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The design and performance of a smog chamber for the study of photochemical reactions under simulated environmental conditions is described. The chamber is thermostated for aerosol experiments, and it comprises a gas chromatographic sample enrichment system suitable for monitoring hydrocarbons at the ppbv level. By irradiating NO x/alkane-mixtures rate constants for the reaction of OH radicals with n-alkanes are determined from n-pentane to n-hexadecane to be (k++_2a)/lO -12 cm 3 at 312K. Rate constants, (k _+ 2a)/10 -17 cm 3 s -l , for the reaction of ozone with trans-2-butene (21.2 _+ 1.0), cis-3-methylpentene-(2) (47.2 _+ 1.7), cyclopentene (62.4_+3.5), cyclohexene (7.8 _+0.5), cycloheptene (28.3 _+ 1.5), c~-pinene (8.6 _+ 1.3), and fl-pinene (1.4 _+ 0.2) are determined in the dark at 297 K using cis-2-bntene (13.0) as reference standard.

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