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- W2155489722 abstract "Abstract Isobutane (RH) dissolved in acetic acid (RH/AcOH = 0.3 g/g) has been oxidized by molecular oxygen ( P o2 ∼20 atm; P total ∼45–55 atm) at 135 and 155°C. Acetone, t ‐butylalcohol ( t ‐BuOH) and methylacetate are the main products. Their distribution does not vary strongly (less than 10%) when the percentage of RH oxidized is between 8 and 25%. In the oxidation initiated by the t ‐butyl‐hydro‐peroxide, the ratio R = t ‐BuOH/acetone, mol.mol −−1 , is about 2.45 at 135°C., and 1.28 at 155°C. The comparison with the results obtained in the thermal decomposition of t ‐butylperoxide shows that R measures the relative reactivities of the t ‐butylperoxidic radicals towards the abstraction of an hydrogen atom, or towards their own isomerization. The variation of R with temperature measures thus the difference (Δ E = E a isom ‐ E a abst ) between the energies of activation relative to these two processes, i.e. 11 kcal. mol −−1 . The soluble acetates of transition elements (VO +2 , Cr +3 , Co +2 , Ni +2 , Ag +1 , Cu +2 , Mn +2 ; 4.10 −−3 cation g/1 (AcOH, 25°C)) accelerate the oxidation and result in low values for R (the lowest being about the third as that for the initiated oxidation). However, there are two exceptions: copper (II) acetate has no depressive effect on R but accelerates the reaction; manganese(II) acetate leads to the formation of AcOH. Catalysis of the isomerization of the t ‐butylperoxidic and t ‐butyloxidic radicals, by the salts of transition elements, explains the results. A relationship is observed between the decrease of R and E , through the use of the catalysts, and the paramagnetic properties of these last. That relationship is interpreted by the theory of the catalysis developed by D. A. Dowden." @default.
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- W2155489722 date "1968-01-01" @default.
- W2155489722 modified "2023-09-24" @default.
- W2155489722 title "Catalyse Des Oxydations A Chaînes Ramifiées" @default.
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- W2155489722 doi "https://doi.org/10.1002/bscb.19680770302" @default.
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