Studies on the influence of vibrational excitation of CF2Cl* radicals on the rate of their reaction with HCl

A method is proposed for studying the influence of vibrational excitation of radicals on their reactivity in bimolecular reactions. Investigations of the reaction CF₂Cl + HCl → CF₂ HCl + Cl by this method show for the first time that this reaction is accelerated by vibrational excitation of CF₂Cl* radicals. Under the experimental conditions, it was found that k^*₁/k₁ ? 6.0.     

Investigations of multiphoton selective dissociation of (CH3)2O in the field of a pulsed CO2 laser

Experimental investigations of multiphoton selective dissociation of (CH₃)₂O induced by a pulsed CO₂ laser have been conducted. Separation of H, C, and O isotopes was performed in enriched mixtures and in samples with the natural abundance. The following coefficients of selectivity have been obtained:K _D/K_H=4.0,K ₁₃/K₁₂=1.7, andK ₁₈/K₁₆≧1.6. We studied the dependences of the selectivity coefficient on ether pressure, on the laser energy and frequency as well as the influence of secondary chemical reactions on the dissociation selectivity. Estimations made by using the RRKM theory have indicated that ether molecules that decompose have an average excitation energy above the dissociation threshold of ∼1.5 kcal/mole.     

Study of selective dissociation in C6F5H?C6F5D mixtures induced by intense CO2 laser pulses

Irradiation of a C₆F₅H–C₆F₅D mixture at 1 Torr by a tunable CO₂ pulse laser brings about chiefly dissociation of one component depending on the frequency of emission absorbed by the proper molecules. The addition of radical acceptors increases the selectivity by suppressing secondary reactions.

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C₆F₅H C₆F₅D 1 CO₂-, , . .

     

Influence of secondary chemical reactions on the selectivity of the multiphoton dissociation process in C6F5H?C6F5D mixtures

Radical acceptors significantly increasing the dissociation selectivity in C₆F₅H–C₆F₅D mixtures have been selected by studying the mechanism of C₆F₅H dissociation in the field of a pulsed CO₂-laser. The contribution of secondary chemical reactions to the total rate of consumption of the initial molecules has been determined.

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C₆F₅H CO₂- , C₆F₅H C₆F₅D. .