ABSOLUTE RATE CONSTANTS FOR THE REACTIONS OF CL ATOMS WITH A SERIES OF ESTERS

Absolute rate coefficient measurements have been carried out for the C l atom reaction with a series of esters, at room temperature (298 +/- 2 K) and in the pressure range 15-60 Torr, using the laser photolysis- resonance fluorescence technique. The rate coefficients obtained (in u nits of cm(3) molecule(-1) s(-1)) are as follows: methyl formate (1.83 +/- 0.21) x 10(-12): ethyl formate (1.34 +/- 0.15) x 10(-11) n-propyl formate (5.63 +/- 0.65) x 10(-11), n-butyl formate (1.41 +/- 0.17) x 10(-10), methyl acetate (2.85 +/- 0.35) x 10(-12), ethyl acetate (2.01 +/- 0.25) x 10(-11), n-propyl acetate (7.76 +/- 0.92) x 10(-11), n-bu tyl acetate (1.74 +/- 0.20) x 10(-10), isopropyl acetate (2.68 +/- 0.3 4) x 10(-11), isobutyl acetate (1.08 +/- 0.13) x 10(-10), tert-butyl a cetate (2.42 +/- 0.28) x 10(-11), sec-butyl acetate (9.1 +/- 1.0) x 10 (-11), methyl propionate (1.98 +/- 0.26) x 10(-11), methyl butyrate (8 .6 +/- 0.9) x 10(-11), methyl valerate (1.7 +/- 0.2) x 10(-10), and me thyl caproate (2.72 +/- 0.32) x 10(-10). The results are discussed in terms of structure-reactivity relationship.