Reaction Kinetics of the OH-Initiated Degradation of 1,1-Diethoxyethane in Conditions Relevant to the Troposphere

Abstract

1,1-Diethoxyethane (DEE) is an oxygenated VOC with several uses in industry. This can result in its emission to the atmosphere, where it will undergo reactions with OH radicals. The kinetics of this reaction and its variation with temperature in the range of 273–363 K were examined in this work using pulsed laser photolysis─laser-induced fluorescence (PLP-LIF) experiment. The rate coefficient at 298 K was measured to be (1.78 ± 0.05) × 10^–11 cm³ molecule^–1 s^–1. The rate coefficients follow an Arrhenius equation k_DEE+OH^PLP-LIF (273–363 K) = (5.50 ± 1.10) × 10^–13 exp [(1026 ± 63)/T] cm³ molecule^–1 s^–1 with an inverse dependence on temperature. The rate coefficients calculated using the variational transition state theory at the CCSD(T)/aug-cc-pVDZ//M06-2X/aug-cc-pVDZ level also show good agreement with the measured values. Acetaldehyde and ethanol were identified as the products of the title reaction, and a mechanism for the degradation of DEE was elucidated. The impact of DEE emissions on the troposphere was also assessed using its atmospheric lifetime, radiative efficiency (RE), global warming potential (GWP) and photochemical ozone creation potential (POCP_E).