Kinetics of disproportionation–combination reactions between the n-propoxyl radical and nitric oxide, and of the pyrolysis of the O–O bond in di-n-propyl peroxide in the gas phase

1970 ◽  
Vol 0 (0) ◽  
pp. 331-334 ◽  
Author(s):  
R. L. East ◽  
L. Phillips
Keyword(s):  
1992 ◽  
Vol 70 (5) ◽  
pp. 1014-1020 ◽  
Author(s):  
W. Duo ◽  
K. Dam-Johansen ◽  
K. Østergaard

1964 ◽  
Vol 17 (5) ◽  
pp. 539
Author(s):  
JJ Batten

A study has been made of the effect of the surface-to-volume ratio of the reaction vessel and of coatings of various inorganic substances on the vessel walls on the gas-phase oxidation of methanol catalysed by nitric oxide. The results show that, whereas packing the vessel does not have a marked effect on the rate, the kinetics of the reaction are profoundly influenced by the nature of the surface. The results suggest that the methanol-oxidation chains are initiated at the surface by reaction between methanol and nitrogen dioxide, and that HO2 radicals play an important role in the subsequent chain reaction.


1952 ◽  
Vol 20 (2) ◽  
pp. 327-329 ◽  
Author(s):  
Edward C. Freiling ◽  
Harold S. Johnston ◽  
Richard A. Ogg

1986 ◽  
Vol 90 (11) ◽  
pp. 2491-2496 ◽  
Author(s):  
Philip D. Hammer ◽  
Edward J. Dlugokencky ◽  
Carleton J. Howard

1964 ◽  
Vol 17 (5) ◽  
pp. 551
Author(s):  
JJ Batten

The homogeneous, gas-phase oxidation of methanol, catalysed by small amounts of hydrogen bromide, has been studied in a boric acid coated vessel at 310�. Under these conditions no reaction takes place in the absence of hydrogen bromide. The kinetics of the reaction and the rate of accumulation of formaldehyde in the products are compared with previously published data on the nitric oxide catalysed reaction at 310� and the uncatalysed reaction at 390�, i.e. at comparable rates of oxidation. The kinetics of the reaction were studied by means of pressure-time curves, and these were found to be of a similar shape to those of the uncatalysed reaction at 390�, and the nitric oxide catalysed reaction at 310�. The maximum rate was increased by the addition of "inert" gas. This rate varied as the methanol and hydrogen bromide pressures raised to the powers 0.7 and 1.3 respectively. On the other hand, increase in the oxygen pressure inhibited the maximum rate. The overall activation energy was 27 kcal mole-1. These kinetic data are similar to those of the nitric oxide catalysed reaction but differ markedly from those of the uncatalysed process at 390�. Under similar conditions, 15 mmHg hydrogen bromide were required to give a rate approximately equal to that obtained when using 2 mmHg nitric oxide. The maximum pressure of formaldehyde in the products was only about one-tenth of that obtained under similar conditions in the other two oxidations.


An apparatus is described for the extraction of ions from flames burning at atmospheric pres­sure, and for the subsequent mass analysis of the ions. It consists essentially of a fine leak in a platinum or quartz diaphragm on which the flame is played, and on the other side of which a low pressure is maintained by pumping. The ions are separated by suitable disposition of electrodes in a series of expansion chambers before passing into the analyzer. It is concluded that secondary ionization is not important in the mass spectrometer, and that charge exchange reactions and other related types of reaction, in so far as they occur inside the spectrometer, largely reflect similar reactions occurring in the external flame. Ionic concentrations as low as 10 5 per cm 3 can be measured for ions ranging in mass from 10 to 400 atomic units. A brief account is given of the ionization observed from premixed flames of hydrogen, oxygen and nitrogen. The most evident positive ion was hydroxonium (H 3 O + ), the other important ones being NH + 4 and NO + . The first two of these also occurred in hydrated forms, associated with up to 4 molecules of water. These hydrates occur to a large extent in the cooler parts of the flame system (just before the reaction zone), and are considered to be a secondary phenomenon, possibly formed by association just inside the entry leak into the spectrometer. Experimental evidence is adduced for the formation of H 3 O + in the homogeneous gas phase in and near the reaction zone, rather than by catalytic interaction with the walls of the leak. The most likely reaction is considered to be H + H + OH = H 3 O + + e - and the kinetics of this are considered. Doubts about the heat of formation of this ion, and about that of the NH + 4 ion preclude quantitative decisions on many points. The ionization of nitric oxide is shown to be essentially a thermal phenomenon, by observations of ionization with known amounts of nitric oxide added to the flame gases. The relatively slow rate of recombination observed beyond the reaction zone is discussed, and found to be in line with previous results.


1954 ◽  
Vol 22 (4) ◽  
pp. 689-692 ◽  
Author(s):  
Harold S. Johnston ◽  
Harvey J. Crosby

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