Temperature dependences of the reactions of the nitrate radical with some alkynes and with ethylene

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Abstract
The temperature dependences of the rate constants for the reactions of NO3 with ethylene and a series of alkynes have been studied using a time-resolved flow method over the temperature range 295–523 K. In all these reactions the variations of the rate constants follow closely the Arrhenius expression, for which the parameters A and Ea, have been calculated. The activation energies were compared with literature values for the addition reactions of OH, O(3P), CH3, CH3O2 and CH3COO2 with alkenes and alkynes as well as with those for the reactions of NO3 with CH3SH, CH3SH, and CH3SSCH3. We conclude that the behaviour of the nitrate radical towards alkenes and alkynes resembles that of the addition of CH3O2 and CH3COO2 to alkenes. Unexpected gas-phase or wall losses of NO3 contribute a first-order decay rate of less than 0.04 s–1 at 523 K. We also obtained upper limits for the rate constants for the interactions of NO3 with O2 and SO2 at 473 K of 1.2×10–17 cm3 molecule–1 s–1.

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