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Because of needs for understanding the chemical kinetic mechanism in chlorocarbon molecule incineration, we have recently completed studies on the thermal decompositions of COCl[sub 2], CH[sub 3]Cl, CH[sub 2]Cl[sub 2], CCl[sub 4], and CF[sub 3] Cl. The shock tube technique combined with atomic resonance absorption spectrometry (ARAS), as applied to Cl atoms, has been used to obtain absolute rate data for these reactions. In all cases, the decompositions are nearly in the second-order regime. Theoretical calculations, using the Troe formalism, have been performed. In these calculations, both the threshold energies for decomposition, E[sub o], and the energy transferred per down collision, [Delta]E[sub down], are varied parametrically for best fitting to the data. The latter quantity determines the collisional deactivation efficiency factor, [beta][sub c].
Unimolecular dissociation reactions of small molecules were investigated. The thermal decomposition of N2O was investigated in a detailed way. By using the methods of shock waves and adiabatic compression the reaction was studied between 1200 and 2500K. All experimental results which describe a variation of the low pressure limiting rate of about eleven orders of magnitude, are in good agreement. This example and others were selected for a detailed theoretical analysis of unimolecular reactions of three- and four-atomic molecules. For shock tube experiments up to about 1000 atmospheres, a shock tube with 70 mm internal diameter was constructed and put into operation. Driving pressures up to about 200 atmospheres were used for experiments on N2O- and N2H4- decomposition, which gave data on the high pressure limiting rate of both dissociations.
The thermal decomposition of CH[sub 2]Cl[sub 2] has been investigated in reflected shock waves experiments at temperatures between 1400--2300 K and at three different loading pressures with various initial CH[sub 2]Cl[sub 2] concentrations. The resulting product Cl-atoms are monitored by the atomic resonance absorption spectrometer (ARAS) technique. A reaction mechanism is used to numerically simulate the measured Cl-atom profiles in order to obtain rate constants for the two primary dissociation reactions: (1) CH[sub 2]Cl[sub 2] [yields] CHCl + HCl and (2) CH[sub 2]Cl[sub 2] [yields] CH[sub 2]Cl + Cl. The experimental second-order Arrhenius expressions for the two reactions are k[sub 1]/[Kr] = 2.26 [times] 10[sup [minus]8] exp( -29007 K/T) cm[sup 3] molecule[sup [minus]1] s[sup [minus]1] and k[sub 2]/[Kr] = 6.64 [times] 10[sup [minus]9] exp( -28404 K/T) cm[sup 3] molecule[sup [minus]1] s[sup [minus]1], with standard deviations of [plus-minus]43% and 40%, respectively. Results are compared to theoretical calculations using the semi-empirical Tore formalism. The best fits to the experimental data obtained with threshold energy and collisional energy transfer parameters of E[sub 10][sup o] = 73.0 kcal mole[sup [minus]1] and [Delta]E[sub 1down] = 630 cm[sup [minus]1]. Similar values for reaction (2) are E[sub 20][sup o] = [Delta]H[sub 20][sup o] = 78.25 kcal mole[sup [minus]1] and [delta]E[sub 2down] = 394 cm[sup [minus]1].
The thermal decomposition of CH2Cl2 has been investigated in reflected shock waves experiments at temperatures between 1400--2300 K and at three different loading pressures with various initial CH2Cl2 concentrations. The resulting product Cl-atoms are monitored by the atomic resonance absorption spectrometer (ARAS) technique. A reaction mechanism is used to numerically simulate the measured Cl-atom profiles in order to obtain rate constants for the two primary dissociation reactions: (1) CH2Cl2 2!CHCl + HCl and (2) CH2Cl2 2!CH2Cl + Cl. The experimental second-order Arrhenius expressions for the two reactions are k1/[Kr] = 2.26 × 10−8 exp( -29007 K/T) cm3 molecule−1 s−1 and k2/[Kr] = 6.64 × 10−9 exp( -28404 K/T) cm3 molecule−1 s−1, with standard deviations of ±43% and 40%, respectively. Results are compared to theoretical calculations using the semi-empirical Tore formalism. The best fits to the experimental data obtained with threshold energy and collisional energy transfer parameters of E10{sup o} = 73.0 kcal mole−1 and [Delta]E{sub 1down} = 630 cm−1. Similar values for reaction (2) are E20{sup o} = [Delta]H20{sup o} = 78.25 kcal mole−1 and [delta]E{sub 2down} = 394 cm−1.