A Chemical Dynamics Study of the Reaction of the Methylidyne Radical (CH, X2Π) with Dimethylacetylene (CH3CCCH3, X1A1g)

2021 ◽  
Author(s):  
Chao He ◽  
Kazuumi Fujioka ◽  
Anatoliy A Nikolayev ◽  
Long Zhao ◽  
Srinivas Doddipatla ◽  
...  
Keyword(s):  
Gas Phase ◽  
Collision Energy ◽  
Experimental Results ◽  
Phase Reaction ◽  
Chemical Dynamics ◽  
Single Collision ◽  
Gas Phase Reaction

The gas-phase reaction of the methylidyne (CH; X2Π) radical with dimethylacetylene (CH3CCCH3; X1A1g) was studied at a collision energy of 20.6 kJ mol-1 under single collision conditions with experimental results...

scholarly journals Bimolecular Reaction Dynamics in the Phenyl - Silane System: Exploring the Prototype of a Radical Substitution Mechanism

2018 ◽  
Author(s):  
Michael Lucas ◽  
Aaron M. Thomas ◽  
Tao Yang ◽  
Ralf I. Kaiser ◽  
Alexander M. Mebel ◽  
...  
Keyword(s):  
Gas Phase ◽  
Hydrogen Abstraction ◽  
Carbon Star ◽  
Bimolecular Reaction ◽  
Circumstellar Envelope ◽  
Phase Reaction ◽  
Chemical Dynamics ◽  
Substitution Reactions ◽  
Single Collision ◽  
Radical Substitution

<p>We present a combined experimental and theoretical investigation of the bimolecular gas phase reaction of the phenyl radical (C<sub>6</sub>H<sub>5</sub>) with silane (SiH<sub>4</sub>) under single collision conditions to investigate the chemical dynamics of forming phenylsilane (C<sub>6</sub>H<sub>5</sub>SiH<sub>3</sub>) via a bimolecular radical substi­tu­tion mechanism at a tetra-coordinated silicon atom. Verified by electronic structure and quasiclassical trajectory calculations, the replacement of a single carbon atom in methane by silicon lowers the barrier to substi­tu­ti­on thus defying conventional wisdom that tetra-coordinated hydrides undergo preferentially hydrogen abstraction. This reaction mechanism provides funda­men­tal insights into the hitherto unexplored gas phase chemical dynamics of radical substitution reactions of mononuclear main group hydrides under single collision conditions and highlights the distinct reactivity of silicon compared to its isovalent carbon. This mechanism might be also involved in the synthesis of cyanosilane (SiH<sub>3</sub>CN) and methylsilane (CH<sub>3</sub>SiH<sub>3</sub>) probed in the circumstellar envelope of the carbon star IRC+10216. </p>

scholarly journals Bimolecular Reaction Dynamics in the Phenyl - Silane System: Exploring the Prototype of a Radical Substitution Mechanism

2018 ◽  
Author(s):  
Michael Lucas ◽  
Aaron M. Thomas ◽  
Tao Yang ◽  
Ralf I. Kaiser ◽  
Alexander M. Mebel ◽  
...  
Keyword(s):  
Gas Phase ◽  
Hydrogen Abstraction ◽  
Carbon Star ◽  
Bimolecular Reaction ◽  
Circumstellar Envelope ◽  
Phase Reaction ◽  
Chemical Dynamics ◽  
Substitution Reactions ◽  
Single Collision ◽  
Radical Substitution

<p>We present a combined experimental and theoretical investigation of the bimolecular gas phase reaction of the phenyl radical (C<sub>6</sub>H<sub>5</sub>) with silane (SiH<sub>4</sub>) under single collision conditions to investigate the chemical dynamics of forming phenylsilane (C<sub>6</sub>H<sub>5</sub>SiH<sub>3</sub>) via a bimolecular radical substi­tu­tion mechanism at a tetra-coordinated silicon atom. Verified by electronic structure and quasiclassical trajectory calculations, the replacement of a single carbon atom in methane by silicon lowers the barrier to substi­tu­ti­on thus defying conventional wisdom that tetra-coordinated hydrides undergo preferentially hydrogen abstraction. This reaction mechanism provides funda­men­tal insights into the hitherto unexplored gas phase chemical dynamics of radical substitution reactions of mononuclear main group hydrides under single collision conditions and highlights the distinct reactivity of silicon compared to its isovalent carbon. This mechanism might be also involved in the synthesis of cyanosilane (SiH<sub>3</sub>CN) and methylsilane (CH<sub>3</sub>SiH<sub>3</sub>) probed in the circumstellar envelope of the carbon star IRC+10216. </p>

Kinetics and Mechanism of the Thermal Gas-Phase Reaction between NO2 and Perfluoropropene

2004 ◽  
Vol 218 (5) ◽  
pp. 575-598 ◽  
Author(s):  
R. M. Romano ◽  
Joanna Czarnowski
Keyword(s):  
Gas Phase ◽  
Rate Constant ◽  
Total Pressure ◽  
Consumption Rate ◽  
Initial Pressure ◽  
Experimental Results ◽  
Unimolecular Dissociation ◽  
Static System ◽  
Phase Reaction ◽  
Gas Phase Reaction

AbstractThe reaction of NO2 with perfluoropropene (C3F6) has been studied at 413.1, 421.0 and 432.8K, using a conventional static system. The initial pressure of NO2 was varied between 43.6 and 204.0Torr and that of C3F6 between 10.2 and 108.5Torr. Several experiments were made adding CF4, varying its pressure from 338.8 to 433.6Torr. Four products were observed: NO and perfluoropropene oxide (PFPO), formed in equivalent amounts, CF3CF(NO2)CF2NO2 and CF3C(O)CF2NO2. The relation R=[PFPO]/([CF3CF(NO2)CF2NO2] + [CF3C(O)CF2NO2]) increases with temperature and decreases as the concentration of NO2 and the total pressure M increase. The yields of PFPO, based on the amount of C3F6 consumed, varied between 63 and 89% and those of CF3CF(NO2)CF2NO2 between 0.33 and 0.08%. Increasing the temperature, the yields of CF3C(O)CF2NO2 decreased from 0.04 to 0.01%. The reaction is homogenous and the consumption rate of perfluoropropene, −d[C3F6]/dt= k1[C3F6][NO2], is independent of the total pressure. The following mechanism is postulated to explain the experimental results: 1) C3F6 + NO2 → CF3C•FCF2NO2, 2) CF3C•FCF2NO2 → PFPO+NO, 3) CF3C•FCF2NO2 + NO2+M → CF3CF(NO2)CF2NO2+M, 4) CF3C•FCF2NO2 + NO2 → CF3C(O)CF2NO2+FNO. k1=(4.57±1.4)×106exp(−(15.44±1.2) kcal mol−1/RT) dm3mol−1s−1. The value of k2, the rate constant for the unimolecular dissociation of the radical CF3C•FCF2NO2, was found to be of order of 1014s−1.

Chemical dynamics study on the gas-phase reaction of the D1-silylidyne radical (SiD; X2Π) with deuterium sulfide (D2S) and hydrogen sulfide (H2S)

2021 ◽  
Author(s):  
Shane J. Goettl ◽  
Srinivas Doddipatla ◽  
Zhenghai Yang ◽  
Chao He ◽  
Ralf I. Kaiser ◽  
...  
Keyword(s):  
Hydrogen Sulfide ◽  
Gas Phase ◽  
Phase Formation ◽  
Mass Velocity ◽  
Center Of Mass ◽  
Phase Reaction ◽  
Chemical Dynamics ◽  
Contour Map ◽  
Gas Phase Reaction

Center-of-mass velocity flux contour map for the reaction of the D1-silylidyne radical (SiD) with deuterium sulfide (D2S) leading to the gas-phase formation of D2-silanethione (D2SiS).

Prediction of Alkanolamine pKa Values by Combined Molecular Dynamics Free Energy Simulations and ab initio Calculations

2019 ◽  
Author(s):  
Javad Noroozi ◽  
William Smith
Keyword(s):  
Molecular Dynamics ◽  
Free Energy ◽  
Ab Initio Calculations ◽  
Gas Phase ◽  
Quantum Chemical ◽  
Phase Reaction ◽  
Pka Values ◽  
Gas Phase Reaction ◽  
Reaction Free Energy ◽  
Energy Simulations

We use molecular dynamics free energy simulations in conjunction with quantum chemical calculations of gas phase reaction free energy to predict alkanolamines pka values. <br>

Metabolic alteration of Methylococcus capsulatus str. Bath during a microbial gas-phase reaction

2021 ◽  
Vol 330 ◽  
pp. 125002
Author(s):  
Yan-Yu Chen ◽  
Yuki Soma ◽  
Masahito Ishikawa ◽  
Masatomo Takahashi ◽  
Yoshihiro Izumi ◽  
...  
Keyword(s):  
Gas Phase ◽  
Phase Reaction ◽  
Methylococcus Capsulatus ◽  
Gas Phase Reaction ◽  
Metabolic Alteration

scholarly journals Influence of Water on the Gas-Phase Reaction of Dimethyl Sulfide with BrO in the Marine Boundary Layer

ACS Omega ◽  
2021 ◽  
Vol 6 (3) ◽  
pp. 2410-2419
Author(s):  
Junyao Li ◽  
Narcisse T. Tsona ◽  
Shanshan Tang ◽  
Xiuhui Zhang ◽  
Lin Du
Keyword(s):  
Boundary Layer ◽  
Gas Phase ◽  
Dimethyl Sulfide ◽  
Marine Boundary Layer ◽  
Phase Reaction ◽  
Gas Phase Reaction ◽  
Influence Of Water

Preparation of SiC hollow particles by gas-phase reaction in the SiH4-CH4-H2 system

1989 ◽  
Vol 24 (10) ◽  
pp. 3679-3685 ◽  
Author(s):  
C. H. Pai ◽  
K. Koumoto ◽  
S. Takeda ◽  
H. Yanagida
Keyword(s):  
Gas Phase ◽  
Phase Reaction ◽  
Hollow Particles ◽  
Gas Phase Reaction

scholarly journals Fabrication and Particle Size Control of Oxide Nanoparticles by Gas Phase Reaction Assisted with DC Plasma

2007 ◽  
Vol 44 (6) ◽  
pp. 447-452 ◽  
Author(s):  
Akira Watanabe ◽  
Motoharu Fujii ◽  
Masayoshi Kawahara ◽  
Takehisa Fukui ◽  
Kiyoshi Nogi
Keyword(s):  
Particle Size ◽  
Gas Phase ◽  
Size Control ◽  
Oxide Nanoparticles ◽  
Phase Reaction ◽  
Dc Plasma ◽  
Gas Phase Reaction ◽  
Particle Size Control
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