cubic. It is shown that the ligand-ligand antibonding effects have the same order of magnitude as the moderate difference in optical electronegativity between Cl- and Br-.

Application of Generalized Differential Quadrature Method to the Bending of Thick Laminated Plates with Various Boundary Conditions

2006 ◽  
Vol 5-6 ◽  
pp. 407-414 ◽  
Author(s):  
Mohammad Mohammadi Aghdam ◽  
M.R.N. Farahani ◽  
M. Dashty ◽  
S.M. Rezaei Niya
Keyword(s):  
Boundary Condition ◽  
Boundary Conditions ◽  
Simple Procedure ◽  
Shear Deformation Theory ◽  
Laminated Plates ◽  
Differential Quadrature ◽  
Governing Equations ◽  
First Order ◽  
Various Boundary Conditions ◽  
Generalized Differential

Bending analysis of thick laminated rectangular plates with various boundary conditions is presented using Generalized Differential Quadrature (GDQ) method. Based on the Reissner first order shear deformation theory, the governing equations include a system of eight first order partial differential equations in terms of unknown displacements, forces and moments. Presence of all plate variables in the governing equations provide a simple procedure to satisfy different boundary condition during application of GDQ method to obtain accurate results with relatively small number of grid points even for plates with free edges .Illustrative examples including various combinations of clamped, simply supported and free boundary condition are given to demonstrate the accuracy and convergence of the presented GDQ technique. Results are compared with other analytical and finite element predictions and show reasonably good agreement.

Aromatic oxidation by cobaltic acetate in acetic acid

1969 ◽  
Vol 47 (3) ◽  
pp. 387-392 ◽  
Author(s):  
Koichiro Sakota ◽  
Yoshio Kamiya ◽  
Nobuto Ohta
Keyword(s):  
Activation Energy ◽  
Electron Transfer ◽  
Acetic Acid ◽  
Bond Energy ◽  
Hydrogen Abstraction ◽  
Steric Factor ◽  
Benzyl Acetate ◽  
Kcal Mole ◽  
First Order ◽  
Reversible Electron Transfer

A detailed kinetic study of oxidation of toluene and its derivatives by cobaltic acetate in 95 vol% acetic acid is reported. The reaction was found to be profoundly affected by a steric factor and rather insensitive to the C—H bond energy. The order of reactivities of various alkylbenzenes is quite reversal to that of hydrogen abstraction reactions. The reaction was of first-order with respect to toluene, of second-order with respect to cobaltic ion and of inverse first-order with respect to cobaltous ion. The oxidation by cobaltic ion seems to proceed via an initial reversible electron transfer from toluene to cobaltic ion, yielding [Formula: see text] which is oxidized into benzyl acetate by another cobaltic ion. The apparent activation energy for toluene was found to be 25.3 kcal mole−1, and the same activation energy was found for ethylbenzene, cumene, diphenylmethane, and triphenylmethane.

Electron-Transfer Reactions in Non-Aqueous Media. V. Solvent Effects in the Reduction of CoN3(NH3)52+ by Iron(II)

1979 ◽  
Vol 32 (10) ◽  
pp. 2139 ◽  
Author(s):  
TJ Westcott ◽  
DW Watts
Keyword(s):  
Electron Transfer ◽  
Aqueous Media ◽  
Activation Parameters ◽  
Transfer Reactions ◽  
Tetrahedral Coordination ◽  
First Order ◽  
Precursor Complex ◽  
Stage Process ◽  
Pseudo First Order ◽  
Reversible Formation

The reduction of CoN3(NH3)52+ by iron(II) is rate-determined by a two-stage process involving the reversible formation of an azide-bridged precursor complex prior to electron transfer in each of the solvents water, Me2SO, aqueous Me2SO and HCONMe2. The activation parameters in H2O and Me2SO, and the trends shown with increasing Me2SO concentrations in aqueous Me2SO, are similar to the properties of the previously studied CoCl(NH3)52+ and CoBr(NH3)52+ systems and contrast with the reduction of COF(NH3)52+. The results are consistent with a bridged precursor complex octahedral at both the iron and cobalt atoms in water but with tetrahedral coordination about the iron in Me2SO. In HCONMe2, as in the reduction of COF(NH3)52+, COCl(NH3)52+ and COBr(NH3)52+, the precursor complex is a significant part of the reacting solutions, and as a result the experimental pseudo-first-order rate constants for the loss of CoIII are not linearly dependent on the concentration of FeII. The initial spectra of the reacting solutions in this system also indicate significant concentrations of the precursor complex.

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