THE REACTION OF ACTIVE NITROGEN WITH AZOMETHANE

1955 ◽  
Vol 33 (11) ◽  
pp. 1649-1655 ◽  
Author(s):  
D. A. Armstrong ◽  
C. A. Winkler
Keyword(s):  
Hydrogen Cyanide ◽  
Activation Energies ◽  
Methyl Radicals ◽  
Atomic Nitrogen ◽  
Reactive Component ◽  
Active Nitrogen ◽  
Steric Factors ◽  
Unstable Product

The main products of the reaction between active nitrogen and azomethane were hydrogen cyanide and ethane. Traces of methane, ethylene, and acetylene were also formed, together with small amounts of an unstable product. Activation energies of about 0.5 ± 0.4 and 1.9 ± 0.3 kcal. per mole, with corresponding steric factors of 10−1 to 10−3 and 10−2 to 10−4, were estimated for the reactions of active nitrogen with methyl radicals and azomethane respectively, on the assumption that atomic nitrogen is the reactive component of active nitrogen. Azomethane appeared to catalyze the deactivation of active nitrogen.

THE REACTIONS OF ACTIVE NITROGEN WITH THE BUTANES

1954 ◽  
Vol 32 (7) ◽  
pp. 718-724 ◽  
Author(s):  
R. A. Back ◽  
C. A. Winkler
Keyword(s):  
Nitrogen Atom ◽  
Rate Constants ◽  
Hydrogen Cyanide ◽  
Main Product ◽  
Activation Energies ◽  
Reactive Species ◽  
Atomic Nitrogen ◽  
Initial Attack ◽  
Active Nitrogen ◽  
Rate Controlling Step

The main product of the reactions of active nitrogen with n- and iso-butanes at 75 °C. and 250 °C. was hydrogen cyanide. Small amounts of C2 hydrocarbons, mainly ethylene and acetylene, were produced in both reactions. Second order rate constants were calculated on the assumption that the reactive species in active nitrogen is atomic nitrogen, and that the initial attack of a nitrogen atom is the rate-controlling step. The activation energies were then estimated to be 3.6 kcal. and 3.1 kcal. and the probability factors 4.5 × 10−4 and 4.4 × 10−4, for the n-butane and isobutane reactions respectively.

THE REACTION OF ACTIVE NITROGEN WITH PROPYLENE

1952 ◽  
Vol 30 (12) ◽  
pp. 915-921 ◽  
Author(s):  
G. S. Trick ◽  
C. A. Winkler
Keyword(s):  
Double Bond ◽  
Nitrogen Atom ◽  
Hydrogen Cyanide ◽  
Atomic Hydrogen ◽  
Atomic Nitrogen ◽  
Active Nitrogen

The reaction of nitrogen atoms with propylene has been found to produce hydrogen cyanide and ethylene as the main products, together with smaller amounts of ethane and propane and traces of acetylene and of a C4 fraction. With excess propylene, the nitrogen atoms were completely consumed and for the reaction at 242 °C., 0.77 mole of ethylene was produced for each mole of excess propylene added. For reactions at lower temperatures, less ethylene was produced. The proposed mechanism involves formation of a complex between the nitrogen atom and the double bond of propylene, followed by decomposition to ethylene, hydrogen cyanide, and atomic hydrogen. The ethylene would then react with atomic nitrogen in a similar manner.

THE REACTION OF ACTIVE NITROGEN WITH METHANOL

1963 ◽  
Vol 41 (5) ◽  
pp. 1097-1103 ◽  
Author(s):  
M. J. Sole ◽  
P. A. Gartaganis
Keyword(s):  
Hydrogen Cyanide ◽  
Flow System ◽  
Main Reaction ◽  
Kcal Mole ◽  
Hydrogen Atoms ◽  
Active Nitrogen ◽  
Steric Factors ◽  
Additional Water ◽  
Fast Flow ◽  
Methane Carbon

The reaction of active nitrogen with methanol has been investigated at several temperatures in the range 30 to 480 °C using a fast-flow system. The only condensable products found in appreciable amounts were water and hydrogen cyanide. The overall activation energy is 3.0 and 3.2 kcal/mole and the steric factors 1.3 × 10−3 and 2.1 × 10−3 for streamline and turbulent flow respectively.It is postulated that the mechanism consists of the initial formation of a collision complex, [NCH3OH], which breaks down to two fragments, NCH3 and OH, from which the two condensable products are formed,[Formula: see text]Attack of the methanol molecules by hydrogen atoms resulting from the main reaction occurs to a lesser extent and is responsible for the production of small quantities of methane, carbon monoxide, and additional water.

ADDITION OF METHYL RADICALS TO UNSATURATED HYDROCARBONS

1954 ◽  
Vol 32 (5) ◽  
pp. 474-484 ◽  
Author(s):  
L. Mandelcorn ◽  
E. W. R. Steacie
Keyword(s):  
Activation Energies ◽  
Methyl Radicals ◽  
Methyl Radical ◽  
Unsaturated Hydrocarbons ◽  
Ethylene Propylene ◽  
Steric Factors ◽  
Kinetics Of

The rates of addition of methyl radicals, produced by the photolysis of acetone between 140 °C. and 240 °C, to unsaturated hydrocarbons were determined by two independent methods. From the kinetics of the addition and the methyl radical combination reactions, addition of methyl radicals to ethylene, propylene, acetylene, and butadiene was found to proceed with activation energies of 7.0, 6.0, 5.5, and ∼2.5 kcal. respectively and steric factors of the order of 10−4.

THE REACTION OF ACTIVE NITROGEN WITH ETHYLENE

1953 ◽  
Vol 31 (1) ◽  
pp. 1-3 ◽  
Author(s):  
J. Versteeg ◽  
C. A. Winkler
Keyword(s):  
Polymeric Material ◽  
Flow Rate ◽  
Hydrogen Cyanide ◽  
Active Nitrogen ◽  
Principal Product

Reinvestigation of the active nitrogen–ethylene reaction has confirmed hydrogen cyanide as the principal product. Smaller quantities of ethane, cyanogen, acetylene, and methane have also been found and the variations in amounts of these products with ethylene flow rate have been established. No significant amount of polymeric material was found.

THE REACTIONS OF TRIFLUOROMETHYL RADICALS WITH PROPANE, n-BUTANE, AND ISOBUTANE

1956 ◽  
Vol 34 (2) ◽  
pp. 103-107 ◽  
Author(s):  
P. B. Ayscough ◽  
E. W. R. Steacie
Keyword(s):  
Rate Constants ◽  
Hydrogen Abstraction ◽  
Activation Energies ◽  
Methyl Radicals ◽  
Kcal Mole

A study of the reactions of trifluoromethyl radicals, produced by the photolysis of hexafluoroacetone, with propane, n-butane, and isobutane has been made. The rate constants of the hydrogen-abstraction reactions have been determined at temperatures between 27 °C and 119 °C and the activation energies found to be 6.5 ± 0.5, 5.1 ± 0.3, and 4.7 ± 0.3 kcal./mole respectively. These values are compared with those obtained for the reactions with methane and ethane, and with the corresponding reactions of methyl radicals.

REACTION OF N2(A3∑U+) WITH ATOMIC NITROGEN

1966 ◽  
Vol 44 (10) ◽  
pp. 1171-1174 ◽  
Author(s):  
Robert A. Young
Keyword(s):  
Excited States ◽  
Rate Coefficient ◽  
Atomic Nitrogen ◽  
Active Nitrogen ◽  
Upper Limit ◽  
Interchange Process

Attempts to measure the actual lifetime of N2(A3∑u+) in active nitrogen resulted only in a very small upper limit of ≈5 × 10−4 s. This result is consistent with quenching of the A3∑u+ state by atomic nitrogen in an atom–atom interchange process,[Formula: see text]having a rate coefficient of [Formula: see text] It is suggested that similar processes are involved in determining the distribution of excited states observed in atom association.

scholarly journals Influence of Active Nitrogen Species on the Nitridation Rate of Sapphire

1998 ◽  
Vol 537 ◽  
Author(s):  
A.J. Ptak ◽  
K.S. Ziemer ◽  
M.R. Millecchia ◽  
C.D. Stinespring ◽  
T.H. Myers
Keyword(s):  
Molecular Nitrogen ◽  
Active Species ◽  
Operating Conditions ◽  
Rf Plasma ◽  
Atomic Nitrogen ◽  
Active Nitrogen ◽  
Plasma Sources ◽  
Electrostatic Deflector ◽  
Low Energy Ions ◽  
Operating Regimes

AbstractThe operating regimes of two rf-plasma sources, an Oxford CARS-25 and an EPI Unibulb, have been extensively characterized. By changing the exit aperture configuration and using an electrostatic deflector, the Oxford source could produce either primarily atomic nitrogen, atomic nitrogen mixed with low energy ions, or a large flux of higher energy ions (>65eV) as the active species in a background of neutral molecular nitrogen. The EPI source produced a significant flux of metastable molecular nitrogen as the active species with a smaller atomic nitrogen component. Nitridation of sapphire using each source under the various operating conditions indicate that the reactivity was different for each type of active nitrogen. Boron contamination originating from the pyrolytic boron nitride plasma cell liner was observed.

Interception of hydrogen cyanide precursor(s) in the reaction of active nitrogen with alcohols in aqueous solution

1970 ◽  
Vol 92 (25) ◽  
pp. 7506-7507 ◽  
Author(s):  
Norman N. Lichtin ◽  
Carl C. T. Chen
Keyword(s):  
Aqueous Solution ◽  
Hydrogen Cyanide ◽  
Active Nitrogen

THE REACTION OF ACTIVE NITROGEN WITH ETHANOL

1965 ◽  
Vol 43 (4) ◽  
pp. 935-939 ◽  
Author(s):  
P. A. Gartaganis
Keyword(s):  
Flow System ◽  
Methyl Radicals ◽  
Kcal Mole ◽  
Hydrogen Atoms ◽  
Active Nitrogen ◽  
Condensed Discharge ◽  
Preliminary Study ◽  
Fast Flow ◽  
Ethyl Radicals ◽  
Water Hydrogen

The reaction of active nitrogen with ethanol has been investigated in the range 300 to 593 °K using a modified condensed-discharge Wood–Bonhoeffer fast-flow system. The only condensable products found in appreciable amounts were hydrogen cyanide and water. Hydrogen was the main noncondensable product. A very small amount of acetaldehyde was also formed along with traces of ethane, ethylene, methane, acetonitrile, cyanogen, and probably carbon monoxide. The overall activation energy is 3.4 kcal/mole. It is postulated that the mechanism consists of the formation of two fragments NC2H5 and OH, from which the condensable products result as follows:[Formula: see text]A number of products found in trace quantities are produced by concomitant reactions of the hydrogen atoms with methyl radicals, and with ethanol as well as by disproportionation of ethyl radicals to produce ethane and ethylene. A preliminary study of the reaction of active nitrogen with isopropanol indicated that the energy of activation is in line with the energies of activation of methanol and ethanol.

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