scholarly journals The Atmospherically Important Reaction of Hydroxyl Radicals with Methyl Nitrate: A Theoretical Study Involving the Calculation of Reaction Mechanisms, Enthalpies, Activation Energies, and Rate Coefficients

2017 ◽  
Vol 121 (35) ◽  
pp. 6554-6567
Author(s):  
Maggie Ng ◽  
Daniel K. W. Mok ◽  
Edmond P. F. Lee ◽  
John M. Dyke
Keyword(s):  
Hydroxyl Radicals ◽  
Reaction Mechanisms ◽  
Theoretical Study ◽  
Activation Energies ◽  
Rate Coefficients ◽  
Methyl Nitrate

A theoretical study of the mechanism of the atmospherically relevant reaction of chlorine atoms with methyl nitrate, and calculation of the reaction rate coefficients at temperatures relevant to the troposphere

2015 ◽  
Vol 17 (11) ◽  
pp. 7463-7476 ◽  
Author(s):  
Maggie Ng ◽  
Daniel K. W. Mok ◽  
Edmond P. F. Lee ◽  
John M. Dyke
Keyword(s):  
Reaction Rate ◽  
Theoretical Study ◽  
Rate Coefficients ◽  
Chlorine Atoms ◽  
Methyl Nitrate ◽  
First Time ◽  
Atmospherically Relevant

Computed rate coefficients of the atmospherically important Cl + CH3ONO2 → HCl + CH2ONO2 reaction reported for the first time.

The application of wave-mechanics to reactions involving hydrogen and diplogen

1934 ◽  
Vol 30 (4) ◽  
pp. 508-513
Author(s):  
R. A. Smith
Keyword(s):  
Activation Energy ◽  
Quantum Theory ◽  
Chemical Reactions ◽  
Reaction Mechanisms ◽  
Reaction Rate ◽  
Theoretical Study ◽  
Electronic States ◽  
Activation Energies ◽  
Wave Mechanics

A considerable amount of work has recently been done on the application of wave-mechanics to the theoretical study of chemical reactions. This has consisted chiefly in calculating activation energies and strengths of various bonds by consideration of electronic states in molecules. Some work has also been done on actual reaction mechanisms. It is evident from the latter that, owing to the large masses of the particles concerned, the quantum theory and the classical treatment will give different results only for reactions involving hydrogen or diplogen. Previous attempts to deal with such reactions have consisted simply of calculating the permeabilityG(W) of a barrier of height equal to the activation energy for protons of energyW.The reaction rate is then assumed to be given by

Determination of Complex Reaction Mechanisms

2006 ◽  
Author(s):  
John Ross ◽  
Igor Schreiber ◽  
Marcel O. Vlad
Keyword(s):  
Reaction Mechanism ◽  
Reaction Mechanisms ◽  
Reaction Pathway ◽  
Chemical Species ◽  
Rate Coefficients ◽  
Chemical System ◽  
Evolutionary Development ◽  
Complex Reaction ◽  
Oscillatory Reactions

In a chemical system with many chemical species several questions can be asked: what species react with other species: in what temporal order: and with what results? These questions have been asked for over one hundred years about simple and complex chemical systems, and the answers constitute the macroscopic reaction mechanism. In Determination of Complex Reaction Mechanisms authors John Ross, Igor Schreiber, and Marcel Vlad present several systematic approaches for obtaining information on the causal connectivity of chemical species, on correlations of chemical species, on the reaction pathway, and on the reaction mechanism. Basic pulse theory is demonstrated and tested in an experiment on glycolysis. In a second approach, measurements on time series of concentrations are used to construct correlation functions and a theory is developed which shows that from these functions information may be inferred on the reaction pathway, the reaction mechanism, and the centers of control in that mechanism. A third approach is based on application of genetic algorithm methods to the study of the evolutionary development of a reaction mechanism, to the attainment given goals in a mechanism, and to the determination of a reaction mechanism and rate coefficients by comparison with experiment. Responses of non-linear systems to pulses or other perturbations are analyzed, and mechanisms of oscillatory reactions are presented in detail. The concluding chapters give an introduction to bioinformatics and statistical methods for determining reaction mechanisms.

Reactivity and reaction mechanisms of sulfate radicals with lindane: An experimental and theoretical study

2021 ◽  
pp. 111523
Author(s):  
Lei He ◽  
Lingjun Bu ◽  
Richard Spinney ◽  
Dionysios D. Dionysiou ◽  
Ruiyang Xiao
Keyword(s):  
Reaction Mechanisms ◽  
Theoretical Study ◽  
Sulfate Radicals

Theoretical study of the dark-oxidation reaction mechanisms for organic polymers

2006 ◽  
Vol 427 (1-3) ◽  
pp. 35-40 ◽  
Author(s):  
Guixiu Wang ◽  
Rongxiu Zhu ◽  
Dongju Zhang ◽  
Chengbu Liu
Keyword(s):  
Reaction Mechanisms ◽  
Oxidation Reaction ◽  
Theoretical Study ◽  
Organic Polymers

scholarly journals H–Abstraction from Dimethyl Sulfide in the Presence of an Excess of Hydroxyl Radicals. A Quantum Chemical Evaluation of Thermochemical and Kinetic Parameters Unveil an Alternative Pathway to Dimethyl Sulfoxide.

2020 ◽  
Author(s):  
Zoi Salta ◽  
Jacopo Lupi ◽  
Vincenzo Barone ◽  
Oscar Ventura
Keyword(s):  
Dimethyl Sulfoxide ◽  
Hydroxyl Radicals ◽  
Quantum Chemical ◽  
Dimethyl Sulfide ◽  
Computational Study ◽  
Alternative Pathway ◽  
Oxidation Mechanism ◽  
State Theory ◽  
Rate Coefficients ◽  
Reduced Sulfur Compounds

<div> Elucidation of the oxidation mechanism of naturally emitted reduced sulfur compounds, especially dimethyl sulfide, plays a central role in understanding background acid precipitation in the natural environment. Most frequently, theoretical studies of the addition and H-elimination reactions of dimethyl sulfide with hydroxyl radicals are studied considering the presence of oxygen that further reacts with the radicals formed in the initial steps. Although the reaction of intermediate species with additional hydroxyl radicals has been considered as part of the global mechanism of oxidation, few if any attention has been dedicated to the possibility of reactions of the initial radicals with a second •OH molecule. In this work we performed a computational study using quantum-chemical methods, of the mechanism of H-abstraction from dimethyl sulfide under normal atmospheric conditions and in reaction chambers at different O2 partial pressure, including complete absence of oxygen. Additionally, important rate coefficients were computed using canonical and variational transition state theory. The rate coefficient for abstraction affords a 4.72 x 10-12 cm3 molecule1 s-1 value, very close to the most recent experimental one (4.13 x 10-12 cm3 molecule-1 s-1). According to our best results, the initial methyl thiomethyl radical was obtained at -25.2 kcal/mol (experimentally -22.4 kcal/mol), and four important paths were identified on the potential energy surface. From the interplay of thermochemical and kinetic arguments, it was possible to demonstrate that the preferred product of the reaction of dimethyl sulfide with two hydroxyl radicals, is actually dimethyl sulfoxide. </div><div> </div>

Contribution to the Theoretical Study of Reaction Mechanisms

1979 ◽  
pp. 91-144 ◽  
Author(s):  
G. Leroy ◽  
M. Sana ◽  
L. A. Burke ◽  
M.-T. Nguyen
Keyword(s):  
Reaction Mechanisms ◽  
Theoretical Study
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