AN ANALYSIS OF THE KINETICS FOR THE N2(A3-SIGMA-U+,UPSILON')+CO(X1-SIGMA+,UPSILON''=0) ENERGY-TRANSFER REACTION AND AN UPPER LIMIT FOR THE RATE CONSTANTS OF THE REACTIONS CO(A3-PI,UPSILON'=0 AND 1)+CF4

The vibrational level distribution of the CO(a 3PI) produced in the title reaction was measured in a rapidly pumped discharge-flow reactor at a total pressure of approximately 2 Torr and approximately 297 K. The emission from the Co(a 3PI,upsilon'-->X1SIGMA+,upsilon") Cameron bands, observed from the product CO(a) formed in the title reaction, was collected with a 2.2-m vacuum-ultraviolet spectrograph-monochromator utilizing both photographic and photoelectric techniques. For N2(A,upsilon' less-than-or-equal-to 4) + CO(X,upsilon"=0) we obtain a CO(a,upsilon') population ratio of 1.00:0.85 for upsilon'=0 and 1, respectively. This branching ratio differs from previous results for N2(A,upsilon' greater-than-or-equal-to 0) which did not correct for competing removal processes of the CO(a) state. In order to obtain these results it was necessary to measure the room temperature biomolecular rate constants, k(upsilon')'s, for the CO(a,upsilon'=0 and 1) + CF4 reactions which were determined to be less-than-or-equal-to 5 x 10(-14) cm3 molecule-1 s-1.