Proton-Catalyzed Decomposition of Multifunctionalized Organic Hydroperoxides Derived from the Reactions of Criegee Intermediates with Ethylene Glycol in Aqueous Organic Media

被引:0
作者
Enami, Shinichi [1 ]
机构
[1] Natl Inst Environm Studies, Tsukuba 3058506, Japan
来源
ACS EARTH AND SPACE CHEMISTRY | 2022年
基金
日本学术振兴会;
关键词
ozone; reactive oxygen species; aerosol; droplets; PM; pH; acidity; mass spectrometry; HYDROXYL RADICALS; FUNCTIONAL-GROUPS; AEROSOL-PARTICLES; HYDROGEN-PEROXIDE; CHEMISTRY; EMISSIONS; OZONOLYSIS; KINETICS; AIR; GENERATION;
D O I
10.1021/acsearthspacechem.2c00142
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Organic hydroperoxides (ROOHs) are ubiquitous, reactive oxygen species that play central roles in atmospheric, environmental, and biological chemistry. Because atmospheric ROOHs possess not only -OOH but in most cases other functionalities such as -C(=O) and -OH, they are expected to reside in condensed phases such as aerosols, fog and cloud droplets, and wet films of leaves and soils. Here, we report a study of the kinetics of the liquid-phase decomposition of multifunctionalized C-12 alpha-alkoxyalkyl hydro-peroxides (alpha-AHs) that possessed an ether, a carbonyl, a hydroperoxide, and two hydroxy groups. We derived the rate coefficients (k) from single exponential decays of the alpha-AH signal in water/ethylene glycol solutions acidified by acids found in the atmosphere. Our discovery that the k of the decomposition of the alpha- AHs increased exponentially from pH 5.1 to 3.9 but independently of the properties of the acid provided firm evidence that the decomposition was catalyzed by H+. The temperature dependence of k and an Arrhenius plot yielded an activation energy (E-a) of 15.0 +/- 0.3 kcal mol(-1) for the decomposition of C-12 alpha-AHs in solution. The proposed H+-catalyzed decomposition of ROOHs may be a general process that provides H2O2 and multifunctionalized compounds to atmospheric condensed phases that are acidic in nature.
引用
收藏
页码:1937 / 1947
页数:11
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