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The catalytic effects of H 2 O , basic and acidic catalysts on the gas‐phase hydrolysis mechanism of carbonyl fluoride ( CF 2 O )
Author(s) -
Lu Yousong,
Zhang Tianlei,
Lily Makroni,
Wang Weina,
Liu Fengyi,
Wang Wenliang
Publication year - 2021
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26657
Subject(s) - catalysis , chemistry , hydrolysis , molecule , base (topology) , reaction mechanism , fluoride , reaction rate constant , inorganic chemistry , photochemistry , kinetics , organic chemistry , mathematical analysis , mathematics , physics , quantum mechanics
The carbonyl fluoride (CF 2 O) is one of the significant atmospheric molecules, and its hydrolysis reaction has been considered the most potential removal process in the earth's troposphere. In this article, the hydrolysis reaction of CF 2 O assisted by H 2 O, basic (NH 3 and CH 3 NHCH 3 ), and acidic (H 2 SO 4 , HCOOH, and CF 3 COOH) catalysts have theoretically investigated using quantum chemical methods. These catalysts significantly decrease the hydrolysis reaction of barrier height by 20.4–28.8 kcal mol −1 . Here two H‐transfer mechanisms have been identified in these catalyzed hydrolytic reactions as asynchronous collaborative caused by base molecules and the synchronous collaborative led by H 2 O and acid molecules. In addition, the rate coefficient and relative rate of all catalytic reactions have calculated using conventional transition state theory (TST) over a temperature range of 280–320 K. The results show that H 2 SO 4 has the best catalytic effect without considering the concentration of catalyst molecules in the atmosphere. On the contrary, a high concentration of HCOOH (10 ppbv) is dominant in the catalytic reaction when considered the concentrations of catalyst molecules. In this work, it was identified that the catalytic efficiencies of H 2 O, acid and base molecules upon addition reaction between CF 2 O and H 2 O is not only related to their catalytic mechanisms but also depending upon their concentrations in the atmosphere.