The equilibrium constant and rate constant for allyl radical recombination in the gas phase

1979 ◽  
Vol 101 (5) ◽  
pp. 1223-1230 ◽  
Author(s):  
M. Rossi ◽  
K. D. King ◽  
D. M. Golden
Keyword(s):  
Equilibrium Constant ◽  
Gas Phase ◽  
Rate Constant ◽  
Allyl Radical ◽  
Radical Recombination

Reaction rate constant of SO3+ NH3in the gas phase

1990 ◽  
Vol 95 (D9) ◽  
pp. 13981 ◽  
Author(s):  
Gaunlin Shen ◽  
Masako Suto ◽  
L. C. Lee
Keyword(s):  
Gas Phase ◽  
Rate Constant ◽  
Reaction Rate ◽  
Reaction Rate Constant

scholarly journals Ruthenium trisbipyridine as a candidate for gas-phase spectroscopic studies in a Fourier transform mass spectrometer

2004 ◽  
Vol 18 (2) ◽  
pp. 387-396 ◽  
Author(s):  
Jill R. Scott ◽  
Jason E. Ham ◽  
Bill Durham ◽  
Paul L. Tremblay
Keyword(s):  
Fourier Transform ◽  
Gas Phase ◽  
Mass Spectrometer ◽  
Rate Constant ◽  
Optical Detection ◽  
Sinapinic Acid ◽  
Spectroscopic Studies ◽  
Fluorescence Lifetimes ◽  
Fourier Transform Mass Spectrometer

Metal polypyridines are excellent candidates for gas-phase optical experiments where their intrinsic properties can be studied without complications due to the presence of solvent. The fluorescence lifetimes of [Ru(bpy)3]1+trapped in an optical detection cell within a Fourier transform mass spectrometer were obtained using matrix-assisted laser desorption/ionization to generate the ions with either 2,5-dihydroxybenzoic acid (DHB) or sinapinic acid (SA) as matrix. All transients acquired, whether using DHB or SA for ion generation, were best described as approximately exponential decays. The rate constant for transients derived using DHB as matrix was 4×107s−1, while the rate constant using SA was 1×107s−1. Some suggestions of multiple exponential decay were evident although limited by the quality of the signals. Photodissociation experiments revealed that [Ru(bpy)3]1+generated using DHB can decompose to [Ru(bpy)2]1+, whereas ions generated using SA showed no decomposition. Comparison of the mass spectra with the fluorescence lifetimes illustrates the promise of incorporating optical detection with trapped ion mass spectrometry techniques.

Multivariate modelling of the rate constant of the gas-phase reaction of haloalkanes with the hydroxyl radical

1991 ◽  
Vol 109-110 ◽  
pp. 307-325 ◽  
Author(s):  
Maria Livia Tosato ◽  
Claudio Chiorboli ◽  
Lennart Eriksson ◽  
Jorgen Jonsson
Keyword(s):  
Hydroxyl Radical ◽  
Gas Phase ◽  
Rate Constant ◽  
Phase Reaction ◽  
Gas Phase Reaction ◽  
Multivariate Modelling

Absolute gas-phase acidities of CH3NH2, C2H5NH2, (CH3)2 NH, and (CH3)3N

1976 ◽  
Vol 54 (10) ◽  
pp. 1624-1642 ◽  
Author(s):  
Gervase I. Mackay ◽  
Ronald S. Hemsworth ◽  
Diethard K. Bohme
Keyword(s):  
Equilibrium Constant ◽  
Gas Phase ◽  
Equilibrium Constants ◽  
Heats Of Formation ◽  
Molecular Orbital Calculations ◽  
Electron Affinities ◽  
Flowing Afterglow ◽  
Experimental Assessment ◽  
Gas Phase Acidity ◽  
Conjugate Bases

The flowing afterglow technique has been employed in measurements of the rate and equilibrium constants at 296 ± 2 K for reactions of the type[Formula: see text]and[Formula: see text]where R1 and R2 may be H, CH3, or C2H5. The equilibrium constant measurements provided absolute values for the intrinsic (gas-phase) acidities of the Brønsted acids CH3NH2, C2H5NH2, (CH3)2NH, and (CH3)3N, the heats of formation of their conjugate bases, and the electron affinities of the corresponding radicals R1R2N. Proton removal energies, ΔG0298/(kcal mol−1), were determined to be 395.7 ± 0.7 for [Formula: see text] 391.7 ± 0.7 for [Formula: see text] 389.2 ± 0.6 for [Formula: see text] and > 396 for [Formula: see text] Heats of formation, ΔH0f.,298, were determined to be 30.5 ± 1.5 for CH3NH−, 21.2 ± 1.5 for C2H5NH−, and 24.7 ± 1.4 for (CH3)2N−. Electron affinities (in kcal mol−1) were determined to be 13.1 ± 3.5 for CH3NH, 17 ± 4 for C2H5NH, and 14.3 ± 3.4 for (CH3)2N. These results quantify earlier conclusions regarding the intrinsic effects of substituents on the gas-phase acidity of amines and provide an experimental assessment of recent molecular orbital calculations of proton removal energies for alkylamines.

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