Nucleophilic decomposition of α-disulfones

1969 ◽  
Vol 47 (6) ◽  
pp. 873-877 ◽  
Author(s):  
Paul Allen Jr. ◽  
Patrick J. Conway
Keyword(s):  
Activation Energy ◽  
Order Reaction ◽  
Second Order ◽  
Hammett Equation ◽  
Second Order Reaction ◽  
Kcal Mole ◽  
Arrhenius Activation Energy ◽  
Hydroxide Ion ◽  
First Order ◽  
Sulfur Bond

The sulfur–sulfur bond of α-disulfones is attacked by hydroxide ion in alcohol to yield sulfinate and sulfonate ion by a second-order reaction, first order in each of the reactants. With aromatic disulfones the ρ value of the Hammett equation is 0.2. The Arrhenius activation energy of the reaction of p-tolyl disulfone is 7.95 kcal/mole.

scholarly journals Pyrolysis of phenylmercaptoacetic acid

1968 ◽  
Vol 46 (2) ◽  
pp. 191-197 ◽  
Author(s):  
A. T. C. H. Tan ◽  
A. H. Sehon
Keyword(s):  
Carbon Dioxide ◽  
Activation Energy ◽  
Carbon Monoxide ◽  
Acetic Acid ◽  
Rate Constant ◽  
Order Reaction ◽  
First Order Reaction ◽  
Kcal Mole ◽  
Dissociation Process ◽  
First Order

The pyrolysis of phenylmercaptoacetic acid was investigated by the toluene-carrier technique over the temperature range 760–835 °K. The main products of the decomposition were phenyl mercaptan, carbon dioxide, acetic acid, phenyl methyl sulfide, carbon monoxide, and dibenzyl.The overall decomposition was a first-order reaction with respect to phenylmercaptoacetic acid and could be represented by the two parallel steps:[Formula: see text]Reaction [1] was shown to be a homogeneous first-order dissociation process, and its rate constant was represented by the expression[Formula: see text]The activation energy of this reaction, i.e. 58 kcal/mole, was identified with D(C6H5S—CH2COOH).

Studies on Blood Coagulation Factor V

1972 ◽  
Vol 27 (01) ◽  
pp. 033-042 ◽  
Author(s):  
H. C Hemker ◽  
M. J. P Kahn
Keyword(s):  
Activation Energy ◽  
Coagulation Factor ◽  
Order Reaction ◽  
Second Order ◽  
Factor V ◽  
Second Order Reaction ◽  
Bovine Plasma ◽  
Coagulation Factor V ◽  
Blood Coagulation Factor V

SummaryThe disappearance of factor V-activity from human plasma on storage can be described as a first order reaction with an activation energy of about 44 kcal/mol.The disappearance of factor V- activity from bovine plasma in vitro is a second order reaction with an activation energy of about 66 kcal/mol.The inactivation of human prothrombinase during coagulation is a second order reaction; the activation energy is about 10 kcal/mol. It is concluded that this inactivation involves a reaction of the factor V moiety of prothrombinase with free factor V.

Vulcanization of Elastomers. 21. Vulcanization of Natural Rubber with Thiuram Disulfides. VI

1959 ◽  
Vol 32 (2) ◽  
pp. 566-576
Author(s):  
Walter Scheele ◽  
Klaus Hummel
Keyword(s):  
Activation Energy ◽  
Natural Rubber ◽  
Temperature Dependence ◽  
Sulfur Content ◽  
Rate Constants ◽  
Order Reaction ◽  
First Order Reaction ◽  
Kcal Mole ◽  
First Order ◽  
Limiting Value

Abstract Bound sulfur in a pure thiuram vulcanizate increases relatively rapidly at first at all temperatures, reaches a poorly defined maximum at about 27 to 30%, independent of temperature, and then recedes slightly to reach a limiting value of 25% also independent of temperature, based on the original thiuram disulfide. The rise in sulfur content at the start points to a temperature-independent limiting value of 33%. It is shown that the combination of sulfur in this region initially follows a first order reaction, and goes at the same rate as the reduction in concentration of thiuram disulfide. It can be seen from the above that sulfur may be combined in thiuram vulcanization without simultaneous crosslinking. The dithiocarbamate formation increases rapidly in the region of longer vulcanization times, after the maximum in bound sulfur has been reached, without further combination of sulfur with the vulcanizate. The rate constants for thiuram decrease, for dithiocarbamate increase and for sulfur combination were calculated. The temperature dependence of each of these reactions has practically the same activation energy, 23 kcal/mole. The bound sulfur content of the vulcanizates in pure thiuram vulcanizations is no criterion of the state of vulcanization.

Kinetics of the reaction of methyl iodide with sulfite and thiosulfate ions in aqueous solution

1969 ◽  
Vol 47 (24) ◽  
pp. 4537-4541 ◽  
Author(s):  
R. A. Hasty ◽  
S. L. Sutter
Keyword(s):  
Activation Energy ◽  
Methyl Iodide ◽  
Reaction Rate ◽  
Reaction Rate Constant ◽  
Order Reaction ◽  
Second Order Reaction ◽  
Kcal Mole ◽  
Rate Of Reaction ◽  
Kinetics Of ◽  
Sulfite Ion

The rate of reaction of methyl iodide with sulfite ion is determined. In addition, the rate of reaction of methyl iodide with thiosulfate ion is reexamined and the rate of reaction of methyl iodide with bisulfite ion is estimated. A pronounced effect of ionic strength on the reaction rate in the methyl iodide – sulfite ion system is observed, this effect does not occur in the methyl iodide – thiosulfate ion system. The second order reaction rate constant and activation energy for the reaction of methyl iodide with the respective nucleophiles are: SO32−, 4.4 × 10−2M−1 s−1, 18.6 kcal mole−1; HSO3−, 1 × 10−3M−1 s−1, 18.4 kcal mole−1; and S2O32− 3.1 × 10−2M−1 s−1, 19.4 kcal mole−1.

The kinetics of formation of ruthenium(II) nitrogen complexes

1970 ◽  
Vol 48 (11) ◽  
pp. 1639-1644 ◽  
Author(s):  
Clive M. Elson ◽  
I. J. Itzkovitch ◽  
John A. Page
Keyword(s):  
Activation Energy ◽  
Order Rate Constant ◽  
Second Order ◽  
Kcal Mole ◽  
Potential Reduction ◽  
First Order ◽  
Kinetics Of Formation ◽  
Controlled Potential ◽  
Kinetics Of ◽  
Electrolyte Ph

The formation of nitrogen monomers by the reaction of Ru(NH3)5(H2O)2+ and cis-Ru(NH3)4(H2O)22+ with N2 has been shown to be first order in N2 and second order overall. The formation of bridging N2 dimers by the reaction of the ruthenium(II) pentaammine and tetraammine with the monomers has been shown to be second order overall.The reactions were studied in a H2SO4–K2SO4 electrolyte pH 3.3, μ = 0.30. The ruthenium(II) species were prepared by controlled potential reduction of known ruthenium(III) species at −0.50 V at a Hg cathode. The reactions of the reduced species with N2 or the monomers were followed spectrophotometrically.The second order rate constant at 25 °C and the activation energy for the substrate Ru(NH3)5(H2O)2+ with the respective nucleophiles are: N2, 8.0 × 10−2 M−1 s−1, 22.0 ± 0.1 kcal/mole; Ru(NH3)5N22+, 3.6 × 10−2 M−1 s−1, 19.9 ± 0.5 kcal/mole; Ru(NH3)4(H2O)N22+, 2.7 × 10−2 M−1 s−1, 20.4 ± 0.8 kcal/mole. For the substrate cis-Ru(NH3)4(H2O)22+ the values are: N2, 1.0 × 10−1 M−1 s−1, 20.4 ± 0.2 kcal/mole; Ru(NH3)5N22+, 6.8 × 10−2 M−1 s−1, 18.2 ± 0.1 kcal/mole; Ru(NH3)4(H2O)N22+, 7.2 × 10−2 M −1 s−1, 17.1 ± 0.2 kcal/mole.

Octahedral cobalt(III) complexes in dipolar aprotic solvents. I. The substitution of thiocyanate into the cis-Chlorodimethylsulphoxidobisethylenediaminecobalt(III) ion in anhydrous dimethylsulphoxide and NN-dimethylformamide

1965 ◽  
Vol 18 (4) ◽  
pp. 453 ◽  
Author(s):  
LF Chin ◽  
WA Millen ◽  
DW Watts
Keyword(s):  
Activation Energy ◽  
Ion Pair ◽  
Second Order ◽  
Aprotic Solvents ◽  
Kcal Mole ◽  
Dissociative Mechanism ◽  
Thiocyanate Ion ◽  
First Order ◽  
Rate Determining Step ◽  
Dipolar Aprotic Solvents

The substitution of thiocyanate ion into the cis-chlorodimethylsulphoxidobisethylenediaminecobalt(III) ion, cis-(Coen2(DMSO)Cl)2+, has been studied in the solvents dimethylsulphoxide (DMSO) and NN-dimethylformamide (DMF). In DMSO the reaction shows second-order characteristics which are accounted for by an ion-pair dissociative mechanism (SNIIP). The activation energy is 30.1 kcal mole-1. In DMF the entry is first-order, the rate determining step being solvolysis to the intermediate cis-(Coen2(DMF)Cl)2+ which has been isolated as the nitrate. In high thiocyanate concentrations the rate shows some thiocyanate dependence due to the competition of ion-paired thiocyanate with the DMF solvent for coordination following the DMSO dissociation. The activation energy for this substitution is 17.5 kcal mole-1.

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