Higher Accuracy Measurements of Photochemical Properties of Very Short-Lived Substances.

Abstract:

Despite the broad applicability of simple fully halogenated hydrocarbons in various industries, the production and use of bromo(chloro)fluorocarbons (Halons) and chlorofluorocarbons (CFCs) has been phased out because of the danger they pose to the Earth's stratospheric ozone layer. In addition, all halogen-containing hydrocarbons are infrared active gases because of their strong absorption bands in the region of the atmospheric transparency window between ca. 8 and 12 mm that can affect the Earth’s radiation balance. However, the effort to find replacements continues to return to bromine (chlorine)-containing compounds because of their excellent properties as industrial solvents and cleaning agents and especially because of bromine efficiency as a chemically active flame suppressant. The primary approach to this problem has been to test candidate replacement compounds that have very short atmospheric lifetimes and therefore substantially reduced ozone depleting and radiative impacts.

Reactions with hydroxyl radicals (OH) and photolysis are the main processes dictating the compound residence time in the atmosphere for a majority of trace gases. In case of very short-lived substances (VSLS) their reaction with OH dictates both the atmospheric lifetime and active halogen release. Therefore, the accuracy of OH kinetic data is of primary importance for the purpose of comprehensive atmospheric modeling of compound’s impact on the atmosphere, such as in ozone depletion and climate change.

We demonstrated the ability to determine the OH reaction rate constants over the temperature range of atmospheric interest with the total uncertainty of ~2-3%, thus making laboratory measurements a negligible source of uncertainty in atmospheric modeling. These studies revealed the different reactivity of molecular isomers toward OH and a non-Arrhenius behavior of the temperature dependence to be a rather common kinetic feature of the OH reactivity, which can be accounted for in atmospheric modeling. High accuracy IR and UV absorption spectra were measured to allow the estimation of GWP and ODPs of candidate replacement compounds and their detection in the atmosphere.