THE REACTION OF ACTIVE NITROGEN WITH MIXTURES OF ETHYLENE AND NITRIC OXIDE

The reaction of active nitrogen, produced in a condensed discharge at 1 mm pressure, with mixtures of ethylene and nitric oxide has been studied with mixtures ranging in composition from pure ethylene to pure nitric oxide. The sum of HCN + 14N16N produced from mixtures of C2H4 and 15NO remained constant and equal to the HCN produced from pure C2H4 for NO concentrations up to 50 mole %. As more NO was added, this sum rose towards the value of 14N15N produced from pure 15NO. These data appear to lend support to the HCN yield from ethylene as the true measure of nitrogen atom concentration. It is suggested that 15NO also undergoes a concerted reaction with excited 14N14N molecules, probably in the A3 Σu+ state, to produce 14N15N, and that these excited molecules can be quenched by collision with ethylene or methane without consuming nitrogen or forming HCN.

THE REACTION OF ACTIVE NITROGEN WITH ETHANOL

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.

Time- and Energy-Resolved Mass Spectroscopy: The Condensed Vacuum Discharge between Solid Electrodes

A method is described to obtain time- and energy-resolved mass spectra of ions from discharges between solid electrodes in vacuum. The method is used to investigate the triggered condensed discharge. The discharge is found to consist of two distinct phases: a short high-voltage breakdown (spark) is followed by a longer low-voltage discharge (arc). A model is proposed to explain the processes involved.

NEW EMISSION BANDS OF ,

Thirty-eight new bands of nitrogen were observed in the region 2050–3070 Å in an a-c. condensed discharge of neon mixed with a small amount of nitrogen. It was determined that these bands result from the transition [Formula: see text] of [Formula: see text].