QUANTITATIVE STUDIES OF CHEMOLUMINESCENCE REACTIONS IN ATMOSPHERIC GASES

The termolecular rate constants of reactions involved in the NO-titration method have been measured at room temperature. A high frequency discharge (f=13.6 MHz) was used in combination with a flow system. The following rate constants, defined by the equations -d[N]/df = 2 k1[N]2[N2], -d[O]/dt = MN][O][N2], -d[O]/dt = 2/k3[O]2[N2], and -d[0]/dt = k4[NO] [O] [N2], have been evaluated:[formula omitted] In the range of 2.5 to 8.5 torr of total pressure the volume emission rates ni of N2(B 3Π-A3∑u+)-, NO-β-bands, and the N02-continuum follow the expressions: n1=k1[N]2,n2 = k2L[N] [O] [N2], and w4 = k4L[NO] [0], as could be confirmed. Based on the standard value k4L = (6.4±1.9) •10-” cm6 s-1 the following specific emission rates result from the measurements: [formula omitted] and [formula omitted] The wall recombination probability,γN, of pyrex decreased with increasing oxygen impurity. Under best conditions of purity a value γN= (2.5 ± 1.3) • 10-5 was measured. © 1969, Walter de Gruyter. All rights reserved.