scholarly journals A CALCULATION ON THE EFFECT OF NONHOMOGENEITY ON THE DETERMINATION OF THE RATE CONSTANT OF A BIMOLECULAR, SECOND-ORDER REACTION.

1967 ◽  
Author(s):  
M.C. Jr. Sauer
Keyword(s):  
Rate Constant ◽  
Order Reaction ◽  
Second Order ◽  
Second Order Reaction

Particular solution for any consecutive second-order reaction

1987 ◽  
Vol 65 (8) ◽  
pp. 1987-1994 ◽  
Author(s):  
Martino Paventi
Keyword(s):  
Rate Constant ◽  
Initial Conditions ◽  
Order Reaction ◽  
Second Order ◽  
Second Order Reaction ◽  
Total Differential ◽  
Particular Solution ◽  
Approach Zero ◽  
Reported Data ◽  
Zero Time

Arguments are presented against the accepted notion that multiple rate constants may be obtained from observed singular or pooled kinetic runs. For any competitive consecutive second-order reaction, the particular solution satisfying the total differential equation, derived from (n + 1) simultaneous differential equations, is S = (aA0 − S0){(aA0/S0)[exp (aA0 − S0)kt] − 1}−1, where S is the concentration of reactant common for all the steps, A is the concentration of the substrate with a reactive sites, A0 and S0 are the concentration of reactants at zero time, k is the observed rate constant, and t is the time. This equation is shown to reproduce the experimental reported data and yields k = min(k(1), …, k(n)), where k(i) is the rate constant assigned to step i. It is also shown that the initial conditions need not be known. For experiments with the initial condition (aA0 = S0), with only species A and S are present at zero time, the expression [Formula: see text] may be useful for an approximate evaluation of k when values of S do not approach zero after an infinite time (i.e., Sx = α ≠ 0, where α is the asymptote for the data).

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%.

Stability of radical anions derived from substituted 5-nitrofurans investigated by ESR spectroscopy

1985 ◽  
Vol 50 (7) ◽  
pp. 1594-1601 ◽  
Author(s):  
Jiří Klíma ◽  
Larisa Baumane ◽  
Janis Stradinš ◽  
Jiří Volke ◽  
Romualds Gavars
Keyword(s):  
Radical Anion ◽  
High Stability ◽  
Esr Spectroscopy ◽  
Reaction Path ◽  
Order Reaction ◽  
Second Order ◽  
Radical Anions ◽  
Second Order Reaction ◽  
Unpaired Electron Density ◽  
The Stability

It has been found that the decay in dimethylformamide and dimethylformamide-water mixtures of radical anions in five of the investigated 5-nitrofurans is governed by a second-order reaction. Only the decay of the radical anion generated from 5-nitro-2-furfural III may be described by an equation including parallel first- and second-order reactions; this behaviour is evidently caused by the relatively high stability of the corresponding dianion, this being an intermediate in the reaction path. The presence of a larger conjugated system in the substituent in position 2 results in a decrease of the unpaired electron density in the nitro group and, consequently, an increase in the stability of the corresponding radical anions.

Kinetics of the reaction between hexamethylenediisocyanate and 1-pentanol

1983 ◽  
Vol 48 (11) ◽  
pp. 3279-3286
Author(s):  
Slavko Hudeček ◽  
Miloslav Bohdanecký ◽  
Ivana Hudečková ◽  
Pavel Špaček ◽  
Pavel Čefelín
Keyword(s):  
Liquid Chromatography ◽  
Rate Constants ◽  
Reversed Phase ◽  
Order Reaction ◽  
Second Order ◽  
Second Order Reaction ◽  
Reversed Phase Liquid Chromatography ◽  
Consecutive Reactions ◽  
Phase Liquid ◽  
Kinetics Of

The reaction between hexamethylenediisocyanate and 1-pentanol in toluene was studied by means of reversed-phase liquid chromatography. By employing this method, it was possible to determine all components of the reaction mixture including both products, i.e. N-(6-isocyanate hexyl)pentylcarbamate and N,N'-bis(pentyloxycarbonyl)hexamethylenediamine. Relations for the calculation of kinetic constants were derived assuming a competitive consecutive second-order reaction. It was demonstrated that the reaction involved in this case is indeed a second-order reaction, and the rate constants of the first and second consecutive reactions were determined.

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