Abstract:
The thermal decomposition of 2,3-di~ethy l - J-hydr operox y-
1 - butene , p r epared f rol") singl e t oxygen, has been studied
i n three solvents over the tempe r a ture r ange from 1500e to
l o00e and t!1e i 111 t ial ~oncentrfttl nn r Ange from O. 01 M to
0.2 M. Analys i s of the kine tic data ind ica te s i nduced homolysis
as the n ost probRble mode of d e composition, g iving rise to a
3/2 f S order dependence upon hy d.roperoxide concent :r8.tl on .
Experimental activation e nergies for the decomposition were
f ound to be between 29.5 kcsl./raole and 30.0 k cal./mole .• \,iith
log A factors between 11 . 3 and 12.3. Product studies were
conducted in R variety of solvents a s well as in the pr esence
of a variety of free r adical initiators . Investigation of
the kinetic ch a in length indicated a chain length of about
fifty.
A degenerat i ve chain branching mechanism 1s proposed
which predicts the multi t ude of products which Rre observed
e xperimentally as well as giving activation energies and
log A factors si~il a r to those found experimentally .
