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Quantitative Structure−Stability Relationships for Oxides and Peroxides of Potential Atmospheric Significance

Grela, M. A. and Colussi, A. J. (1996) Quantitative Structure−Stability Relationships for Oxides and Peroxides of Potential Atmospheric Significance. Journal of Physical Chemistry, 100 (24). pp. 10150-10158. ISSN 0022-3654 . http://resolver.caltech.edu/CaltechAUTHORS:20150623-154803850

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Abstract

A critical analysis of the most recent experimental and ab initio thermochemical data on gas-phase species reveals that (1) isodesmic metathetical reactions among simple oxides, 1/2 XOX + 1/2 YOY ↔ XOY, and those exclusively involving peroxides 1/2 XOOX + 1/2 YOOY ↔ XOOY, are nearly thermoneutral (ΔH_r = 0 ± 3 kcal/mol), but exchange reactions between oxides and peroxides, XOX + YOOY ↔ YOY + XOOX, are generally not, (2) bond additivity values BAV[X−(O−O)−X]'s for the contributions of the peroxide bond to the heats of formation of H-, C-, N-, S-, F-, and Cl-containing peroxides decrease linearly with Pauling electronegativities χ(X)'s and (3) semiempirically evaluated (MOPAC) thermochemical datasets, even when inaccurate in absolute terms, are internally consistent with such rules. These findings happen to provide the basis for the rapid and systematic assessment of the stability of novel oxides and peroxides. In this paper, that focuses on species that could be formed in the terrestrial atmosphere, we briefly discuss XOO−H bond energy trends in hydroperoxides, the existence of stable and metastable peroxy XOO• radicals, the thermochemistry of peroxyacyl nitrates, of Br- and S-containing peroxides, and the mechanism of the (FO + ClO), (FO + NO_2), (OH + OClO), (HO_2 + ClO), (ClO + NO_2), and (ClO + NO_3) reactions, among other issues.


Item Type:Article
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http://dx.doi.org/10.1021/jp952763sDOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp952763sPublisherArticle
ORCID:
AuthorORCID
Colussi, A. J.0000-0002-3400-4101
Additional Information:© 1996 American Chemical Society. Received: September 15, 1995; In Final Form: April 1, 1996.
Record Number:CaltechAUTHORS:20150623-154803850
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150623-154803850
Official Citation:Quantitative Structure−Stability Relationships for Oxides and Peroxides of Potential Atmospheric Significance M. A. Grela and A. J. Colussi The Journal of Physical Chemistry 1996 100 (24), 10150-10158 DOI: 10.1021/jp952763s
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58506
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:24 Jul 2015 19:38
Last Modified:24 Jul 2015 19:38

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