Premium
Kinetic modeling of the reactions of C 3 H 3 + with acetylene, deuteroacetylene, and diacetylene
Author(s) -
Wiseman Floyd L.,
Ozturk Feza,
Zerner Michael C.,
Eyler John R.
Publication year - 1990
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.550221108
Subject(s) - diacetylene , chemistry , acetylene , deuterium , fourier transform ion cyclotron resonance , kinetic isotope effect , kinetic energy , ion , photochemistry , atomic physics , organic chemistry , physics , polymerization , quantum mechanics , polymer
The reactions of ℓ‐C 3 H 3 + (propargylium cation) with acetylene and diacetylene have been modeled kinetically. Data were obtained from Fourier Transform Ion Cyclotron Resonance (FTICR) experiments on these systems, which are themselves models for soot particle initiation. Acetylene forms an encounter complex with ℓ‐C 3 H 3 + , but, in the absence of a third body collision, the complex decomposes to acetylene and c ‐C 3 H 3 + (cyclopropenylium cation) at about 1/3 the rate it decomposes to acetylene and ℓ‐C 3 H 3 + , in spite of the fact that c ‐C 3 H 3 + is ca. 115 kJ/mol more stable than ℓ‐C 3 H 3 + . The encounter complex is long enough lived, and energetic enough, to scramble deuterium in reactions between ℓ‐C 3 H 3 + and C 2 D 2 . These reactions have been successfully modeled, yielding a nearly statistical distribution of deuterium, and a rather large kinetic isotope effect. The more complex reactions of ℓ‐C 3 H 3 + with diacetylene have also been modeled.