ChemInform Abstract: LASER-INITIATED CHEMICAL REACTIONS- ATOMIC CHLORINE + HYDROGEN SULFIDE → HYDROGEN CHLORIDE + HYDROGEN MONOSULFIDE- RATE CONSTANT, PRODUCT ENERGY DISTRIBUTION, AND DIRECT DETECTION OF A CHAIN MECHANISM

1978 ◽  
Vol 9 (46) ◽  
Author(s):  
M. BRAITHWAITE ◽  
S. R. LEONE
Keyword(s):  
Hydrogen Sulfide ◽  
Energy Distribution ◽  
Hydrogen Chloride ◽  
Chemical Reactions ◽  
Rate Constant ◽  
Direct Detection ◽  
Chain Mechanism ◽  
A Chain ◽  
Atomic Chlorine

The expected time to attain chemical equilibrium from a thermodynamic probabilistic analysis

2012 ◽  
Vol 90 (3) ◽  
pp. 243-255
Author(s):  
Christopher Pastore ◽  
Moishe Garfinkle
Keyword(s):  
Experimental Data ◽  
Chemical Reactions ◽  
Chain Mechanism ◽  
Reaction Paths ◽  
Probabilistic Algorithm ◽  
Third Order ◽  
Expected Time ◽  
The Subject ◽  
A Chain ◽  
Stochastic Reaction

Employing a stochastic model, both Planck and Fokker proposed almost a century ago that stoichiometric chemical reactions proceed by a chain mechanism involving discrete reaction steps. To determine whether such a chain mechanism was in fact a valid mechanism for chemical reactions was the subject of a recent study (Garfinkle, M. 2002. J. Phys. Chem. 106A: 490). Using a thermodynamic–probabilistic algorithm the stochastic reaction paths were found to be in excellent agreement with the observed reaction paths plotted from experimental data. This study was then extended to test the conclusions of Ehrenfest and Prigogine that a chain mechanism dictates that the number of discrete reaction steps required for a chemical reaction to attain equilibrium must be finite. The stochastic and empirical reaction paths were compared using experimental data for first-, second-, and third-order reactions as well as fractional order reactions. The empirical verification was excellent.

Photoisomerization of 2-Alkenes in the Presence of Hydrogen Sulfide

1972 ◽  
Vol 50 (15) ◽  
pp. 2400-2406 ◽  
Author(s):  
Guy J. Collin ◽  
Patrick M. Perrin
Keyword(s):  
Hydrogen Sulfide ◽  
Liquid Phase ◽  
Quantum Yields ◽  
Chain Mechanism ◽  
Thiyl Radicals ◽  
Trans Isomerization ◽  
A Chain ◽  
Effect Of Oxygen

In far u.v. photochemistry, the radicals formed react with hydrogen sulfide to give, amongst others, thiyl radicals (HS•). These radicals initiate the cis–trans isomerization of 2-olefins in a chain mechanism. We have tried to demonstrate that the thiyl radicals are also chain carriers. Quantum yields for the isomerization of cis to trans compound are probably of the order of 6–7 × 103 and the length of the chain, of the order of 4.7 × 103. We have also studied the radiolysis of these reactions in the liquid phase. The effect of oxygen and of conjugated di-olefins, such as 1,3-butadiene and 1,3-pentadiene is also discussed.

THE KINETICS OF THE OXIDATION OF GASEOUS ACETALDEHYDE

1932 ◽  
Vol 7 (2) ◽  
pp. 149-161 ◽  
Author(s):  
W. H. Hatcher ◽  
E. W. R. Steacie ◽  
Frances Howland
Keyword(s):  
Carbon Dioxide ◽  
Formic Acid ◽  
Induction Period ◽  
Reaction Vessel ◽  
Oxidation Products ◽  
Main Reaction ◽  
Chain Mechanism ◽  
Subsequent Reaction ◽  
A Chain ◽  
Kinetics Of

The kinetics of the oxidation of gaseous acetaldehyde have been investigated from 60° to 120 °C. by observing the rate of pressure decrease in a system at constant volume. A considerable induction period exists, during which the main products of the reaction are carbon dioxide, water, and formic acid. The main reaction in the subsequent stages involves the formation of peroxides and their oxidation products. The heat of activation of the reaction is 8700 calories per gram molecule. The indications are that the reactions occurring during the induction period are heterogeneous. The subsequent reaction occurs by a chain mechanism. The chains are initiated at the walls of the reaction vessel, and are also largely broken at the walls.

Réactions ion–molécule dans les méthylbutènes: radiolyse du méthane

1976 ◽  
Vol 54 (4) ◽  
pp. 555-559
Author(s):  
Guy J. Collin
Keyword(s):  
Tertiary Structure ◽  
Ionic Mechanism ◽  
Chain Mechanism ◽  
A Chain

The radiolysis of gaseous methane has been studied in the presence of one of the three methylbutenes. We have observed an important isomerization of the added olefin. An ionic mechanism initiated by the CH5+ and C2H5+ ions seems to be compatible with the observations reported. Isomerization proceeds through a chain mechanism where the chain carrier may be the tert-C5H11+ ion. In the presence of 3-methyl-1-butene, the initially formed (CH3)2CHCHCH3+ ion isomerizes to the tertiary structure before producing the observed isomerization.

scholarly journals On apparent barrier-free reactions

2020 ◽  
Vol 3 (1) ◽  
pp. 3-8
Author(s):  
Maikel Ballester
Keyword(s):  
Low Temperature ◽  
Chemical Reactions ◽  
Rate Constant ◽  
Kinetic Models ◽  
Rate Coefficient ◽  
Minimum Energy ◽  
Temperature Limit ◽  
Rate Coefficients ◽  
Minimum Energy Path ◽  
Full Dimension

Rate coefficients of bi-molecular chemical reactions are fundamental for kinetic models. The rate coefficient dependence on temperature is commonly extracted from the analyses of the reaction minimum energy path. However, a full dimension study of the same reaction may suggest a different asymptotic low-temperature limit in the rate constant than the obtained from the energetic profile.

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