Abstract:
Kinetics and product studies of
the decompositions of allyl-t-butyl peroxide and 3-hydroperoxy-
l-propene (allyl hydroperoxide ) in tolune were investigated.
Decompositions of allyl-t-butyl peroxide in toluene at 130-1600
followed first order kinetics with an activation energy of
32.8 K.cals/mol and a log A factor of 13.65. The rates of decomposition
were lowered in presence of the radical trap~methyl
styrene. By the radical trap method, the induced decomposition
at 1300 is shown to be 12.5%. From the yield of 4-phenyl-l,2-
epoxy butane the major path of induced decomposition is shown
to be via an addition mechanism. On the other hand, di-t-butYl
peroxyoxalate induced decomposition of this peroxide at 600
proceeded by an abstraction mechanism. Induced decomposition
of peroxides and hydroperoxides containing the allyl system is
proposed to occur mainly through an addition mechanism at these
higher temperatures. Allyl hydroperoxide in toluene at 165-1850
decomposes following 3/2 order kinetics with an Ea of 30.2 K.cals
per mole and log A of 10.6. Enormous production of radicals
through chain branching may explain these relatively low values
of E and log A. The complexity of the reaction is indicated a
by the formation of various products of the decomposition. A
study of the radical attack of the hydro peroxide at lower temperatures
is suggested as a further work to throw more light on
the nature of decomposition of this hydroperoxide.
