Kinetics of the reactions of acenaphthene and acenaphthylene and structurally‐related aromatic compounds with OH and NO₃ radicals, N₂O₅ and O₃ at 296 ± 2 K

The kinetics of the atmospherically important gas‐phase reactions of acenaphthene and acenaphthylene with OH and NO 3 radicals, O 3 and N 2 O 5 have been investigated at 296 ± 2 K. In addition, rate constants have been determined for the reactions of OH and NO 3 radicals with tetralin and styrene, and for the reactions of NO 3 radicals and/or N 2 O 5 with naphthalene, 1‐ and 2‐methylnaphthalene, 2,3‐dimethylnaphthalene, toluene, toluene‐α,α,α‐ d 3 and toluene‐ d 8 . The rate constants obtained (in cm 3 molecule −1 s −1 units) at 296 ± 2 K were: for the reactions of O 3 ; acenaphthene, <5 × 10 −19 and acenaphthylene, ca. 5.5 × 10 −16 ; for the OH radical reactions (determined using a relative rate method); acenaphthene, (1.03 ± 0.13) × 10 −10 ; acenaphthylene, (1.10 ± 0.11) × 10 −10 ; tetralin, (3.43 ± 0.06) × 10 −11 and styrene, (5.87 ± 0.15) × 10 −11 ; for the reactions of NO 3 (also determined using a relative rate method); acenaphthene, (4.6 ± 2.6) × 10 −13 ; acenaphthylene, (5.4 ± 0.8) × 10 −12 ; tetralin, (8.6 ± 1.3) × 10 −15 ; styrene, (1.51 ± 0.20) × 10 −13 ; toluene, (7.8 ± 1.5) × 10 −17 ; toluene‐α,α,α‐ d 3 , (3.8 ± 0.9) × 10 −17 and toluene‐ d 8 , (3.4 ± 1.9) × 10 −17 . The aromatic compounds which were observed to react with N 2 O 5 and the rate constants derived were (in cm 3 molecule −1 s −1 units): acenaphthene, 5.5 × 10 −17 ; naphthalene, 1.1 × 10 −17 ; 1‐methylnaphthalene, 2.3 × 10 −17 ; 2‐methylnaphthalene, 3.6 × 10 −17 and 2,3‐dimethylnaphthalene, 5.3 × 10 −17 . These data for naphthylene and the alkylnaphthalenes are in good agreement with our previous absolute and relative N 2 O 5 reaction rate constants, and show that the NO 3 radical reactions with aromatic compounds proceed by overall H‐atom abstraction from substituent‐XH bonds (where X = C or O), or by NO 3 radical addition to unsaturated substituent groups while the N 2 O 5 reactions only occur for aromatic compounds containing two or more fused six‐membered aromatic rings.