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):  
Yousong Lu ◽  
Tianlei Zhang ◽  
Makroni Lily ◽  
Weina Wang ◽  
Fengyi Liu ◽  
...  
Catalysts ◽  
2019 ◽  
Vol 9 (8) ◽  
pp. 638 ◽  
Author(s):  
Sugiyama ◽  
Sakuwa ◽  
Ogino ◽  
Sakamoto ◽  
Shimoda ◽  
...  

In the present study, the production of propylene oxide (PO) from propylene via gas-phase epoxidation was investigated using various catalysts. Although Ag is known to be a highly active catalyst for the epoxidation of ethylene, it was not active in the present reaction. Both Al and Ti showed high levels of activity, however, which resulted in confusion. The present study was conducted to solve such confusion. Although the employment of MCM-41 modified with Ti and/or Al was reported as an active catalyst for epoxidation, the combination resulted in the formation of PO at a less than 0.1% yield. Since this research revealed that the acidic catalyst seemed favorable for the formation of PO, versions of ZSM-5 that were both undoped and doped with Na, Ti, and Ag were used as catalysts. In these cases, small improvements of 0.67% and 0.57% were achieved in the PO yield on H‒ZSM-5 and Ti‒ZSM-5, respectively. Based on the results of the Ti-dopant and acidic catalysts, Ag metal doped on carbonate species with a smaller surface area was used as a catalyst. As reported, Ag‒Na/CaCO3 showed a greater yield of PO at 1.29%. Furthermore, the use of SrCO3 for CaCO3 resulted in a further improvement in the PO yield to 2.17%. An experiment using CO2 and NH3 pulse together with SEM and TEM examinations for Ag‒Na/CaCO3 revealed that the greatest activity was the result of the greater particle size of metallic Ag rather than the acid‒base properties of the catalysts.


1978 ◽  
Vol 56 (8) ◽  
pp. 1069-1074 ◽  
Author(s):  
Terrance Brian McMahon ◽  
Colleen Joan Northcott

The gas phase ion molecule reactions of a number of potential fluoride donors with carbon dioxide and carbonyl fluoride have been studied. By determination of preferential directions of fluoride transfer the fluoride affinities of carbon dioxide and carbonyl fluoride have been bracketed and found to be 33 ± 3 kcal/mol and 35 + 3 kcal/mol respectively. In addition, from gas phase acidity studies of acetyl fluoride and 2-fluoropropene the fluoride affinities of ketene and allene have been calculated to be 38 ± 2 kcal/mol and 15 ± 2 kcal/mol respectively. The order of fluoride affinities (Lewis acidities) of carbon dioxide, ketene, and allene have been examined and explained in terms of the electron affinities of the F—C(A)(B) species (A,B=O,CH2) and the C—F bond dissociation energies. These quantities have been estimated and the latter interpreted on the basis of the π bond energies of the three compounds.


1981 ◽  
Vol 46 (5) ◽  
pp. 1254-1257 ◽  
Author(s):  
Josef Pola ◽  
Pavel Engst ◽  
Milan Horák

The cw-CO2 laser-induced gas phase decomposition of hexafluoroacetone sensitized with sulfur hexafluoride (both 0.7-5.2 kPa) affords, besides perfluorinated hydrocarbons and minor amounts of trifluoroacetyl fluoride, carbonyl fluoride the formation of that obeys first-order kinetics and is favored with higher SF6 content.


Carbon tetrachloride vapour accelerates the gas phase decomposition of di- t -butyl peroxide, the rate constant k n, z , for a given pressure, n , of the peroxide rising with the chloride pressure, x , to a limiting value k n, ∞ . The normal products of the reaction are somewhat changed, acetone being still a major product but methane largely replacing ethane while methyl chloride and probably iso -butene oxide also appear. The effects of the carbon tetrachloride can be largely inhibited by the addition of ammonia, propylene or iso -butene. Similar phenomena are observed with certain other chlorine compounds, and the accelerations are now interpreted in terms of a chain reaction involving chlorine atoms. Acceleration of the peroxide decomposition is also caused by silicon tetrafluoride, sulphur hexafluoride or fluoroform. Propylene considerably inhibits the actions of these compounds and ammonia slightly. Although the interpretation is less certain, it seems likely that the catalytic effects of the fluorides are at least partly due to chemical chain processes.


Chemosphere ◽  
2020 ◽  
Vol 252 ◽  
pp. 126292
Author(s):  
Xiaohui Ma ◽  
Xianwei Zhao ◽  
Zhezheng Ding ◽  
Wei Wang ◽  
Yuanyuan Wei ◽  
...  

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