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Reactions of (CO 2 ) 2 + and (CO) 2 + association ions
Author(s) -
Sieck L. Wayne
Publication year - 1978
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.550100403
Subject(s) - chemistry , photoionization , ion , analytical chemistry (journal) , kinetics , chemical kinetics , ambipolar diffusion , cationic polymerization , torr , mass spectrometry , diffusion , chemical reaction kinetics , inorganic chemistry , ionization , electron , thermodynamics , organic chemistry , physics , chromatography , quantum mechanics
The reactons of (CO 2 ) 2 + and (CO) 2 + with various additives have been investigated using the NBS high‐pressure photoionization mass spectrometer at total pressures of 0.4–1.0 torr of either CO 2 or CO. The additives include CH 4 , CD 4 , C 2 H 2 , O 2 , H 2 O, 15,14 N 2 O, and CO in both CO 2 and 13 CO 2 . Second‐ and third‐order rate coefficients based on an ambipolar diffusion model are reported for 25 separate reaction pairs at 295°K, as well as sequential cationic reaction mechanisms. An approximate value of 225 ± 3 kcal/mol (941 ± 13 kJ/mol) was derived for Δ H f (CO) 2 + based on the kinetics observed in various CO‐additive mixtures. Some projections regarding the utility of the data under other conditions are also included.