Comments on the linear free-energy correlation between O/sub 3/ and OH addition reactions reported in Rate Constants for the Gas-Phase Reactions of O/sub 3/ with a Series of Carbonyls at 296 K

Journal Article · Fri Jan 01 00:00:00 EST 1982 · Int. J. Chem. Kinet.; (United States)

DOI:https://doi.org/10.1002/kin.550141111· OSTI ID:6310129

Gaffney, J S; Levine, S Z

Recently, Atkinson et al. reported measurements on the reaction of ozone with a series of carbonyls. In that study a correlation between ozone addition and hydroxyl-radical addition reactions was employed to predict OH addition coefficients for acrolein and crotonaldehyde of approximately 2 x 10/sup -12/ and 5 x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/, respectively. These estimates, as pointed out by the authors, are in disagreement (factor of 2 to 3 lower) with the rate coefficients previously predicted by ourselves for the same OH addition reactions using linear correlations with both ionization potentials and O(/sup 3/P) rate data. It was also suggested in that paper that this discrepancy was probably due to the likelihood that O(/sup 3/P) atoms react significantly with carbonyls via an abstraction mechanism, that is, O(/sup 3/P) rate data could not be appropriately correlated with OH addition reaction data. We believe that another, more probable, explanation exists for the above-mentioned discrepancy in rate constant estimates, and that this explanation involves the manner in which the correlation method is handled. Because this method of evaluating rate constants represents a potentially important predictive tool for chemical modelers, we feel it is necessary to reconcile the apparent disagreement in the OH-acrolein and OH-crotonaldehyde addition reaction coefficients estimated from O/sub 3/ correlations as compared to ionization potential and O(/sup 3/P) correlations. In doing so, we will also demonstrate the necessity of employing linear correlations in a consistent manner.

• Research Organization: Brookhaven National Lab., Upton, NY
• OSTI ID: 6310129
• Journal Information: Int. J. Chem. Kinet.; (United States), Vol. 14
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBONYLS
CHEMICAL REACTION KINETICS
HYDROXIDES
OZONE
ACROLEIN
ADDITIVES
ALDEHYDES
ALKENES
CHEMICAL REACTIONS
FREE ENERGY
ENERGY
HYDROCARBONS
HYDROGEN COMPOUNDS
KINETICS
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
REACTION KINETICS
THERMODYNAMIC PROPERTIES
400201* - Chemical & Physicochemical Properties
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)