Determination of the rate constants for reactions of gaseous substrates with adsorbed O? radical anions

1996 ◽  
Vol 32 (2) ◽  
pp. 67-69
Author(s):  
V. P. Tret'yakov
Keyword(s):  
Rate Constants ◽  
Radical Anions

Free-radical reductions of arenediazonium ions in aqueous solution. V. Pulse-radiolytic determination of rate constants for some para-substitutedbenzenediazonium ions

1981 ◽  
Vol 34 (7) ◽  
pp. 1433 ◽  
Author(s):  
JE Packer ◽  
J Monig ◽  
BC Dobson
Keyword(s):  
Aqueous Solution ◽  
Free Radical ◽  
Rate Constants ◽  
Substituent Effect ◽  
Reduction Potential ◽  
Radical Anions ◽  
Semiquinone Radical ◽  
Substituent Group

Some rate constants for the reduction of para-substituted benzenediazonium ions by the radicals eaq-, ·CH2OH, (CH3)2·COH and some semiquinone radical anions have been measured. The substituent group has no effect on the rates with eaq-, but as the reduction potential of the reducing radical becomes more positive, the substituent effect increases, electron-withdrawing groups enhancing the rates. No free halide is formed on reduction of p-BrC6H4N2+ or p-IC6H4N2+ by eaq- or ·CH2OH.

Determination of rate constants for electron transfer from radical anions of aromatic compounds to diaryl disulfides

1981 ◽  
Vol 103 (18) ◽  
pp. 5484-5489 ◽  
Author(s):  
Hideyuki Tagaya ◽  
Tamotsu Aruga ◽  
Osamu Ito ◽  
Minoru Matsuda
Keyword(s):  
Electron Transfer ◽  
Rate Constants ◽  
Aromatic Compounds ◽  
Radical Anions

Determination of rate constants of redox reactions of second order from current-less potential-time curves by a simplified graphical-numerical method

1983 ◽  
Vol 48 (5) ◽  
pp. 1358-1367 ◽  
Author(s):  
Antonín Tockstein ◽  
František Skopal
Keyword(s):  
Numerical Method ◽  
Explicit Form ◽  
Rate Constant ◽  
Optimization Algorithm ◽  
Rate Constants ◽  
Redox Reactions ◽  
Second Order ◽  
Wide Region ◽  
Recurrent Formula

A method for constructing curves is proposed that are linear in a wide region and from whose slopes it is possible to determine the rate constant, if a parameter, θ, is calculated numerically from a rapidly converging recurrent formula or from its explicit form. The values of rate constants and parameter θ thus simply found are compared with those found by an optimization algorithm on a computer; the deviations do not exceed ±10%.

Determination of the Accurate Values of the Rate Constant and Thermodynamic Parameters for the Rotation About the C(sp2)-C(aryl) Bond; Adamantan-1-yl 3-Bromo-2,4,6-trimethylphenyl Ketone

1998 ◽  
Vol 63 (7) ◽  
pp. 955-966
Author(s):  
Eva Přibylová ◽  
Miroslav Holík
Keyword(s):  
Thermodynamic Parameters ◽  
Shape Analysis ◽  
Rate Constants ◽  
Line Shape ◽  
Microsoft Excel ◽  
Hindered Rotation ◽  
H Nmr ◽  
Line Shape Analysis ◽  
Coalescence Temperature

Four programs for the 1H NMR line shape analysis: two commercial - Winkubo (Bruker) and DNMR5 (QCPE 165) and two written in our laboratory - Newton (in Microsoft Excel) and Simtex (in Matlab) have been tested in order to get highly accurate rate constants of the hindered rotation about a single bond. For this purpose four testing criteria were used, two of them were also developed by us. As supplementary determinations the rate constants obtained for the coalescence temperature and for the thermal racemization of chromatographically separated enantiomers were used which fitted well the temperature dependence of the rate constants determined by the line shape analysis. As a test compound adamantan-1-yl 3-bromo-2,4,6-trimethylphenyl ketone was prepared and studied. It was shown that supermodified simplex method used in our algorithm (Simtex), though time consuming, gives the most accurate values of the rate constants and consequently the calculated thermodynamic parameters Ea, ∆H≠, and ∆S≠ lay in relatively narrow confidence intervals.

Determination of the Nucleophilicity of Tricarbonyliron Coordinated Cyclohepta-1,3,5-triene

1999 ◽  
Vol 64 (11) ◽  
pp. 1770-1779 ◽  
Author(s):  
Herbert Mayr ◽  
Karl-Heinz Müller
Keyword(s):  
Gibbs Energy ◽  
Ambient Temperature ◽  
Rate Constants ◽  
Second Order ◽  
Order Rate ◽  
Electrophilic Additions ◽  
Kinetics Of

The kinetics of the electrophilic additions of four diarylcarbenium ions (4a-4d) to tricarbonyl(η4-cyclohepta-1,3,5-triene)iron (1) have been studied photometrically. The second-order rate constants match the linear Gibbs energy relationship log k20 °C = s(E + N) and yield the nucleophilicity parameter N(1) = 3.69. It is concluded that electrophiles with E ≥ -9 will react with complex 1 at ambient temperature.

Interfacial catalysis by phospholipase A2: determination of the interfacial kinetic rate constants

Biochemistry ◽  
1991 ◽  
Vol 30 (29) ◽  
pp. 7283-7297 ◽  
Author(s):  
Otto G. Berg ◽  
Bao Zhu Yu ◽  
Joe Rogers ◽  
Mahendra Kumar Jain
Keyword(s):  
Phospholipase A2 ◽  
Rate Constants ◽  
Kinetic Rate ◽  
Kinetic Rate Constants ◽  
Interfacial Catalysis
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