Rate constants for addition of phenoxyl radicals to the vinyl monomer double bond

1992 ◽  
Vol 41 (12) ◽  
pp. 2147-2151 ◽  
Author(s):  
I. V. Utkin ◽  
A. V. Sokolov ◽  
E. M. Pliss
Keyword(s):  
Double Bond ◽  
Rate Constants ◽  
Vinyl Monomer ◽  
Phenoxyl Radicals ◽  
Rate Constants For Addition

The analysis of muonium hyperfine interaction measurements of thermal rate constants for addition reactions

1991 ◽  
Vol 94 (4) ◽  
pp. 2794-2806 ◽  
Author(s):  
Ronald J. Duchovic ◽  
Albert F. Wagner ◽  
Ralph Eric Turner ◽  
David M. Garner ◽  
Donald G. Fleming
Keyword(s):  
Hyperfine Interaction ◽  
Rate Constants ◽  
Addition Reactions ◽  
Thermal Rate Constants ◽  
Muonium Hyperfine ◽  
Rate Constants For Addition

Rate Constants for Reactions of Phenoxyl Radicals in Solution

2005 ◽  
Vol 34 (1) ◽  
pp. 109-199 ◽  
Author(s):  
Pedatsur Neta ◽  
Jan Grodkowski
Keyword(s):  
Rate Constants ◽  
Phenoxyl Radicals

Influence of the double bond on the hydrogen abstraction reactions of methyl esters with hydrogen radical: an ab initio and chemical kinetic study

RSC Advances ◽  
2015 ◽  
Vol 5 (84) ◽  
pp. 68314-68325 ◽  
Author(s):  
Quan-De Wang ◽  
Weidong Zhang
Keyword(s):  
Double Bond ◽  
Hydrogen Atom ◽  
Ab Initio ◽  
Kinetic Study ◽  
Rate Constants ◽  
Methyl Esters ◽  
Hydrogen Abstraction ◽  
Chemical Kinetic ◽  
Hydrogen Atom Abstraction ◽  
Hydrogen Radical

This work reports a systematic ab initio and chemical kinetic study of the rate constants for hydrogen atom abstraction reactions by hydrogen radical on the isomers of unsaturated C6 methyl esters.

scholarly journals Aqueous Reactions of Organic Triplet Excited States with Atmospheric Alkenes

2018 ◽  
Author(s):  
Richie Kaur ◽  
Brandi M. Hudson ◽  
Joseph Draper ◽  
Dean J. Tantillo ◽  
Cort Anastasio
Keyword(s):  
Double Bond ◽  
Excited States ◽  
Rate Constants ◽  
Hydrogen Abstraction ◽  
Oxidation Potential ◽  
Water Soluble ◽  
Oxidation Products ◽  
Bond Dissociation ◽  
Alkyl Substitution ◽  
Triplet Excited States

Abstract. Triplet excited states of organic matter, a.k.a. triplets, are formed when brown carbon absorbs light. While triplets can be important photooxidants in atmospheric drops and particles (e.g., they rapidly oxidize phenols), very little is known about their reactivity toward many classes of organic compounds in the atmosphere. Here we measure the bimolecular rate constants of the triplet excited state of benzophenone (3BP*), a model species, with 17 water-soluble C3–C6 alkenes that have either been found in the atmosphere or are reasonable surrogates for identified species. Measured rate constants (kALK+3BP*) vary by a factor of 30 and are in the range of (0.24–7.5) × 109 M−1 s−1. Biogenic alkenes found in the atmosphere – e.g., cis-3-hexen-1-ol, cis-3-hexenyl acetate, and methyl jasmonate – react rapidly, with rate constants above 1 × 109 M−1 s−1. Rate constants depend on alkene characteristics such as the location of the double bond, stereochemistry, and alkyl substitution on the double bond. There is a reasonable correlation between kALK+3BP* and the calculated one-electron oxidation potential (OP) of the alkenes (R2 = 0.58); in contrast, rate constants are not correlated with bond dissociation enthalpies, bond dissociation free energies, or computed energy barriers for hydrogen abstraction. Using the OP relationship, we estimate aqueous rate constants for a number of unsaturated isoprene and limonene oxidation products with 3BP*: values are in the range of (0.080–1.7) × 109 M−1 s−1, with generally faster values for limonene products. Using our predicted rate constants, along with values for other reactions from the literature, we conclude that triplets are probably minor oxidants for isoprene and limonene-related compounds in cloudy or foggy atmospheres, except in cases where the triplets are very reactive.

Absolute Rate Constants for Hydrocarbon Autoxidation. XXII. The Autoxidation of some Vinyl Compounds

1972 ◽  
Vol 50 (14) ◽  
pp. 2298-2304 ◽  
Author(s):  
J. A. Howard
Keyword(s):  
Rate Constants ◽  
Addition Reaction ◽  
Peroxy Radical ◽  
Stabilization Energy ◽  
Peroxy Radicals ◽  
Absolute Rate ◽  
Termination Rate ◽  
Vinyl Compound ◽  
Rate Constants For Addition

Absolute propagation and termination rate constants have been determined for the autoxidation of some vinyl compounds at 30°. Rates of propagation depend on the structure of both the peroxy radical and the vinyl compound. The reactivity of peroxy radicals towards addition increases as the electron-withdrawing capacity of the α-substituent increases. Rate constants for addition of t-butylperoxy radicals to vinyl compounds, [Formula: see text] fit the equation[Formula: see text]where Es is the estimated stabilization energy of the β-peroxyalkyl radical (in kcal/mol) formed in the addition reaction.

Chemistry of amidyl radicals: intramolecular reactivities of alkenyl amidyl radicals

1985 ◽  
Vol 63 (8) ◽  
pp. 2203-2210 ◽  
Author(s):  
Yuan L. Chow ◽  
Richard A. Perry
Keyword(s):  
Double Bond ◽  
Rate Constants ◽  
Side Chain ◽  
Double Bonds ◽  
Kinetic Rate ◽  
Cyclic Radical ◽  
Kinetic Rate Constants ◽  
Acyl Side Chain ◽  
Complete Reversal

Amidyl radicals possessing Δ4,5, Δ5,6, and Δ6,7 double bonds were generated from the photodecomposition of nitrosamides and chloramides and the products were identified. Dichotomies of amidyl radical reactivities were discovered and compared with published kinetic rate constants. In complete reversal to intermolecular reactivities, intramolecularly the alkenyl amidyl radicals preferentially add to the double bonds rather than abstract a C-5 hydrogen even if it is allylic. In intramolecular competition, amidyl radicals add to an acyl side chain double bond more efficiently than to an alkyl one; this is just the opposite to intramolecular H-abstraction of amidyl radicals. Taken together with the published results, it is established that, in intramolecular attacks of double bonds, amidyl radicals selectively undergo the propia-addition to generate an exo-cyclic radical rather than the longa-addition to an endo-cyclic radical: this rule should replace the old one that amidyl radicals preferentially cyclize to form five-membered rings if choices are available.

Solvent, Substituent, and Temperature Effects on the Absolute Rate Constants for Addition of Methoxytrimethylsilane to 1,1-Diarylsilenes

2001 ◽  
Vol 20 (5) ◽  
pp. 932-936 ◽  
Author(s):  
William J. Leigh ◽  
Christine J. Bradaric ◽  
Tracy L. Morkin ◽  
Xiaojing Li
Keyword(s):  
Rate Constants ◽  
Temperature Effects ◽  
Absolute Rate ◽  
The Absolute ◽  
Rate Constants For Addition
Sign in / Sign up

Export Citation Format

Share Document