W. Kessler et al., IN-SITU RAMAN-SPECTROSCOPY FOR THE STUDY OF HIGH-PRESSURE REACTIONS, Berichte der Bunsengesellschaft fur Physikalische Chemie, 101(4), 1997, pp. 698-702
Citations number
6
Categorie Soggetti
Chemistry Physical
Journal title
Berichte der Bunsengesellschaft fur Physikalische Chemie
An optical high-pressure cell has been developed for spectroscopic inv
estigations of rapid high-pressure reactions. It can be coupled with c
ommercial Raman spectrometer. The measuring cell is suitable for use a
t pressures of up to 2000 bar and temperatures of up to 200 degrees C.
The advantages of in situ Raman spectroscopy are demonstrated in the
course of an investigation of the decomposition of tertiary butyl pero
xypivalate in solution. This organic peroxide is a standard initiator
for the radical high-pressure polymerisation of olefins for which it i
s used at pressures of 1300 to 3000 bar and temperatures of 160 to 190
degrees C. The rate of decomposition was measured within a wide press
ure and temperature range. From the results the half-life, the frequen
cy factor, the energy of activation and the activation volume of the p
eroxide decomposition reaction were determined. The data thus obtained
were compared with data in the literature which had been obtained by
other methods.