ABSOLUTE DETERMINATIONS OF THE ADDITION RATE CONSTANTS FOR THE REACTIONS OF O (3P) ATOMS WITH HALOGENATED PROPENES AND BUTENES. A STRUTURE-ACTIVITY RELATIONSHIP FOR THE ESTIMATION OF RATE CONSTANTS

COMETTO, PABLO M.; TERUEL, MARIANO A.; TACCONE, RAÚL A.; LANE, SILVIA I.

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY

Año: 2005 p. 142 - 147

0894-3230

The kinetics of the reactions of O(3P) atoms with CF3CH=CH2, CF3CCl=CCl2, CF3CF=CClCF3and CF3CCl=CClCF3 were studied at 298K using a discharge flow tube system. This is the first absolute kinetic study of these reactions. The overall rate constants based on the measured afterglow reactions were (3.4±0.4)x10-14, (3.3±0.6) x10-14, (1.3±0.3) x10-14and (1.9±0.4) x10-14 cm3 molecule-1 s-1  , respectively. The experiments were carried out under pseudo-first-order conditions with [O(3P)]0>>[alkene]0.  The effect of substituent atoms or groups on the reactivity was analyzed. A simple method, using a structure–activity relationship based on the structure of the alkene, was applied for the first time to the reactions of O(3P) with haloalkenes. It is shown that this approach is useful in obtaining an initial estimate of unknown rate constants for reactions of O(3P) with alkenes. [O(3P)]0>>[alkene]0.  The effect of substituent atoms or groups on the reactivity was analyzed. A simple method, using a structure–activity relationship based on the structure of the alkene, was applied for the first time to the reactions of O(3P) with haloalkenes. It is shown that this approach is useful in obtaining an initial estimate of unknown rate constants for reactions of O(3P) with alkenes. [O(3P)]0>>[alkene]0.  The effect of substituent atoms or groups on the reactivity was analyzed. A simple method, using a structure–activity relationship based on the structure of the alkene, was applied for the first time to the reactions of O(3P) with haloalkenes. It is shown that this approach is useful in obtaining an initial estimate of unknown rate constants for reactions of O(3P) with alkenes. cm3 molecule-1 s-1  , respectively. The experiments were carried out under pseudo-first-order conditions with [O(3P)]0>>[alkene]0.  The effect of substituent atoms or groups on the reactivity was analyzed. A simple method, using a structure–activity relationship based on the structure of the alkene, was applied for the first time to the reactions of O(3P) with haloalkenes. It is shown that this approach is useful in obtaining an initial estimate of unknown rate constants for reactions of O(3P) with alkenes. [O(3P)]0>>[alkene]0.  The effect of substituent atoms or groups on the reactivity was analyzed. A simple method, using a structure–activity relationship based on the structure of the alkene, was applied for the first time to the reactions of O(3P) with haloalkenes. It is shown that this approach is useful in obtaining an initial estimate of unknown rate constants for reactions of O(3P) with alkenes. [O(3P)]0>>[alkene]0.  The effect of substituent atoms or groups on the reactivity was analyzed. A simple method, using a structure–activity relationship based on the structure of the alkene, was applied for the first time to the reactions of O(3P) with haloalkenes. It is shown that this approach is useful in obtaining an initial estimate of unknown rate constants for reactions of O(3P) with alkenes. cm3 molecule-1 s-1  , respectively. The experiments were carried out under pseudo-first-order conditions with [O(3P)]0>>[alkene]0.  The effect of substituent atoms or groups on the reactivity was analyzed. A simple method, using a structure–activity relationship based on the structure of the alkene, was applied for the first time to the reactions of O(3P) with haloalkenes. It is shown that this approach is useful in obtaining an initial estimate of unknown rate constants for reactions of O(3P) with alkenes. [O(3P)]0>>[alkene]0.  The effect of substituent atoms or groups on the reactivity was analyzed. A simple method, using a structure–activity relationship based on the structure of the alkene, was applied for the first time to the reactions of O(3P) with haloalkenes. It is shown that this approach is useful in obtaining an initial estimate of unknown rate constants for reactions of O(3P) with alkenes. [O(3P)]0>>[alkene]0.  The effect of substituent atoms or groups on the reactivity was analyzed. A simple method, using a structure–activity relationship based on the structure of the alkene, was applied for the first time to the reactions of O(3P) with haloalkenes. It is shown that this approach is useful in obtaining an initial estimate of unknown rate constants for reactions of O(3P) with alkenes. cm3 molecule-1 s-1  , respectively. The experiments were carried out under pseudo-first-order conditions with [O(3P)]0>>[alkene]0.  The effect of substituent atoms or groups on the reactivity was analyzed. A simple method, using a structure–activity relationship based on the structure of the alkene, was applied for the first time to the reactions of O(3P) with haloalkenes. It is shown that this approach is useful in obtaining an initial estimate of unknown rate constants for reactions of O(3P) with alkenes. [O(3P)]0>>[alkene]0.  The effect of substituent atoms or groups on the reactivity was analyzed. A simple method, using a structure–activity relationship based on the structure of the alkene, was applied for the first time to the reactions of O(3P) with haloalkenes. It is shown that this approach is useful in obtaining an initial estimate of unknown rate constants for reactions of O(3P) with alkenes. [O(3P)]0>>[alkene]0.  The effect of substituent atoms or groups on the reactivity was analyzed. A simple method, using a structure–activity relationship based on the structure of the alkene, was applied for the first time to the reactions of O(3P) with haloalkenes. It is shown that this approach is useful in obtaining an initial estimate of unknown rate constants for reactions of O(3P) with alkenes. [O(3P)]0>>[alkene]0.  The effect of substituent atoms or groups on the reactivity was analyzed. A simple method, using a structure–activity relationship based on the structure of the alkene, was applied for the first time to the reactions of O(3P) with haloalkenes. It is shown that this approach is useful in obtaining an initial estimate of unknown rate constants for reactions of O(3P) with alkenes.