scholarly journals Reactions of Thiyl Radicals. VIII. Photolysis of Methyl Ethyl Sulfide Vapor

1972 ◽  
Vol 50 (11) ◽  
pp. 1734-1742 ◽  
Author(s):  
D. R. Tycholiz ◽  
A. R. Knight
Keyword(s):  
Absorption Spectrum ◽  
Mass Balance ◽  
Vapor Phase ◽  
Exposure Time ◽  
Quantum Yields ◽  
Methyl Ethyl ◽  
Chemical Decomposition ◽  
Thiyl Radicals ◽  
A Value ◽  
Single Substrate

Methyl ethyl sulfide has been photolyzed in the vapor phase with wavelengths between 2000 and 2350 Å and the effects of pressure, temperature, and exposure time investigated. The vapor phase absorption spectrum of the sulfide has been determined and the variation in the nature and rates of formation of products in the presence of CO2, CF4, propylene, and 2-pentene measured. Quantum yields of products from the decomposition of the pure substrate were determined at 2288 Å.The products of the reaction are, in order of decreasing importance, C2H6, CH3SSC2H5, C2H5SSC2H5, CH4, CH3SCH3, C2H5SC2H5, C3H8, C2H4, CH3SSCH3, C4H10, C2H5SH, and CH3SH. A carbon/sulfur mass balance is obtained at all substrate pressures at 25 °C, and at the single substrate pressure examined at 120 °C. In the presence of propylene four additional products, n-C5H12, CH3S(CH2)2CH3, (CH3CH2CH2)2S, and CH2=CH—CH2SC2H5, were found.Only a small fraction of photochemically excited methyl ethyl sulfide molecules undergoes chemical decomposition. The two primary processes[Formula: see text]and subsequent reactions of the radicals so formed account for the observed products. R3a/R3b has a value of 1.32 at 25 °C.

The absorption spectrum of SO and the flash photolysis of sulphur dioxide and sulphur trioxide

1959 ◽  
Vol 249 (1259) ◽  
pp. 498-512 ◽  
Keyword(s):  
Absorption Spectrum ◽  
Dissociation Energy ◽  
Sulphur Dioxide ◽  
Flash Photolysis ◽  
Ultra Violet ◽  
Vibrationally Excited ◽  
A Value ◽  
Continuous Absorption ◽  
Sulphur Trioxide ◽  
Normal Spectrum

The flash photolysis of sulphur dioxide under adiabatic conditions results in the complete temporary disappearance of its spectrum , which then slowly regains its original intensity over a period of several milliseconds. Simultaneously with the disappearance of the sulphur dioxide spectrum a continuous absorption appears in the far ultra-violet and fades slowly as the sulphur dioxide reappears. It is shown that the effect of the flash is thermal rather than photochemical, and the possibility of the existence of an isomer of sulphur dioxide at high temperatures is discussed; the disappearance of the normal spectrum on flashing is explained in this way. Several previously unrecorded bands of SO observed in the photolysis indicate that the vibrational numbering of its spectrum should be revised by the addition of 2 to the present values of v' . This leads to a value of the dissociation energy of 123.5 kcal. In formation about the levels v' = 4, 5 and 6 has also been obtained. The isothermal flash photolysis of sulphur trioxide results in the appearance of vibrationally excited SO, and the primary photochemical step in this reaction is discussed.

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.

THE REACTION OF ISOPROPANOL VAPOR WITH Hg 6 (3P1) ATOMS: PART I. PURE SUBSTRATE

1962 ◽  
Vol 40 (6) ◽  
pp. 1134-1139 ◽  
Author(s):  
Arthur R. Knight ◽  
Harry E. Gunning
Keyword(s):  
Quantum Yield ◽  
Hydrogen Production ◽  
Exposure Time ◽  
Resonance Line ◽  
Light Period ◽  
Inert Gas ◽  
Quantum Yields ◽  
Volatile Product ◽  
Intermittent Illumination ◽  
Static Conditions

The reaction of isopropanol vapor with Hg 6(3P1) atoms has been investigated under static conditions at 25 °C under continuous and intermittent illumination. The effect of added inert gas and isolation of the 2537 Å Hg resonance line were also studied.The products of the reaction are H2 (0.72), CH3COCH3 (0.25), CO, CH4, C2H6, CH3CHO, and H2O, with the numbers in parentheses representing the quantum yields at zero exposure time. The non-volatile product remaining in the cell was a mixture of C6-glycols, containing 98.6% pinacol, 1.2% 2-methyl-2,4-pentanediol, and ca. 0.2% or less of 2,5-hexanediol.Under intermittent illumination, the quantum yield of hydrogen production, measured as a function of light period, tL, rose linearly with log tL, and had a constant value of unity for tL < 0.45 msec. A mechanism is proposed involving the primary formation with perfect efficiency of isopropoxy radicals and H atoms.

The optical properties and chemical decomposition of lead iodide

1964 ◽  
Vol 280 (1383) ◽  
pp. 566-585 ◽  
Keyword(s):  
Optical Properties ◽  
Absorption Spectrum ◽  
Valence Band ◽  
Conduction Band ◽  
Electron Irradiation ◽  
Irradiation Damage ◽  
Lead Iodide ◽  
Chemical Decomposition ◽  
Excitation Processes ◽  
Split Valence

The optical properties of lead iodide have been measured and the fundamental absorption spectrum is interpreted in terms of ionization and excitation processes. These processes may be regarded as transitions from a split valence band to the conduction band and to exciton levels lying above and below the minimum of the conduction band. This inter­pretation is supported by measurements of photoconductivity and photodecomposition. Two mechanisms are suggested to explain the occurrence of photodecomposition and electron irradiation damage in this substance.

Rydberg series and autoionization resonances in the Y I absorption spectrum

1973 ◽  
Vol 333 (1592) ◽  
pp. 17-24 ◽  
Keyword(s):  
Absorption Spectrum ◽  
Ionization Potential ◽  
Excited States ◽  
Spectral Range ◽  
Ground State ◽  
Rydberg Series ◽  
A Value ◽  
Doublet Ground State ◽  
Ionization Limit ◽  
First Ionization Potential

The absorption spectrum of yttrium vapour has been photographed in the spectral range 1650 to 2250 À, with a 10 m spectrograph. Series of autoionization resonances, which converge on excited states of the Y + ion have been identified, as combinations with the doublet ground-state of Y I , 5s 2 4d 2 D 3/2 , 5/2 . Although the lines of these series show broadened and often asymmetrical profiles, the lines are sufficiently well defined to fix a value for the first ionization potential of Y I , which differs from the previously accepted value by approximately 2500 cm -1 . In addition, approximately 400 new Y I lines, which involve excited levels below the first ionization limit of Y I , namely 4s 2 1 S o , have been found. The majority of these are unclassifiable at present but, the value for the first ionization-potential being known from the resonances above-mentioned, two series of the character 5s 2 4d 2 D 3/2 , 5/2 -5s 2 nf 2 F o have been identified. In addition to the identifications of series, 152 new lines below the 5s 2 1 S o limit identify 76 new levels of Y I , of odd parity.

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.

scholarly journals Modelling of quantum yields in photocatalytic membrane reactors immobilising titanium dioxide

2006 ◽  
Vol 2006 ◽  
pp. 1-8 ◽  
Author(s):  
Ignazio Renato Bellobono ◽  
Giulia de Martini ◽  
Paola Maria Tozzi ◽  
Carmen Canevali ◽  
Franca Morazzoni ◽  
...  
Keyword(s):  
Hydroxyl Radicals ◽  
Membrane Reactors ◽  
Quantum Yields ◽  
Peroxide Formation ◽  
Initial Concentration ◽  
A Value ◽  
Maximum Value ◽  
Radiant Power ◽  
Hydrogen Peroxide Formation ◽  
Kinetics Of

For some model molecules (methanoic and ethanoic acids, methane, and phenol), systematic investigations of quantum yields were carried out in the present paper, as a function of concentration and of absorbed radiant power. Quantum yieldsΦ∞, calculated from rates, followed an apparently Langmuirian function of initial concentrationC0, by whichΦ∞values at “infinite” concentration could be obtained. By having thus established that quantum yields of photomineralisationΦ∞are independent of radiation wavelength, within the absorption range of semiconductor, but depend on radiant power, such a dependency was experimentally investigated. For all the investigated molecules, the maximum allowable values reached in the low radiant power range clearly appeared as a plateau. On the contrary, at high radiant power values, another plateau, at a value of about 1/4-1/5 with respect to the maximum value, was evident. This was interpreted on the basis of a competition kinetics of hydroxyl radicals with themselves, leading to hydrogen peroxide formation, other than with substrate or intermediate molecules leading to full mineralisation. Modelling of quantum yields as a function of concentration and radiant power thus allows a fully consistent and trustworthy design of photoreactors.

Sign in / Sign up

Export Citation Format

Share Document