FLUORINATION OF ORGANIC COMPOUNDS WITH COBALT TRIFLUORIDE
961
column. The GC-MS analysis was performed on a
Hewlett-Packard device comprising an HP-5890 gas
chromatograph, an HP5972 mass-selective detector,
and a Vectra 5/100 working station with software
for data processing and Wiley138.L and NBS75K.L
database.
The fluorination rate constants and activation en-
ergy [9] were calculated from the concentration-vs.-
time plots for 150, 180, 220, and 250 C.
ACKNOWLEDGMENTS
The work was financially supported by ISTC.
REFERENCES
Chromatographic separation was performed on
a 30 m HP-5MS capillary column in the programmed-
heating mode. Chromatograms were recorded by the
total ion current within the 35 700 mass range. The
impurities were identified by comparing the mass
spectra of separated mixture components with those
from the Wiley138.L and NBS75K.L databases and
by calculation.
1. Kornilov, V.V., Kosteev, R.A., Maksimov, B.N., et al.,
Zh. Prikl. Khim., 1995, vol. 68, no. 9, pp. 1409 1418.
2. Advances in Fluorine Chemistry, vol. I II, Stacey, M.,
Tatlow, J.C.,and Sharpe, A.G., Eds., London: Butter-
worths Scientific Publications, (1960 1961).
3. Zakharov, V.Yu., Denisov, A.K., and Novikova, M.D.,
The kinetics of fluorination of I was studied in
a vertical reactor made from a nickel tube (inner di-
ameter 36 mm). The reactor was packed with CoF3
with bed height of 300 mm. A thermocouple pocket
was arranged along the reactor axis. The temperature
variation throughout the bed did not exceed 3 C. From
a batcher, a mixture of I (25 wt %) with (C3F7)3N
(75 wt %) and fluorine were supplied at definite and
constant rates into a mixer-evaporator, which was
a 500-mm nickel tube 36 mm in diameter, equipped
with a controllable heater. The fluorine excess did
not exceed 20% relative to the stoichiometry. From
the evaporator, the reaction mixture passed through
a catalyst bed (with particle size of 0.035 0.05 mm)
and condensed in a trap cooled with liquid nitrogen.
After process completion, the trap was warmed to
room temperature and weighed, and the reaction prod-
ucts were analyzed by GLC. Low-boiling products
containing fluorine and HF were neutralized in a col-
umn with lime and analyzed by GLC. The experi-
ments were performed at 150, 180, 220, and 250 C.
Zh. Org. Khim., 1994, vol. 30, no. 12, pp. 1844 1846.
4. Zakharov, V.Yu., Denisov, A.K., and Novikova, M.D.,
Abstracts of Papers, Mezhdunarodnaya konferentsiya
Khimiya, tekhnologiya i primenenie ftorsoderzha-
shchikh soedinenii v promyshlennosti (Int. Conf.
Chemistry, Technology, and Application of Fluorine-
Containing Compounds in Industry ), St. Petersburg,
1994, p. 11.
5. Moldavsky, D.D., Bisren, T.A., Kaurova, G.I., and
Furin, G.G., J. Fluorine Chem., 1999, vol. 94,
pp. 157 167.
6. Rozovskii, A.Ya., Katalizator i reaktsionnaya sreda
(Catalyst and Reaction Medium), Moscow: Nauka,
1988.
7. Asovich, V.S. and Kosteev, R.A., Zh. Prikl. Khim.,
1994, vol. 67, no. 8, pp. 1320 1323.
8. Asovich, V.S., Kornilov, V.V., Kosteev, R.A., and
Maksimov, B.N., Zh. Prikl. Khim., 1994, vol. 67, no. 1,
pp. 103 106.
9. Leidler, K., Reaction Kinetics, vol. I: Homogeneous
gas reactions, vol. II: Reactions in Solution, Oxford:
Pergamon, 1963.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 75 No. 6 2002