Formation Mechanism Of By-products Research Articles

Experimental and theoretical analysis on decomposition and by-product formation process of (CF3)2CFCN mixture

Although sulfur hexafluoride (SF6) is widely used in gas-insulated electrical equipment due to the excellent electrical insulation and arc-interruption behaviors, its strong greenhouse effect with high glow warming potential (GWP) has been driving the research on environmentally friendly gases for SF6 alternatives. Recently, the heptafluoro-isobutyrontrile (CF3)2CFCN (3M NovecTM 4710) is reported to have the potential to replace SF6. The decomposition characteristic of gas insulating medium is one of the basic conditions to measure whether it has the feasibility of replacing SF6. However, the decomposition characteristic of (CF3)2CFCN and the formation mechanism of by-products are still unclear. In this paper, a series of AC corona discharge experiments were performed, and the gas by-products of (CF3)2CFCN mixed with CO2, N2 and air were qualitatively analyzed by gas chromatography mass spectrometry (GC/MS) method, respectively. Then, the decomposition mechanism of (CF3)2CFCN molecule and the formation mechanism of gas by-products were studied via density functional theory (DFT) method. The results show that the major gas by-products are CO, CO2, C2O3F6, CF4, C2F6, C3F6, C3F8, C2F4, (CF3)3CF, CF3CN, C2F5CN and CNCN, in addition to trace amounts of F3CC≡CCF3 and CF3CF=CFCF3. Among the three initial dissociation pathways of (CF3)2CFCN molecule, a C-CF3 bond fission pathway that produces CF3CFCN and CF3 radicals is identified as the thermodynamically favorable channel. The bond energy of C–CF3 bond calculated at M06-2X/def2-QZVP//M06-2X/6-311G(d,p) level is 94.7 kcal/mol.

Mechanism of byproduct formation in oxidative dehydrogenation of ethylbenzene to styrene on magnesium ferrite-containing catalyst

It has been shown by application of the kinetic isotope method that in the oxidative dehydrogenation of ethylbenzene to styrene on a magnesium ferrite catalyst, benzene and toluene are formed from ethylbenzene and also from styrene. Carbon dioxide appears mainly as a result of exhaustive oxidation of the side chain of the aromatic hydrocarbon.

Mechanisms of antioxidant action: Auto-synergistic antioxidants based on thiol rubber adducts

The mechanism of by-product formation in the reaction of a thiol antioxidant, 3,5-di-tertbutyl-4-hydroxybenzyl mercaptan (BHBM), with rubber latices is shown to involve two processes, viz dimerization of the intermediate thiyl radical to give disulphide (BHBDS) and the reaction of the intermediate quinonemethide with water to give the aldehyde and with BHBM to give the monosulphide (BHBMS). The two sulphides themselves react with rubber in a slower reaction. The bound antioxidants obtained with natural rubber and nitrile-butadiene rubber are very much more effective than the present generation of commercial heat ageing antioxidants under conditions where the antioxidants can be lost from the rubbers by volatilization or solvent or detergent leaching. This is partly due to their resistance to removal from the polymers but there is also evidence that the auto-synergistic antioxidant bound to the rubber is more effective than single function antioxidants, due to the presence of the sulphide linkage.