Reactions of hydrocarbons with mixtures of active nitrogen and hydrogen atoms. II. "Anomalous" reactions: the reactions of cyanogen, hydrogen cyanide, and acetylene

1968 ◽  
Vol 72 (9) ◽  
pp. 3305-3318 ◽  
Author(s):  
David R. Safrany ◽  
Walter Jaster
Keyword(s):  
Hydrogen Cyanide ◽  
Hydrogen Atoms ◽  
Active Nitrogen

THE REACTION OF ACTIVE NITROGEN WITH HYDRAZINE

1955 ◽  
Vol 33 (4) ◽  
pp. 692-698 ◽  
Author(s):  
G. R. Freeman ◽  
C. A. Winkler
Keyword(s):  
Hydrogen Cyanide ◽  
Chemical Reactivity ◽  
Large Contribution ◽  
Ammonia Production ◽  
Hydrogen Atoms ◽  
Active Nitrogen ◽  
Flow Rates ◽  
Production Of Hydrogen ◽  
Secondary Reactions ◽  
Excited Nitrogen

Hydrazine was completely destroyed by active nitrogen, at both 150 °C. and 480 °C., up to a hydrazine flow rate of about 22 × 10−6 mole per sec., whereas ammonia production was small at hydrazine flow rates below about 12 × 10−6 mole per sec. Thus it appears that ammonia is formed in secondary reactions only. The results indicate that NH2 radicals rather than hydrogen atoms may be prominent in secondary reactions. Comparison of the rate of hydrazine destruction with the rate of production of hydrogen cyanide from ethylene indicates that excited nitrogen molecules do not make a large contribution to the chemical reactivity of active nitrogen.

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.

THE REACTIONS OF ACTIVE NITROGEN WITH METHANE AND ETHANE

1956 ◽  
Vol 34 (10) ◽  
pp. 1457-1463 ◽  
Author(s):  
P. A. Gartaganis ◽  
C. A. Winkler
Keyword(s):  
Hydrogen Atom ◽  
Flow Rate ◽  
Hydrogen Cyanide ◽  
Induction Effect ◽  
Hydrogen Atoms ◽  
Active Nitrogen ◽  
Temperature Range ◽  
Methane Flow Rate ◽  
Methane Flow

Reinvestigation of the active nitrogen – methane reaction in the temperature range 45° to 500 °C. has confirmed hydrogen cyanide as the only product, other than hydrogen, formed in measurable amounts. An “induction” effect in the hydrogen cyanide production was observed with increase of methane flow rate. This induction decreased with increase of temperature and was shown to be due to concomitant hydrogen atom reactions, since it could be eliminated by addition of hydrogen atoms to the reaction mixture. Reinvestigation of the active nitrogen – ethane reaction over the temperature range −100° to 475 °C. also confirmed hydrogen cyanide to be the only measurable product, other than hydrogen, of that reaction. There was some indication that an induction effect was present with ethane, as with methane, and it may be concluded tentatively that both reactions are carried substantially by hydrogen atom reactions.

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 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 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.

Reactions of hydrocarbons with mixtures of active nitrogen and hydrogen atoms. III. Reactions of methylacetylene and allene

1968 ◽  
Vol 72 (9) ◽  
pp. 3323-3326 ◽  
Author(s):  
David R. Safrany ◽  
Walter Jaster
Keyword(s):  
Hydrogen Atoms ◽  
Active Nitrogen

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.

THE REACTION OF HYDROGEN ATOMS WITH METHYL CYANIDE

1955 ◽  
Vol 33 (12) ◽  
pp. 1814-1818 ◽  
Author(s):  
W. Forst ◽  
C. A. Winkler
Keyword(s):  
Discharge Tube ◽  
Hydrogen Cyanide ◽  
Main Product ◽  
Initial Step ◽  
Methyl Radicals ◽  
Methyl Radical ◽  
Hydrogen Atoms ◽  
Methyl Cyanide ◽  
Secondary Reactions

Hydrogen atoms produced in a discharge tube were found to react with methyl cyanide to produce hydrogen cyanide as the main product, together with smaller amounts of methane and ethane. The proposed mechanism involves the formation of hydrogen cyanide and a methyl radical in the initial step; methane and ethane are attributed to secondary reactions of the methyl radicals.

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