Prediction of rate constants for the gas phase reactions of triphenylene with OH and NO3 radicals using a relative rate method in CCl4 liquid phase-system.

The kinetics of CCl(4) liquid-phase reactions of ten kinds of polycyclic aromatic compounds (PACs) including triphenylene (TP) with NO(3) radicals have been investigated at 273K by a relative rate method using naphthalene (NA) as a reference compound. The obtained relative reaction rates of the tested PACs to NA in CCl(4) were as follows: 2.57±0.24 (acenaphthene), 2.11±0.30 (2,3-dimethylnaphthalene), 1.21±0.13 (fluoranthene), 0.56±0.07 (fluorene), 1.85±0.19 (1-methylnaphthalene), 1.77±0.12 (2-methylnaphthalene), 0.11±0.03 (1-nitronaphthalene), 1.59±0.23 (phenanthrene), 2.40±0.29 (pyrene), 0.22±0.04 (TP). TP is a semi-volatile PAC with four aromatic rings and it is chemically changed into mutagenic 2-nitrotriphenylene (2-NTP) via the gas-phase OH or NO(3) radical-initiated reactions. On the basis of the relative reactivity of the PACs in the CCl(4) liquid phase-system, the rate constants of the gas-phase reactions of TP with OH and NO(3) radicals at 298 K were predicted to be (8.6±1.2)×10(-12) cm(3) molecule(-1) s(-1) and (6.6±1.5)×10(-29)[NO(2)] cm(3) molecule(-1) s(-1), respectively. Based on the ambient concentrations of TP and 2-NTP and the obtained rate constant for the reaction of TP with OH radicals, the atmospheric loss rate of 2-NTP was also evaluated.