Radicals and scavengers. 7. Diffusion controlled scavenging of phenyl radicals and absolute rate constants of several phenyl radical reactions

1977 ◽  
Vol 99 (23) ◽  
pp. 7589-7600 ◽  
Author(s):  
Roy G. Kryger ◽  
John P. Lorand ◽  
Neal R. Stevens ◽  
Nelson R. Herron
Keyword(s):  
Rate Constants ◽  
Radical Reactions ◽  
Phenyl Radical ◽  
Absolute Rate ◽  
Phenyl Radicals ◽  
Diffusion Controlled

ChemInform Abstract: ABSOLUTE RATE CONSTANTS FOR REACTIONS OF PHENYL RADICALS

1978 ◽  
Vol 9 (20) ◽  
Author(s):  
V. MADHAVAN ◽  
R. H. SCHULER ◽  
R. W. FESSENDEN
Keyword(s):  
Rate Constants ◽  
Absolute Rate ◽  
Phenyl Radicals

Kinetics of cyclopropyl radical reactions. 1. Absolute rate constants for some addition and abstraction reactions

1984 ◽  
Vol 106 (17) ◽  
pp. 4877-4881 ◽  
Author(s):  
Linda J. Johnston ◽  
J. C. Scaiano ◽  
K. U. Ingold
Keyword(s):  
Rate Constants ◽  
Radical Reactions ◽  
Absolute Rate ◽  
Kinetics Of

ChemInform Abstract: KINETICS OF CYCLOPROPYL RADICAL REACTIONS. 1. ABSOLUTE RATE CONSTANTS FOR SOME ADDITION AND ABSTRACTION REACTIONS

1984 ◽  
Vol 15 (49) ◽  
Author(s):  
L. J. JOHNSTON ◽  
J. C. SCAIANO ◽  
K. U. INGOLD
Keyword(s):  
Rate Constants ◽  
Radical Reactions ◽  
Absolute Rate ◽  
Kinetics Of

Absolute Rate Constants for Alkoxycarbonyl Radical Reactions

1998 ◽  
Vol 63 (4) ◽  
pp. 1226-1232 ◽  
Author(s):  
Pavel A. Simakov ◽  
Felix N. Martinez ◽  
John H. Horner ◽  
Martin Newcomb
Keyword(s):  
Rate Constants ◽  
Radical Reactions ◽  
Absolute Rate

Proton Transfer Kinetics in Medium-strong Inorganic Acids

1973 ◽  
Vol 51 (14) ◽  
pp. 2297-2305 ◽  
Author(s):  
David Charles Hodgkin ◽  
Peeter Kruus
Keyword(s):  
Proton Transfer ◽  
Aqueous Solutions ◽  
Rate Constants ◽  
Reasonable Agreement ◽  
Ultrasonic Absorption ◽  
Absolute Rate ◽  
Absorption Data ◽  
Inorganic Acids ◽  
Diffusion Controlled ◽  
Excess Absorption

A method of obtaining relative and absolute rate constants for proton transfer equilibria is described. It is suitable for equilibria of the type[Formula: see text]in dilute (< 0.1 M) solutions of medium strong inorganic acids. To obtain absolute values of kd, kr it is necessary to know the value of ΔV0 for the equilibrium. Ultrasonic absorption data for aqueous solutions of H3PO4, H3AsO4, and H2SO4 at 20, 10, and 0 °C are presented together with data at 20 °C for H3PO3, H2SeO3, HIO4, NaHSO4, KHSO4, and NH4HSO4. From analysis of the concentration dependence of the excess absorption, values of Ka are calculated for these acids, and values of kd, kr for those where ΔV0 is available. The Ka obtained are in reasonable agreement with literature values except for HIO4 and H2SeO4. The absolute values of kr for H3PO4, H3AsO4, and HSO4− indicate that the diffusion controlled recombination process postulated is complete when the ions are about 15 Å from each other.

Direct detection of methylphenylgermylene and 1,2-dimethyl-1,2-diphenyldigermene — Kinetic studies of their reactivities in solution

2006 ◽  
Vol 84 (7) ◽  
pp. 934-948 ◽  
Author(s):  
William J Leigh ◽  
Ileana G Dumbrava ◽  
Farahnaz Lollmahomed
Keyword(s):  
Acetic Acid ◽  
Rate Constants ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Direct Detection ◽  
Kinetic Studies ◽  
Laser Flash ◽  
Absolute Rate ◽  
Hydrocarbon Solvents ◽  
Diffusion Controlled

Photolysis of 1,3,4-trimethyl-1-phenylgermacyclopent-3-ene (5) in hydrocarbon solvents containing isoprene, methanol, or acetic acid affords 2,3-dimethyl-1,3-butadiene (DMB) and the expected trapping products of methyl phenylgermylene (GeMePh) in chemical yields exceeding 90%. The germylene has been detected in hexane solution by laser flash photolysis as a short-lived species (τ ~ 2 µs) exhibiting a UV-vis absorption spectrum centered at λmax = 490 nm. It decays with second-order kinetics and a rate constant close to the diffusion-controlled limit, with the concomitant growth of a second longer-lived transient (λmax = 420 nm) that is assigned to a mixture of (E)- and (Z)-1,2-dimethyl-1,2-diphenyldigermene (4). Absolute rate constants have been determined for the reactions of the germylene with primary and tertiary amines (n-BuNH2 and Et3N, respectively), acetic acid (AcOH), a terminal alkyne and alkene, isoprene, DMB, CCl4, and the group 14 hydrides Et3SiH and Bu3SnH. GeMePh is slightly more reactive than GePh2 towards all the reagents studied in this work; both are significantly less reactive than GeMe2 toward the same substrates. Absolute rate constants for the reactions of 4 have also been measured or assigned upper limits in every case and are compared to previously reported values for tetraphenyl- and tetramethyl-digermene with the same reagents.Key words: germylene, digermene, kinetics, laser flash photolysis, germirane, germirene, vinylgermirane, complex, UV–vis spectrum, insertion, addition.

Absolute rate constants for the hydroxyl radical reactions with CH3SH and C2H5SH at room temperaturea)

1983 ◽  
Vol 78 (11) ◽  
pp. 6646-6649 ◽  
Author(s):  
J. H. Lee ◽  
I. N. Tang
Keyword(s):  
Hydroxyl Radical ◽  
Rate Constants ◽  
Radical Reactions ◽  
Absolute Rate

Novel Chemiluminescence Methods for Determination of Absolute Rate Constants for Elementary Radical Reactions in the Liquid Phase

Nature ◽  
1965 ◽  
Vol 206 (4981) ◽  
pp. 292-293 ◽  
Author(s):  
A. A. VICHUTINSKII
Keyword(s):  
Liquid Phase ◽  
Rate Constants ◽  
Radical Reactions ◽  
Absolute Rate
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