scholarly journals THE REACTIONS OF ACTIVE NITROGEN WITH CHLOROMETHANES

1958 ◽  
Vol 36 (9) ◽  
pp. 1223-1226 ◽  
Author(s):  
S. E. Sobering ◽  
C. A. Winkler
Keyword(s):  
Carbon Tetrachloride ◽  
Hydrogen Chloride ◽  
Hydrogen Cyanide ◽  
Active Nitrogen ◽  
Flow Rates ◽  
Product Yields ◽  
Gaseous Products ◽  
Cyanogen Chloride ◽  
Limiting Values ◽  
Reactant Flow

Cyanogen chloride and chlorine were the only gaseous products observed in the reaction of active nitrogen with carbon tetrachloride at 110° and 420 °C. The product yields tended towards limiting values at higher reactant flow rates, and increased with increase of temperature at all flow rates. The reactions of active nitrogen with chloroform and dichloromethane at 260° and 420 °C yielded hydrogen chloride, hydrogen cyanide, and cyanogen, in addition to cyanogen chloride and chlorine. The behavior of the product yields with reactant flow rates and temperature was similar to that of the products from carbon tetrachloride.

THE REACTIONS OF ACTIVE NITROGEN WITH ALKYL CHLORIDES

1956 ◽  
Vol 34 (8) ◽  
pp. 1074-1082 ◽  
Author(s):  
B. Dunford ◽  
H. G. V. Evans ◽  
C. A. Winkler
Keyword(s):  
Hydrogen Cyanide ◽  
Methyl Chloride ◽  
The Other ◽  
Alkyl Chloride ◽  
Initial Attack ◽  
Fast Reaction ◽  
Ethyl Vinyl ◽  
Active Nitrogen ◽  
Flow Rates ◽  
Reactant Flow

The reactions of active nitrogen with methyl, ethyl, vinyl, propyl, and isopropyl chlorides yielded hydrogen cyanide and hydrogen chloride as the main products. Small amounts of cyanogen and a polymer were formed from all the halides, and all except methyl chloride also yielded small amounts of C2 and C3 hydrocarbons. The observed changes in amounts of products recovered with different reactant flow rates were characteristic of a fast reaction in which complete consumption of either reactant occurs when the other is present in excess. Mechanisms for the reactions are suggested on the basis that relatively long-lived complexes are formed in the initial attack of a nitrogen atom on the alkyl chloride.

Reaction of active nitrogen with perfluorinated olefins

1968 ◽  
Vol 46 (22) ◽  
pp. 3483-3489 ◽  
Author(s):  
N. Madhavan ◽  
W. E. Jones
Keyword(s):  
Microwave Discharge ◽  
Flow System ◽  
Active Nitrogen ◽  
Flow Rates ◽  
Gaseous Products ◽  
Nitrogen Containing Compounds ◽  
Reactant Flow

The reactions of the fluorocarbon olefins, C2F4, C3F6, and C4F8-2, with active nitrogen were studied in a flow system. The active nitrogen was produced by a microwave discharge at a concentration of 2.1 × 10−6 mole/s. The major gaseous products of the reactions are fluorocarbons and their production was studied quantitatively at the temperatures 25, 250, and 400 °C and at a large number of reactant flow rates to a maximum of approximately 3 × 10−6 mole/s.Three nitrogen-containing compounds, FCN, N2O, and a polymer of composition (C3F5N)n were detected as products in all three reactions; FCN and N2O are found only in very small amounts.Mechanisms for each of the reactions are discussed.

Reaction of Active Nitrogen with Tetrachloroethylene

1973 ◽  
Vol 51 (22) ◽  
pp. 3680-3683 ◽  
Author(s):  
William Ernest Jones ◽  
Manit Rujimethabhas
Keyword(s):  
Carbon Tetrachloride ◽  
Active Nitrogen ◽  
Glass Wall ◽  
Cyanogen Chloride

The reaction of active nitrogen with tetrachloroethylene yielded cyanogen chloride, trichloroacetonitrile, cyanogen, chlorine, and carbon tetrachloride. In addition, a yellow–brown polymer was found on the glass wall. A brief discussion of a possible mechanism is given.

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 PROPANE

1954 ◽  
Vol 32 (4) ◽  
pp. 351-355 ◽  
Author(s):  
M. Onyszchuk ◽  
L. Breitman ◽  
C. A. Winkler
Keyword(s):  
Activation Energy ◽  
Flow Rate ◽  
Rate Constants ◽  
Hydrogen Cyanide ◽  
Main Product ◽  
Second Order ◽  
Steric Factor ◽  
Active Nitrogen ◽  
Flow Rates ◽  
Order Rate

The reaction of nitrogen atoms with propane has been found to produce hydrogen cyanide as the main product, together with smaller amounts of acetylene, ethylene, and ethane, which were recovered at all propane flow rates. Complete consumption of nitrogen atoms was not attained at any propane flow rate used at 63 °C, but was attained at 250 °C for ratios of propane to nitrogen atoms greater than 1.3. An activation energy of 5.6 ± 0.6 kcal. and a steric factor between 10−2 and 10−3 was estimated from second order rate constants.

scholarly journals THE REACTIONS OF ACTIVE NITROGEN WITH ACETYLENE, METHYLACETYLENE, AND DIMETHYLACETYLENE

1959 ◽  
Vol 37 (4) ◽  
pp. 655-659 ◽  
Author(s):  
A. Schavo ◽  
C. A. Winkler
Keyword(s):  
Flow Rate ◽  
Hydrogen Cyanide ◽  
Linear Increase ◽  
Low Flow ◽  
Active Nitrogen ◽  
Flow Rates ◽  
Polymer Formation

Hydrogen cyanide was the main nitrogen-containing product of all three reactions, but whereas only about one-half the available active nitrogen was converted to product in the acetylene reaction, the conversion by methyl- and dimethyl-acetylene was substantially complete. A faster-than-linear increase of HCN production with acetylene flow rate was observed at low flow rates. Similar behavior was just perceptible in the corresponding curve for methylacetylene, while no observable inflection was present with dimethylacetylene. Polymer formation was pronounced with acetylene, less so with methylacetylene, and practically absent with dimethylacetylene. Small amounts of cyanogen resulted from all three reactions, while condensable hydrocarbons were obtained in significant yields from the methyl- and dimethyl-acetylene reactions only at higher flow rates of the alkynes.

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.

CH2ClN Hydrogen cyanide - hydrogen chloride (1/1)

2005 ◽  
pp. 1-1
Author(s):  
G. Graner ◽  
E. Hirota ◽  
T. Iijima ◽  
K. Kuchitsu ◽  
D. A. Ramsay ◽  
...  
Keyword(s):  
Hydrogen Chloride ◽  
Hydrogen Cyanide

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.

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