Rapid Gas-Phase Reactions. Amines and Boron Trifluoride. II. Pressure Dependence of Rate Constant

1969 ◽  
Vol 91 (27) ◽  
pp. 7607-7610 ◽  
Author(s):  
Sol Glicker ◽  
R. A. Marcus

The technique outlined in part I of this paper has been employed to study the photo­sensitized decomposition of acetone vapour. A theoretical interpretation of the non-stationary state applied to non-chain photochemical gas phase reactions with second-order termination has been given and the effects of non-homogeneous absorption of radiation have been considered. A value has been obtained for the rate constant for the recombination of methyl radicals in the gas phase at room temperature.



2013 ◽  
Vol 10 (3) ◽  
pp. 145 ◽  
Author(s):  
Sara M. Aschmann ◽  
Janet Arey ◽  
Roger Atkinson

Environmental context Alkanes, major constituents of vehicle exhausts, are emitted to the atmosphere where they react, chiefly by gas-phase reactions with the hydroxyl radical, to form products which can also react further. In laboratory experiments, we studied the further reactions of a model first-generation alkane reaction product. Understanding alkane reaction chains is important because the toxicity, secondary aerosol formation and other properties of vehicle emissions can change as new compounds are formed. Abstract 1,4-Hydroxycarbonyls are major products of the gas-phase reactions of alkanes with OH radicals, and in the atmosphere they will react with OH radicals or undergo acid-catalysed cyclisation with subsequent dehydration to form highly reactive dihydrofurans. 3-Oxobutanal (CH3C(O)CH2CHO) and 4-oxopentanal (CH3C(O)CH2CH2CHO) are first-generation products of the OH radical-initiated reaction of 5-hydroxy-2-pentanone (CH3C(O)CH2CH2CH2OH). The behaviours of 3-oxobutanal and 4-oxopentanal have been monitored during OH+5-hydroxy-2-pentanone reactions carried out in the presence of NO, using solid phase microextraction fibres coated with O-(2,3,4,5,6,-pentafluorobenzyl)hydroxyl amine (PFBHA) for on-fibre derivatisation of carbonyl compounds and an annular denuder coated with XAD resin and further coated with PFBHA. The time-concentration data for 4-oxopentanal during OH+5-hydroxy-2-pentanone reactions were independent of relative humidity (0–50%), and were consistent with a rate constant for OH+4-oxopentanal of (1.2±0.5)×10–11cm3 molecule–1s–1 at 296±2K, a factor of 2 lower than both literature rate constants for other aldehydes and that estimated using a structure-reactivity approach. The molar formation yield for 4-oxopentanal from OH+5-hydroxy-2-pentanone in the presence of NO was determined to be 17±5%, consistent with predictions based on a structure-reactivity relationship and current knowledge of the subsequent reaction mechanisms.



1981 ◽  
Vol 42 (C6) ◽  
pp. C6-323-C6-325
Author(s):  
C. Carlone ◽  
N. K. Hota ◽  
H. J. Stolz ◽  
M. Elbert ◽  
H. Kuzmany ◽  
...  


Author(s):  
Victor N. Kondratiev ◽  
Evgeniĭ E. Nikitin


Author(s):  
Jonathan R. Church ◽  
Veronica Vaida ◽  
Rex T. Skodje


2012 ◽  
Vol 1 (1) ◽  
pp. P46-P53 ◽  
Author(s):  
Ran Zuo ◽  
Haiqun Yu ◽  
Nan Xu ◽  
Xiaokun He


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