Hydrogen abstraction from organosilicon compounds. The reactions of fluoromethyl radicals with tetramethylsilane. Polar effects in gas phase reactions

1971 ◽  
Vol 3 (1) ◽  
pp. 69-84 ◽  
Author(s):  
J. A. Kerr ◽  
D. M. Timlin
Keyword(s):  
Gas Phase ◽  
Hydrogen Abstraction ◽  
Organosilicon Compounds ◽  
Gas Phase Reactions

Methylene. III. Gas phase reactions with 1-chloropropane

1969 ◽  
Vol 312 (1509) ◽  
pp. 141-161 ◽  
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Hydrogen Abstraction ◽  
The Other ◽  
Gas Phase Reactions ◽  
Other Hand ◽  
Chlorine Substituent ◽  
High Degree ◽  
Singlet Methylene

The work described in this and the following paper is a continuation of that in parts I and II, devoted to elucidation of the mechanism of the reactions of methylene with chloroalkanes, with particular reference to the reactivities of singlet and triplet methylene in abstraction and insertion processes. The products of the reaction between methylene, prepared by the photolysis of ketene, and 1-chloropropane have been identified and estimated and their dependence on reactant pressures, photolysing wavelength and presence of foreign gases (oxygen and carbon mon­oxide) has been investigated. Both insertion and abstraction mechanisms contribute significantly to the over-all reaction, insertion being relatively much more important than with chloroethane. This type of process appears to be confined to singlet methylene. If, as seems likely, there is no insertion into C—Cl bonds under our conditions (see part IV), insertion into C2—H and C3—H bonds occurs in statistical ratio, approximately. On the other hand, the chlorine substituent reduces the probability of insertion into C—H bonds in its vicinity. As in the chloroethane system, both species of methylene show a high degree of selectivity in their abstraction reactions. We find that k S Cl / k S H >7.7, k T Cl / k T H < 0.14, where the k ’s are rate constants for abstraction, and the super- and subscripts indicate the species of methylene and the type of atom abstracted, respectively. Triplet methylene is discriminating in hydrogen abstraction from 1-C 3 H 7 Cl, the overall rates for atoms attached to C1, C2, C3 being in the ratios 2.63:1:0.

scholarly journals Unimolecular Gas-phase Reactions of Organosilicon Compounds. Part XV. Acetyltrimethylsilane, CH3COSi(CH3)3

2003 ◽  
Vol 51 (2) ◽  
pp. 365-367 ◽  
Author(s):  
Susumu TAJIMA ◽  
Daisuke WATANABE ◽  
Satoshi NAKAJIMA ◽  
Nico M. M. NIBBERING
Keyword(s):  
Gas Phase ◽  
Organosilicon Compounds ◽  
Gas Phase Reactions

Excimer Laser Photofragmentation of TMA on Aluminum: Identification of Photoproduct Desorption Dynamics

1988 ◽  
Vol 131 ◽  
Author(s):  
T. E. Orlowski ◽  
D. A. Mantell
Keyword(s):  
Gas Phase ◽  
Excimer Laser ◽  
Direct Evidence ◽  
Hydrogen Abstraction ◽  
Sample Surface ◽  
Translational Energy ◽  
Quadrupole Mass ◽  
Gas Phase Reactions ◽  
Si Substrates ◽  
Site Binding

ABSTRACTNew mechanistic details regarding aluminum deposition by ArF excimer laser photodecomposition of trimethylaluminum (TMA) adsorbed on aluminum covered SiO 2/Si substrates have been obtained using a time-of-flight quadrupole mass spectrometer. CH3 radicals and Al-(CH3)n (n = 1,2,3) species are efficiently photoejected from the surface with up to 0.22 eV of translational energy. Experiments at various TMA dosing levels reveal differences in desorbed fragment translational energy presumably associated with variations in surface site binding energy. No direct evidence is found for desorption of A1 from the surface indicating that A1 is more tightly bound than methyl-aluminum fragments. By carefully monitoring changes in fragment translational energy as an A1 deposit forms on the clean SiO2/Si substrate, we examine how the surface influences the onset of A1 growth. No evidence of ethane or methane desorption from the sample surface is found implying that radical recombination and hydrogen abstraction are primarily secondary gas phase reactions which are not surface initiated.

Methylene II. Gas phase reactions with ethyl chloride

1968 ◽  
Vol 306 (1485) ◽  
pp. 135-158 ◽  
Keyword(s):  
Carbon Monoxide ◽  
Gas Phase ◽  
Energy Content ◽  
Incident Light ◽  
Hydrogen Abstraction ◽  
Relative Concentration ◽  
Radical Mechanism ◽  
Gas Phase Reactions ◽  
Free Radical Mechanism ◽  
Singlet Methylene

In this work methylene was prepared by the photolysis of ketene, and the experiments include observations of the effects of changing the wavelength of the photolysing light and of introducing foreign gases. Results are consistent with a free-radical mechanism in which CH 2 abstracts a chlorine or a hydrogen atom from C 2 H 5 Cl: CH 2 +CH 3 CH 2 Cl→ k cl ĊH 2 Cl+CH 3 ĊH 2 , CH 2 +CH 3 CH 2 Cl→ k h1 ĊH 3 +ĊH 3 CH 3 Cl, } CH 2 +CH 3 CH 2 Cl→ k H2 ĊH 3 +CH 3 ċHCl. } ( k H ) All the fourteen products of the radical recombinations have been identified. Disproportionation of radicals and decomposition of excited molecules formed by recombinations yield additional products. Methylene insertion does not appear to play a significant role. When the incident light contains wavelengths in the region 2450 to 4000Å we find that k Cl / k H =1·62, k H1 / k H2 =0·098. If shorter wavelengths are excluded, or if nitrogen is added, lower values of k Cl / k H are obtained. On the other hand, in the presence of carbon monoxide the value of k Cl / k H may be greatly increased. It is suggested that these findings are attributable to differences in reactivity between singlet and triplet methylene. At longer wavelengths, or when nitrogen is present, the relative concentration of the singlet is reduced, but in the presence of carbon monoxide the triplet is removed preferentially (De Graff & Kistiakowsky 1967). Singlet methylene appears to be highly discriminating in its reactions, abstracting chlorine preferentially, while the triplet discriminates in favour of hydrogen abstraction. A kinetic analysis based on these ideas and consistent with the experimental observations shows that k S Cl / k S H >16·3, k T Cl / k T H <0·14. The selectivities shown by the two species of methylene are thought to be a result of differences in electronic structure rather than energy content.

Theoretical Study on Gas Phase Reactions of OH Hydrogen-Abstraction from Formyl Fluoride with Different Catalysts

2016 ◽  
Vol 29 (3) ◽  
pp. 325-334 ◽  
Author(s):  
Ding-mei Wang ◽  
Zheng-wen Long ◽  
Xing-feng Tan ◽  
Bo Long ◽  
Wei-jun Zhang
Keyword(s):  
Gas Phase ◽  
Theoretical Study ◽  
Hydrogen Abstraction ◽  
Gas Phase Reactions

scholarly journals Warm dust surface chemistry

2020 ◽  
Vol 634 ◽  
pp. A42 ◽  
Author(s):  
W. F. Thi ◽  
S. Hocuk ◽  
I. Kamp ◽  
P. Woitke ◽  
Ch. Rab ◽  
...  
Keyword(s):  
Gas Phase ◽  
Hydrogen Abstraction ◽  
Gas Phase Reactions ◽  
Weakly Bound ◽  
Detailed Model ◽  
Physico Chemical ◽  
Polycyclic Aromatic ◽  
Deuterium Hydride ◽  
Dust Grain ◽  
Grain Surface

Context. Molecular hydrogen (H2) is the main constituent of the gas in the planet-forming disks that surround many pre-main-sequence stars. H2 can be incorporated in the atmosphere of the nascent giant planets in disks. Deuterium hydride (HD) has been detected in a few disks and can be considered the most reliable tracer of H2, provided that its abundance throughout the disks with respect to H2 is well understood. Aims. We wish to form H2 and HD efficiently for the varied conditions encountered in protoplanetary disks: the densities vary from 104 to 1016 cm−3; the dust temperatures range from 5 to 1500 K, the gas temperatures go from 5 to a few 1000 Kelvin, and the ultraviolet radiation field can be 107 stronger than the standard interstellar field. Methods. We implemented a comprehensive model of H2 and HD formation on cold and warm grain surfaces and via hydrogenated polycyclic aromatic hydrocarbons in the physico-chemical code PROtoplanetary DIsk MOdel. The H2 and HD formation on dust grains can proceed via the Langmuir-Hinshelwood and Eley-Ridel mechanisms for physisorbed or chemisorbed H (D) atoms. H2 and HD also form by H (D) abstraction from hydrogenated neutral and ionised PAHs and via gas phase reactions. Results. H2 and HD are formed efficiently on dust grain surfaces from 10 to ~700 K. All the deuterium is converted into HD in UV shielded regions as soon as H2 is formed by gas-phase D abstraction reactions. The detailed model compares well with standard analytical prescriptions for H2 (HD) formation. At low temperature, H2 is formed from the encounter of two physisorbed atoms. HD molecules form on the grain surfaces and in the gas-phase. At temperatures greater than 20 K, the encounter between a weakly bound H- (or D-) atom or a gas-phase H (D) atom and a chemisorbed atom is the most efficient H2 formation route. H2 formation through hydrogenated PAHs alone is efficient above 80 K. However, the contribution of hydrogenated PAHs to the overall H2 and HD formation is relatively low if chemisorption on silicate is taken into account and if a small hydrogen abstraction cross-section is used. The H2 and HD warm grain surface network is a first step in the construction of a network of high-temperature surface reactions.

Gas-Phase Reactions

1981 ◽  
Author(s):  
Victor N. Kondratiev ◽  
Evgeniĭ E. Nikitin
Keyword(s):  
Gas Phase ◽  
Gas Phase Reactions
Sign in / Sign up

Export Citation Format

Share Document