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Primary processes in the 147‐nm photolysis of 1,1‐dichloroethane
Author(s) -
Salomon D.,
Kirk A. W.,
TschuikowRoux E.
Publication year - 1977
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550090410
Subject(s) - chemistry , 1,2 dichloroethane , excited state , photodissociation , acetylene , rydberg formula , torr , chlorine , ground state , dichloroethane , chlorine atom , photochemistry , decomposition , analytical chemistry (journal) , medicinal chemistry , atomic physics , organic chemistry , thermodynamics , catalysis , ionization , ion , physics
The room temperature photolysis of 1,1‐dichloroethane at 147 nm in the pressure range of 1.34‐196.2 torr is characterized almost entirely by the molecular elimination of HCl, Cl 2 , and small quantities of H 2 . Acetylene is also produced. While it is possible that the C 2 H 2 arises, in part, from the decomposition of vibrationally excited ground states of C 2 H 3 Cl and/or C 2 H 4 , in this particlar case serious consideration has to be given to alternative explanations where the products of the primary processes are formed in electronically excited states. The ±, elimination of molecular chlorine is not inconsistent with an increased degree of ClCl interaction predicted for a «Rydberg «state of 1,1‐C 2 H 4 Cl 2 . Varying small yields of CH 4 are observed in the presence and absence of NO. The effect of large pressures of CF 4 on the quantum yields of the major products is extremely small. The extinction coefficient for 1,1‐C 2 H 4 Cl 2 at 147 nm and 296°K is 246 ± 29 cm −1 ± atm −1 .