1965 Volume 38 Issue 12 Pages 2156-2159
The rate of the cobalt-catalyzed decomposition of tetralin hydroperoxide in fatty acid solvents was first order with respect to hydroperoxide and second order with respect to the cobalt, and it was inversely proportional to the square of the acid concentration; i.e., -dROOH/dt=″(Co)2·(ROOH)/(Acid)2. The rate constant, k″, was found to be almost constant, regardless of the molecular weight of the acid. The values of k3⁄k61⁄2 obtained from the limiting rate of the oxidation showed an excellent linear correlation against the dielectric function of (D−1)/(2D+1). The rate of the oxidation of tetralin calculated by -dO2/dt=k3(k1′⁄2k6)1⁄2(RH)(Co)−k1′(Co)2/2 showed an excellent agreement with the value observed at cobalt concentrations lower than 3×104 mol./l. Strong organic acids such as chloroacetic acids deactivated the cobalt catalyst, and oxalic acid, which has shown the strongest deactivating effect of all the acids tested, deactivated equimolar cobalt salt.
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