ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

On thermal dehydrochlorination of model compounds for poly(vinyl chloride). V. Frequency factor calculations

P. Kovařík, L. Valko, and A. Gatial

Department of Physical Chemistry, Slovak Technical University, 812 37 Bratislava

Abstract: The statistical thermodn. method was used to calc. activation entropies and det. frequency factors (A) for thermal dehydrochlorination of 49 alkyl and alkenyl chlorides, many of which are model substances of PVC [9002-86-2]. The entropic contributions of stretching and bending vibrations, restricted internal rotations, and torsional vibrations were detd. The degeneration of the reaction pathway was also taken into account. The calcns. were carried out on the assumption that the investigated reactions follow the monomol. mechanism through a 4-centric, planar and a polar activated complex. The calcd. frequency factors were statistically averaged and compared with exptl. lit. values. There was a good agreement of the measured and calcd. frequency factors; the differences between these values varied in the interval Δ log (A/s^-1) = ± 0.5.

Full paper in Portable Document Format: 365a611.pdf

Chemical Papers 36 (5) 611–626 (1982)