E. K. ZABOLOTNY, H. GESSERAND -11. BANCROFT
40sti
Vol. s4
[ P A R K E R CHEMISTRY LABORATORY, r X I V E R S I T V O F M A S I T O B A , WIIV'NIPEG, CAh'ADA 1
The Reaction of Active Nitrogen with Simple Hydrocarbons at - 19601 BY E.R. ZABOLOTXY, H. GESSERAND AI. BANCROFT RECEIVED DECEMBER 23, 1961 Active nitrogen reacted with methane, ethdne, eth? lene, acetylene and 111drogen cyanide a t nisnis which may account for the reactions and product5 are discussed
The reactions of methane, ethane, ethylene, acetylene, and hydrogen cyanide with active nitrogen, which was produced in a condensed discharge, were studied at - 196'. Methane showed little or no reactivity but considerable amounts of ammonia and hydrogen cyanide were produced from ethane and ethylene. Some hydrogen cyanide was produced from acetylene. In the reaction of active nitrogen with hydrogen cyanide, about lZY0 of the decomposed hydrogen cyanide was recovered as cyanogen.
TABLE I DECOMPOSITIOX OF ETHANE BY ACTIVESITROCEN AT - 196" X11 quantities in micromoles Reaction t i m e , min.
CIH~ reactant
C?H6 decomposed
HCN produced
produced
5.0 10.0 20.0 30.0 40.0
81.5 81.0 73.5 78.0 74.5
23.2 42.5 11.9 73.6 56.6
11.2 16.8 20.8 28.6 28.8
0.5 3.8 2.8 2.4 2.4
"3
The erratic destruction of ethane probably was due to surface effects. Since both hydrogen cyanide and ammonia are destroyed by active nitrogen a t - 196O, the quantities produced in the ethane reaction must have been minimum, and not actual amounts produced. The maximum extent of decomposition of the ethane under these conditions was found to be about 20 Mmoles;min. The results of a time study of the reaction of active nitrogen with ethylene are shown in Table 11. The maximum extent of decomposition of ethylene was found to be about 30 pmoles/min. The reaction of active nitrogen with acetylene a t - 196' gave extremely erratic and irreproducible results, apparently because the acetylene is incorporated in the polymer produced in almost all active nitrogen-hydrocarbon reactions. \%'hen active nitrogen reacted with the polymer produced in the acetylene reaction, as much as 307c of the sup(1) T h c research for t h i s ~ i a p e rwa4 -uplmrteri hy t h e 1)efenie Research Board of Canada. (2) 1s I
