The catalytic effects of H₂O, basic and acidic catalysts on the gas‐phase hydrolysis mechanism of carbonyl fluoride (CF₂O)

Abstract

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.

Reactions of Anthropogenic Gas CHF2OCH2CF2CHF2 (HFE-356pcf3): Climatic Influences and Formation of Carbonyl Intermediates

“…As shown in Scheme , CHF 2 OCHO further underwent H-abstraction with the OH radical and subsequent C–O bond scission and H-abstraction by O 2 to form COF 2 . COF 2 is lost through hydrolysis in the lower atmosphere, − while photolysis is the major route to yield CO 2 and HF in the stratosphere , with a local lifetime of 5–10 days…”