Reactions of Thiyl Radicals. VII. Photolysis of Methyl Sulfide Vapor

1972 ◽  
Vol 50 (6) ◽  
pp. 844-852 ◽  
Author(s):  
P. M. Rao ◽  
A. R. Knight
Keyword(s):  
Wavelength Range ◽  
Sulfur Hexafluoride ◽  
Quantum Yields ◽  
Primary Process ◽  
Methyl Radicals ◽  
Methyl Sulfide ◽  
Thiyl Radicals ◽  
Several Variables ◽  
Bond Scission ◽  
Function Of Several Variables

The photolysis of methyl sulfide vapor has been investigated as a function of substrate pressure, exposure time, and temperature in the wavelength range 2000 to 2300 Å. The effects of added propane, sulfur hexafluoride, and 2-methylpentane have been studied. The principal products of the decomposition are CH4, C2H6, CH3SSCH3, and CH3SH. The data indicate direct C—S bond scission in the primary process giving rise to "hot" CH3 and CH3S radicals. A mechanism in which disproportionation of methylthiyl radicals is a very minor process is proposed.The reactions of CH3 and CH3S radicals with methyl sulfide have been examined also by photolyzing CH3SSCH3 and CH3COCH3 in the presence of CH3SCH3. Quantum yields at 2288 Å have been determined as a function of several variables. A number of rate parameters for the reactions of methyl radicals and methylthiyl radicals have been calculated.

PRIMARY PROCESS STUDIES BY MONOISOTOPIC PHOTOSENSITIZATION ON THE REACTIONS OF Hg 6(3P1) ATOMS WITH ALKYL CHLORIDES

1964 ◽  
Vol 42 (9) ◽  
pp. 2056-2064 ◽  
Author(s):  
J. K. S. Wan ◽  
O. P. Strausz ◽  
W. F. Allen ◽  
H. E. Gunning
Keyword(s):  
Mercury Vapor ◽  
Quantum Yields ◽  
Primary Process ◽  
Reaction Parameters ◽  
Specific Nature ◽  
Electrodeless Discharge ◽  
Discharge Source ◽  
Bond Scission ◽  
Decomposition Formula ◽  
Process Studies

The specific nature of the primary process in the reaction of 202Hg 6(3P1) atoms, photoexcited in natural mercury vapor by a cool 202Hg electrodeless discharge source, with CH3Cl has been examined in detail. Primary C–Cl bond scission occurs with unit efficiency. Quantum yields (φ) for the two primary modes of decomposition[Formula: see text]were found to have values of 0.71 (b) and 0.29 (a). The effect of various reaction parameters on the 202Hg enrichment in the calomel product has been investigated and the importance of isotopic mercury depletion in the reaction zone demonstrated by the use of intermittent illumination.A brief study of the reaction of ethyl, n-propyl, i-propyl, t-butyl, and n-amyl chlorides has revealed a relation between the molecular structure of the alleyl chloride and the efficiency of the monoisotopic route (a) to calomel formation. Thus, while the reactions of all the normal alkyl chlorides have φa values between 0.29 and 0.32, φa (isopropyl chloride) is only 0.22 and φa (t-butyl chloride) is 0.17.

THE Hg 6(3P1) PHOTOSENSITIZATION OF CHLORODIFLUOROMETHANE

1965 ◽  
Vol 43 (5) ◽  
pp. 1022-1029 ◽  
Author(s):  
M. G. Bellas ◽  
O. P. Strausz ◽  
H. E. Gunning
Keyword(s):  
Incident Light ◽  
Strong Dependence ◽  
Quantum Yields ◽  
Primary Process ◽  
Reaction Products ◽  
Light Intensities ◽  
Principal Reaction ◽  
Bond Scission ◽  
Circulatory Apparatus ◽  
Cl Atoms

The reaction was studied in a circulatory apparatus under a variety of conditions. The sole primary process occurring is C—Cl bond scission. The Cl atoms formed in the primary step, through an abstractive attack on the substrate, generate chlorodifluoromethyl radicals (CF2Cl) All principal reaction products, CF2H2, CF2Cl2, CF2ClCF2Cl, CF2HCF2H, and CF2HCF2Cl, can be accounted for by the combination–disproportionation reactions of the CF2H• and CF2Cl• radicals. The observed strong dependence of the primary quantum yields on the incident light intensities has been ascribed to a rapid substrate-reforming step.

Reactions of thiyl radicals. XII. Triplet mercury photosensitized decomposition of ethyl sulfide in the gas phase

1976 ◽  
Vol 54 (8) ◽  
pp. 1290-1295 ◽  
Author(s):  
Conrad S. Smith ◽  
Arthur R. Knight
Keyword(s):  
Quantum Yield ◽  
Gas Phase ◽  
Quantum Yields ◽  
Second Step ◽  
Primary Process ◽  
Reaction Products ◽  
Process Comparison ◽  
Thiyl Radicals ◽  
Ethyl Radicals ◽  
High Sulfide

The triplet mercury photosensitized decomposition of ethyl sulfide vapour has been studied at 25 °C. The reaction products include C2H4 (Φ0 = 0.075), C2H6 (Φ0 = 0.043), C4H10 (Φ0 = 0.011), C2H5SH (Φ0 = 0.068), 4-methyl-3-thiahexane (Φ0 = 0.011), and C2H5SSC2H5 (Φ0 = 0.175). The overall decomposition quantum yield is 0.38 at high sulfide pressures. The initial decomposition gives principally ethyl radicals and ethylthiyl radicals; a second step which yields ethylene and ethanethiol may account for up to 20% of the primary process. Comparison of the direct and sensitized decompositions indicates that both likely originate in the triplet manifold of ethyl sulfide.Primary decomposition quantum yields have been accurately redetermined for the direct, 254 nm, photolysis of methyl sulfide (0.51), methylethyl sulfide (0.46), and ethyl sulfide (0.49).

Reactions of Thiyl Radicals. X. Photolysis of Ethyl Sulfide Vapor

1973 ◽  
Vol 51 (5) ◽  
pp. 780-786 ◽  
Author(s):  
Conrad S. Smith ◽  
Arthur R. Knight
Keyword(s):  
Reaction Rates ◽  
Quantum Yields ◽  
Minor Role ◽  
Primary Decomposition ◽  
Primary Process ◽  
Temperature Reaction ◽  
Reaction Products ◽  
Thiyl Radicals ◽  
Pressure Time ◽  
A Minor

The photolysis of ethyl sulfide vapor at 2537 Å has been investigated as a function of substrate and CF4 pressure, time, and temperature. Reaction products with quantum yields in parentheses are ethyl disulfide (0.178), ethane (0.138), butane (0.086), ethanethiol (0.096), 4-methyl-3-thiahexane (0.034) and 4-methyl-3,5-dithiaheptane.Ethyl and ethylthiyl radicals are formed in the primary process and the product yields indicate a net primary decomposition quantum yield of 0.48. A reaction mechanism involving subsequent reactions of the primary fragments is proposed and explains the observed products and the observed variation in rates. Excited radicals and hot radical combination products play a minor role in this system, in contrast to the behavior of lower molecular weight sulfides. Secondary photolysis of the disulfide produced and consumption of ethanethiol are important factors in determining the time dependence of reaction rates in this system.

The Mechanism of the HgH A22Π3/2 → X2Σ+ Emission in the Hg(63P0) Photosensitization of Hydrogen and the Alkanes

1973 ◽  
Vol 51 (8) ◽  
pp. 1207-1214 ◽  
Author(s):  
A. C. Vikis ◽  
D. J. Le Roy
Keyword(s):  
Ground State ◽  
Quantum Yields ◽  
Primary Process ◽  
Relative Quantum

The mechanism of the HgH A22Π3/2 → X2Σ+ emission detected in the Hg(63P0) photosensitized decomposition of H2 and some of the lower alkanes, RH, was investigated. It was concluded that ground state HgH was formed in the primary process Hg(63P0) + RH(or H2) → HgH(X2Σ+) + R(or H). The HgH A22Π3/2 → X2Σ+ emission and presumably the A12Π1/2 → X2Σ+ and B2Σ+ → X2Σ+ emission, also observed in the above systems, result from secondary excitation of ground state HgH on collision with Hg(63P0). Studies of the emission made possible the estimation of relative quantum yields for the above primary process.

Reactions of Thiyl Radicals. XI. Further Investigations of Thiol–Disulfide Photolyses in the Liquid Phase

1973 ◽  
Vol 51 (9) ◽  
pp. 1410-1415 ◽  
Author(s):  
Donna D. Carlson ◽  
Arthur R. Knight
Keyword(s):  
Liquid Phase ◽  
Room Temperature ◽  
Liquid Mixtures ◽  
Quantum Yields ◽  
Chain Reaction ◽  
Photochemical Process ◽  
High Quantum Efficiency ◽  
Thiyl Radicals ◽  
Exchange Processes ◽  
A Chain

The photolysis of C2H5SH liquid at 2537 Å has been shown to give H2 and C2H5SSC2H5 at equal rates with a quantum yield of 0.25. The photolysis of ethanethiol – methyl disulfide liquid mixtures leads, via a chain reaction involving propagation by attack of thiyl radicals on the disulfide S—S bond, to the formation with high quantum efficiency of CH3SH, C2H5SSC2H5 and, as an intermediate that is consumed after long exposures, CH3SSC2H5. The net result of the sequence of exchange processes is the essentially irreversible conversion of the methyl disulfide into methanethiol. The same overall reaction occurs thermally at room temperature, but the rate is appreciably less than that of the photochemical process. The quantum yields of formation of the unsymmetrical disulfides arising from the photochemically initiated exchange reaction in equimolar mixtures of CH3SSCH3 + n-C3H7SSC3H7 and C2H5SSC2H5 + n-C3H7SSC3H7 have been shown to be 6.9 and 4.4, compared to 355 for CH3-SSCH3 + C2H5SSC2H5 mixtures. In all three types of system examined in this investigation all thiyl radicals can be accounted for stoichiometrically on the basis of exchange and combination reactions alone, indicating negligible disproportionation of these species in condensed phase.

On The Factorization of Partial Differential Equations

1987 ◽  
Vol 39 (4) ◽  
pp. 825-834 ◽  
Author(s):  
W. Dale Brownawell
Keyword(s):  
Differential Equation ◽  
Partial Differential Equations ◽  
Differential Equations ◽  
Nevanlinna Theory ◽  
Algebraic Differential Equation ◽  
List Type ◽  
Variable Result ◽  
Several Variables ◽  
Function Of Several Variables ◽  
Degenerate Cases

In [4] N. Steinmetz used Nevanlinna theory to establish remarkably versatile theorems on the factorization of ordinary differential equations which implied numerous previous results of various authors. (Here factorization is taken in the sense of function composition as introduced by F. Gross in [2].) The thrust of Steinmetz’ central results on factorization is that if g(z) is entire and f(z) is meromorphic in C such that the composite fog satisfies an algebraic differential equation, then so do f(z) and, degenerate cases aside, g(z). In addition, the more one knows about the equation for fog (e.g. degree, weight, autonomy), the more one can conclude about the equations for f and g.In this note we generalize Steinmetz’ work to show the following:a) Steinmetz’ two basic results, Satz 1 and Korollar 1 of [4] can be seen as one-variable specializations of a single two variable result, andb) the function g(z) can itself be allowed to be a function of several variables.

Sign in / Sign up

Export Citation Format

Share Document