A study of the gas-phase ozonolysis of terpenes: the impact of radicals formed during the reaction

Abstract

The gas-phase ozonolysis of α-pinene, Δ 3-carene and limonene was investigated at ppb levels and the impact of the ozone, relative air humidity (RH), and time was studied using experimental design. The amounts of terpene reacted varied in the different settings and were as high as 8.1% for α-pinene, 10.9% for Δ 3-carene and 23.4% for limonene. The designs were able to describe almost all the variation in the experimental data and were also successful in predicting omitted values. The results described the effects of time and ozone and also showed that RH did not have a statistically significant effect on the ozonolysis. The results also showed that all three terpenes were affected by an additional oxidation of OH radicals and/or other reactive species. The results from the designs states that this additional oxidation was responsible for 40% of the total amount of α-pinene reacted, 33% of the total amount of Δ 3-carene reacted and 41% of the total amount of limonene reacted at the settings 20 ppb terpene, 75 ppb ozone, 20% RH and a reaction time of 213 s. Additional experiments with 2-butanol as OH radical scavenger showed that the reaction with OH radicals was responsible for 37% of the total α-pinene reacted and 39% of the total Δ 3-carene reacted at the same settings. The scavenger experiments also showed that there were no significant amounts of OH radicals formed during the ozonolysis of limonene. The results from the designs were also compared to a mathematical model in order to evaluate further the data.