THE REACTION OF ACTIVE NITROGEN WITH ETHYLENE

1953 ◽  
Vol 31 (1) ◽  
pp. 1-3 ◽  
Author(s):  
J. Versteeg ◽  
C. A. Winkler

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.


1953 ◽  
Vol 31 (2) ◽  
pp. 129-133 ◽  
Author(s):  
J. Versteeg ◽  
C. A. Winkler

The main products of this reaction were hydrogen cyanide and polymer that contained approximately 32% nitrogen. Yields of these substances increased to constant values with increase of acetylene flow rate. Some cyanogen and methane were also formed. The yield of cyanogen passed through a maximum with increased flow rate of acetylene, but the methane yields were quite erratic.



1954 ◽  
Vol 32 (4) ◽  
pp. 351-355 ◽  
Author(s):  
M. Onyszchuk ◽  
L. Breitman ◽  
C. A. Winkler

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.



1959 ◽  
Vol 37 (4) ◽  
pp. 655-659 ◽  
Author(s):  
A. Schavo ◽  
C. A. Winkler

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.



1956 ◽  
Vol 34 (10) ◽  
pp. 1457-1463 ◽  
Author(s):  
P. A. Gartaganis ◽  
C. A. Winkler

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.



1952 ◽  
Vol 30 (12) ◽  
pp. 915-921 ◽  
Author(s):  
G. S. Trick ◽  
C. A. Winkler

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.



1997 ◽  
Vol 15 (7) ◽  
pp. 531-540 ◽  
Author(s):  
P.J.C. Anstice ◽  
J.F. Alder

An ASC/T (Cu2+, Cr6+, Ag and triethylenediamine impregnated) Whetlerite activated carbon sample was exposed to a flow rate of 1 l/min, 0.746 mg/l SO2 in 80% RH air at 22°C for up to 510 min. Samples were subsequently challenged with 2 mg/l HCN in an identical diluent gas stream. Increasing SO2 exposure resulted in accelerated HCN and (CN)2 bed penetration. The basic shapes of the breakthrough profiles were however essentially unchanged. This observation is in accordance with numerical analysis of these results using Hinshelwood's adsorption model, which suggested that the adsorption rate constant was not significantly affected by SO2 but rather the pollutant exposure resulted in the number of active centres on the carbon surface being reduced and the effective bed depth of the sample being shortened. This loss in active centres was thought most likely to result from the reduction of Cr6+ to Cr3+.



1954 ◽  
Vol 32 (7) ◽  
pp. 718-724 ◽  
Author(s):  
R. A. Back ◽  
C. A. Winkler

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.





1956 ◽  
Vol 34 (8) ◽  
pp. 1074-1082 ◽  
Author(s):  
B. Dunford ◽  
H. G. V. Evans ◽  
C. A. Winkler

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.



1958 ◽  
Vol 36 (9) ◽  
pp. 1223-1226 ◽  
Author(s):  
S. E. Sobering ◽  
C. A. Winkler

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.



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