The configuration of alkyl substituents about carbon-carbon unsaturated bonds exerts a controlling influence on the rate of the ozonolysis reaction. Alkyl substituents can increase ( via the inductive effect) and decrease ( via the steric effect) the activity of unsaturated bonds, and an accurate description of this information ought to correlate with the ozonolysis rate coefficient. A strong linear relationship is observed (R-2 = 0.94), providing the basis of our SAR method. SAR estimates were tested against literature measurements of ozonolysis rate coefficients for 48 aliphatic alkenes and dialkenes, and were found to be accurate to within a factor of 2.3 of the measured value for the entire dataset. This represents a significant improvement over methods reported in the literature, where quoted predictions are at best accurate to within a factor of 6.5. Rates of gas-phase ozonolysis of alkenes and dialkenes can now be predicted with unprecedented accuracy using a simple SAR. The SAR was then validated against new experimental data. Absolute rate coefficients for the gas-phase reaction of ozone with a series of alkenes were determined in a simulation chamber at 295 +/- 2 K and atmospheric pressure by monitoring the loss of ozone in the presence of excess alkene. The rate coefficients ( in units of 1 x 10(-18) cm 3 molecule(-1)s(-1)) are: 5.12 +/- 0.93 for 1-pentene, 2,3-dimethyl; 406 +/- 49 for 2-pentene, 2-methyl; 151 +/- 5 for ( E)-2-hexene, 14.5 +/- 1.0 for 1,5-hexadiene and 20.7 +/- 3.1 for 1,5-hexadiene, 2-methyl. There is good agreement between the experimental and predicted values and the adjustable parameters of the SAR are shown to be insensitive to the inclusion of the new data. The use of the SAR in atmospheric chemical modelling is investigated. Ozonolysis and OH radical rate coefficients are estimated for each alkene and dialkene present in the MCM v3.1. The effects of error within predicted rate coefficients upon modelled concentrations of a number of key species, including O-3, OH, HO2, NO and NO2 were rather small and is not in itself a major cause of uncertainty in modelled concentrations. ; McGillen, Max R. Carey, Trevor J. Archibald, Alex T. Wenger, John C. Shallcross, Dudley E. Percival, Carl J. 32 ROYAL SOC CHEMISTRY CAMBRIDGE 276BM