Uptake kinetics of three epoxides into sulfuric acid solution

This work presents a study of the uptake of isoprene epoxide, butadiene epoxide (BMO) and butadiene diepoxide (BDO) into sulfuric acid solutions which helps to understand the reactivity of epoxides existing in the atmosphere toward acidic aerosols. The uptake of these three compounds into 0−30 wt % H2SO4 solutions were measured using a rotated wetted-wall reactor (RWW) coupled to a single-photon ionization time of flight mass spectrometer (SPI-TOFMS). The epoxides were found to be very easily taken up by H2SO4 solutions even in dilute concentrations of pH levels. Isoprene epoxide was found to partition reversibly into solution at pH = 4, whereas irreversible uptake was observed when pH ≤ 3. We reported the reactive uptake coefficients from 1.87 × 10−5 to 2.67 × 10−3 for pH = 3−20 wt % H2SO4 solutions. A chemical reaction for isoprene epoxide was responsible for the reactive uptake. By means of mass spectrometry, gas chromatography and FTIR spectroscopy, a gas product was identified to be 2-methyl-3-butenal. The uptake behavior of butadiene epoxide was similar with that of isoprene epoxide, while butadiene diepoxide partitioned irreversibly over the whole acidity range of 0–30 wt %, and the reactive uptake coefficients increased slightly (0.849 × 10−4–1.36 × 10−4) from pure water to pH = 1. The reactivity that displayed close dependence on the hydrolysis rates of the three epoxides was analyzed and compared according to their molecular structural differences. The atmospheric lifetimes were calculated and atmospheric implication was discussed based on the corresponding reactive uptake coefficients.

► The uptake of three epoxides on H2SO4 was studied. ► The reactive uptake coefficients increase with increasing acidity. ► Isoprene monoxide transformed to 2-methyl-3-butenal on H2SO4. ► The chemical mechanism of isoprene monoxide was proposed. ► This process may play an important role in SOA formation in upper troposphere.