Zeitschrift fur Physikalische Chemie Neue Folge, Bd. 125, S.

255-257 by Akademische Verlagsgesellschaft, Wiesbaden 1981

(1981)

Short Communications

The Thermal Decomposition of 1,1-Dichlorocyclopropane

(Received February 16, 1981)
Reaction kinetics

Isomerization

/ Unimolecular

reaction

The thermal gas phase isomerization of 1,1-dichlorocyclopropane yields 2,3-dichloropropene and 1,1-dichloropropene in two parallel reaction channels. The product ratio was studied in the range 610 725 K. Die thermische Isomerisierung in derGasphase von 1,1-Dichlorcyclopropan verlauft inzwei parallelen Reaktionskanalen und fiihrt zu den Produkten 2,3-Dichlorpropen und 1,1-Dichlorpropen. Das Produktverhaltnis wurde im Temperaturbereich von 610 725 K studiert.

Introduction

Recently we have discovered that in the unimolecular decomposition of chemically activated 1,1-dichlorocyclopropane 2,3-dichloropropene (2,3 DCP) and 1,1-dichloropropene (1,1 DCP) are formed as primary products [1,2]. The thermal unimolecular isomerization of 1,1-dichlorocyclopropane however is reported to yield 2,3 DCP as the only product [3]. Parry et al. [3] were unable to detect 1,1 DCP because this component remains unseparated under the analytical conditions employed by these authors. We have therefore reinvestigated the thermal decomposition of 1,1dichlorocyclopropane between 610 and 725 K and could show, that under these conditions also both dichloropropenes are found: chlorine and hydrogen migration evidently take place in two parallel reaction channels. Experimental 1,1-Dichlorocyclopropane was prepared according to a description given by Stevens [4] and could be obtained in 93,4 % purity. It was contaminated by monochlorocyclopropane (3,9 %), 1-chloropropane (1,2 %), and diethylether (1,5%). The two chlorocompounds decompose in well known reactions [5] and diethylether is stable under the reaction conditions. Therefore an
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256

Short Communication

interference of these components with the isomerization reactions of interest is not expected. Addition of NO did not effect the product composition and thus radical reactions were absent. The experiments were done with a conventional static system in a seasoned 101 reaction vessel at 14mbar total pressure. After an appropriate length of time dependent on the reaction temperature the product mixture was collected and analysed by gaschromatography. A 12 m Carbowax column was used for the separation (10 % Carbowax 20 M on chromosorb R NAW 60-80 mesh).

Results and discussion

The ratio of the amounts of the two dichloropropenes equals the ratio of the rate constants for the unimolecular reactions of their formation:

(1,1 DCP)/(2,3 DCP)

and

k2K

is known from the work

=

kjk2, of Parry et al. [3]:

=

From this indicated above

k2x 1015,3010exp(-241.9 OkJV/vr^1. equation and 13 runs spread out over the temperature
we

(1)
range

derived:

A:loo

1014500-38exp(-250 SkJ/^^s"1.
least square fits

(2)

These two rate constant expressions obtained by following product ratios: at 610 K; (1,1 DCP)/(2,3 DCP) 0.050; and 0.064. at 725 K; (1,1 DCP)/(2,3 DCP)
= =

yield

the

Eichler et al. [2] suggested the following Arrhenius isomerization of 1,1-dichlorocyclopropane to 1,1 DCP:

equation

for the

fcloo

l015 32exp(-26lkJ//?r)s-1.

(3)

This equation gave the best fit to all experimental data of chemical [2,6] and thermal activation which corresponds to an energy content of 1,1-dichlorocyclopropane ranging between 327 kJ mol~1 and 400 kJ mol~Furthermore (3) includes a value for EA which agrees better with the cyclopropane isomerizations [5] that also proceed with hydrogen atom migration. Using Eqs. (1) and (3) one calculates:

at610K;(l,l DCP)/(2,3DCP) at 725 K; (1,1 DCP)/(2,3 DCP)

0.037 and 0.069.

our

This is considered to be still in reasonable agreement with data.

experimental

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Short Communication
References

257

1. H. Heydtmann, K. Eichler and B. Hildebrandt, Z. Phys. Chem. Neue Folge 113 (1978) 1. 2. a) K. Eichler and H. Heydtmann, Int. J. Chem. Kin., to be published. b) K. Eichler, Dissertation, Frankfurt/M. 1980. 3. a) K. A. W. Parry and P. J. Robinson, J. Chem. Soc. (B) 1969, 49. b) K. A. Holbrook, J. S. Palmer and K. A. W. Parry, Trans. Faraday Soc. 66 (1970) 869. 4. P. G. Stevens, J. Am. Chem. Soc. 68 (1946) 620. 5. P. J. Robinson and K. A. Holbrook, Unimolecular Reactions, Wiley Interscience, London 1972. 6. H. Rullmann and H. Heydtmann, Ber. Bunsenges. Phys. Chem. 81 (1977) 490.
-

H.
Institut fur

Heydtmann

and B. Korbitzer

physikalische und theoretische Chemie Universitat Frankfurt, Robert-Mayer-StraBe 11, D-6000 Frankfurt am Main

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