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- W2034131053 abstract "The gas phase reaction of iodine (2.8–43.3 torr) with methyl ethyl ketone (MEK) (7.4–303.4 torr) has been studied over the temperature range 280–355°C in a static system. The initial rate of disappearance of I2 is first order in MEK and half order in I2. The rate-determining step is the abstraction of a secondary hydrogen atom by an iodine atom: where k1 is given by and θ = 2.303RT in kcal/mole. This activation energy is equivalent to a secondary CH bond strength of 92.3 ± 1.4 kcal/mole and ΔH of the methylacetonyl radical = -16.8 ± 1.7 kcal/mole. By comparison with 95 kcal/mole for the secondary CH bond strength, when delocalization of the unpaired electron with a pi bond is not possible, the resonance stabilization of the methylacetonyl radical is calculated to be 2.7 ± 1.7 kcal/mole. This value is 10 kcal/mole less than the stabilization energy of the isoelectronic methylallyl radical. The difference in pi bond energies in the canonical forms of the methylacetonyl radical is shown to account for the variation in stabilization energies." @default.
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- W2034131053 date "1970-09-01" @default.
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- W2034131053 title "Kinetics and thermochemistry of the gas phase reaction of methyl ethyl ketone with iodine. I. The resonance energy of the methylacetonyl radical" @default.
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- W2034131053 doi "https://doi.org/10.1002/kin.550020504" @default.
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