KINETICS OF OXIDATIVE AMMONOLYSIS OF 4-BROMO-o-XYLENE: I.
1675
We found that n value in Eq. (1) is close to 0.5 (see
the figure). As follows from data given on the figure,
parallel way of 4-bromophthalonitrile formation is not
S
Bo-TN
1
0
.0
.8
1
2
3
4
realized. Small divergence of SBо-TN from 1 at (РBо-TN
/
РBо-Xy) = 0 is connected with 4-bromo-о-xylene
oxidation into СО , which was neglected in this report
2
since the value S(CO ) even at 693 K did not exceed
2
n
0.6
0
.086. The analysis of the ratio WBо-Xy/P
showed
Bo-Xy
that f(P ) ≡ 1 at all the temperatures. Therefore, the
i
0
0
.4
.2
reaction rates of 4-bromo-о-xylene and 4-bromo-о-
tolunitrile conversion are described by the half-order
equations with respect to the corresponding com-
7
.55
ponents. We found that k =10
exp (–94680.8/RT);
1
8
.01
0.0
k2 = 10 exp(–101492.4/RT). The activation energy is
0
.0 0.2 0.4 0.6 0.8 1.0 1.2
–
1
given in J mol .
0
.5
(PBo-TN/PBo-Xy)
Rate values are given it Tables 1–3 calculated using
the found constants. The divergence between
experimental and calculated values does not exceed
experiment accuracy.
Dependence of selectivity of 4-bromo-о-tolunitrile forma-
tion on the partial pressures of 4-bromo-о-xylene and 4-
bromo-о-tolunitrile in coordinates of Eq. (1) at different
temperatures, K: (1) 633, (2) 653, (3) 673, and (4) 693.
EXPERIMENTAL
determined by titration results of the unreacted sulfuric
acid in the second trap. The analysis of the products
absorbed with 1,4-dioxane was carried out on a
Khrom-5 chromatograph with flame-ionization
detector. A mixture of Apiezon L (21%) and PEG-
40000 (0.5%) on Chromaton N-AW (0.2–0.25 mm) or
only polysorb-1 (0.25–0.5 mm) were used as stationary
phase, by which column (1200´4 mm) was filled.
Kinetic measurements were performed on an
installation equipped with flowing non-gradient reactor
20 cm ) made of “12Х18Н10Т” steel with vibro-
liquified catalyst layer. The part of the installation was
maintained at 500–520 K to avoid the condensation of
high-boiling products. Oxygen and nitrogen were
purified from traces of organic compounds and dried
before use. Ammonia was passed through an oil filter.
3
(
–
1
Carrier gas nitrogen, flow-rate 80 ml min .
Temperature of the tests inlet is 353 K; rate of the
4
4
-Bromo-о-xylene of chemically pure grade was used.
-Bromophthalonitrile, 4-bromophthalimide, 4-bromo-
–
1
programmed temperature rise 20 deg min .
о-tolunitrile, and 4-bromobenzonitrile were isolated
from the products of 4-bromo-о-xylene oxidative
ammonolysis and purified by distillation.
The calculation of the chromatograms was made
by the internal reference method (relative to
tetradecane).
4
-Bromophthalonitrile, 4-bromo-о-tolunitrile, 4-
REFERENCES
bromophthalimide, 4-bromobenzonitrile, carbon
dioxide, and unreacted 4-bromo-о-xylene, oxygen and
gas-diluent nitrogen were chromatographically
identified in the reaction products. Chromatographic
analysis was performed by the following scheme.
Reaction gases were sequentially passed through a trap
1.
Rizaev, R.G., Bagirzade, G.A., Sheinin, V.E., et. al.,
Abstracts of Papers, Nauchnaya konferentsiya
posvyashchennaya 95-letnemu yubileyu akademika M.F.
Nagieva (Scientific Conference Devoted to 95 Anni-
versary of Academician М.F. Nagiev), Baku: IKhP
NANA, 2003, p. 14.
with
1,4-dioxane
to
absorb
nitriles,
4-
bromophthalimide and 4-bromo-о-xylene and with
sulfuric acid to absorb ammonia. The analysis of
carbon dioxide was performed on a LKhM-8MD
chromatograph. TEGNM on INZ-600 was used as
2
3
.
.
Mikhalenko, S.A., Derkacheva, V.M., and Lukya-
nets, Е.А., Zh. Obshch. Khim., 1981, vol. 51, no. 7,
p. 1650.
Rizaev, R.G., Sheinin, V.E., Magerramova, Z.Yu., et. al.,
stationary phase. Separation of О and N was made on
2
2
Abstracts
of
Papers,
Nauchno-tekhnicheskaya
this chromatograph using parallel column filled with
NaX. Ammonia concentration at the reactor output was
konferentsiya v oblasti neorganocheskoi i fizicheskoi
khimii posvyashchennaya 60-letiyu instituta (Scientific
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 8 2010