Modelling of organic liquid-phase decomposition reactions through gas-phase product analysis: Model systems and peracetic acid

2006 ◽  
Vol 61 (21) ◽  
pp. 6918-6928 ◽  
Author(s):  
Niko Musakka ◽  
Tapio Salmi ◽  
Johan WärnÅ ◽  
Johan Ahlkvist ◽  
Marjatta Piironen
Keyword(s):  
Liquid Phase ◽  
Gas Phase ◽  
Peracetic Acid ◽  
Organic Liquid ◽  
Model Systems ◽  
Phase Decomposition ◽  
Analysis Model ◽  
Product Analysis ◽  
Decomposition Reactions

The photolysis of tetrahydrofuran and of some of its methyl derivatives at 185 nm

1980 ◽  
Vol 58 (24) ◽  
pp. 2819-2826 ◽  
Author(s):  
Nuray Klzilkilic ◽  
Heinz-Peter Schuchmann ◽  
Clemens von Sonntag
Keyword(s):  
Liquid Phase ◽  
Quantum Yield ◽  
Gas Phase ◽  
Carbonyl Compounds ◽  
Quantum Yields ◽  
Product Analysis ◽  
A Value ◽  
Steric Factors ◽  
Methyl Derivatives ◽  
Group 1

The uv photolysis of tetrahydrofuran, 1, 2-methyltetrahydrofuran, 2, cis-2,5-dimethyltetrahydrofuran, 3, trans-2,5-dimethyltetrahydrofuran, 4, and 2,2,5,5-tetramethyltetrahydrofuran, 5, has been investigated by product analysis in the liquid phase, and quantum yields have been determined. The photolysis of tetrahydrofuran itself was also studied in the gas phase at pressures ranging from 1 to 120 atm (pressurizing gas N2); and very little difference was found between the photolytic behaviour of the vapour at 120 atm and that of the liquid. The major products are in ail cases the cyclopropanes and the corresponding carbonyl compounds, as well as the olefinic alcohols and the carbonyl compounds that are isomeric with the starting material. These products are considered to be formed by the two major primary processes [i] and [ii].[Formula: see text]The cyclopropanes formed in reaction [i] retain some excess energy (apparently more than is needed to realize the trimethylene form), and in the photolysis of tetrahydrofuran vapour the hot cyclopropane rearranges to a considerable extent into propene. The propene to cyclopropane yield ratio falls strongly with increasing pressure, to a value of 0.065 at 120 atm. A similar value is observed in the liquid phase photolysis.The five-membered oxyl alkyl diradical from reaction [ii] is the likely intermediate in the cis-trans photoisomerization that is observable with the 2,5-dimethyltetrahydrofurans [Formula: see text]. The photolysis of these compounds also demonstrates that steric factors have a strong bearing on the course of the reaction, e.g. the quantum yield of methylcyclopropane from the cis compound is 0.22, vs. 0.08 from the trans compound.Molecular hydrogen is produced if the tetrahydrofurans carry hydrogen in α-position. Its production is enhanced if the α-position is shared with a methyl group (1 gives a hydrogen quantum yield of 0.07, 2 of 0.17, 3 of 0.27, 4 of 0.29, and 5 of zero).

Investigation Into the Detection of Nitrated Organic Compounds and Explosives by Direct Chemiluminescent Emission During Thermally Induced Gas Phase Decomposition Reactions

1997 ◽  
Vol 34 (8) ◽  
pp. 213-216 ◽  
Author(s):  
Andrew Crowson ◽  
Robin W. Hiley ◽  
Trevor Ingham ◽  
Tom McCreedy ◽  
Alexandra J. Pilgrim ◽  
...  
Keyword(s):  
Gas Phase ◽  
Organic Compounds ◽  
Phase Decomposition ◽  
Thermally Induced ◽  
Decomposition Reactions

Ab Initio Kinetics of Gas Phase Decomposition Reactions

2010 ◽  
Vol 114 (48) ◽  
pp. 12656-12661 ◽  
Author(s):  
Onise Sharia ◽  
Maija M. Kuklja
Keyword(s):  
Ab Initio ◽  
Gas Phase ◽  
Phase Decomposition ◽  
Decomposition Reactions ◽  
Kinetics Of

Gas-Phase Decomposition Reactions of Tris(dimethylamino)phosphine, -Arsine, and -Stibine Reagents

1995 ◽  
Vol 7 (3) ◽  
pp. 507-516 ◽  
Author(s):  
Sateria Salim ◽  
Chee Kiang Lim ◽  
Klavs F. Jensen
Keyword(s):  
Gas Phase ◽  
Phase Decomposition ◽  
Decomposition Reactions
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