VAPOR-PHASE PHOTOLYSIS OF FORMIC ACID<sup>1</sup>

Gorden, R.; Ausloos, P.

doi:10.1021/j100824a037

Cited by 21 publications

(22 citation statements)

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“…The simple decomposition of carboxyl (reaction [4]) appears t o be relatively unimportant under the present experimental conditions, which would tend t o support the higher value for the COO-H bond strength. This behavior is in contrast to that in the photolysis of formic acid (9), in which the carboxyl radical apparently decomposed rapidly, so that added olefin had almost no effect on the yields of CO and COz. Excess energy from the primary photolytic process may account for this difference in behavior, as the carboxyl radical would undoubtedly carry away more of the excess energy from formic acid than from the larger CF3COOH molecule with its additional degrees of freedom.…”

Section: Picontrasting

confidence: 61%

The Photolysis of Trifluoroacetic Acid Vapor

Mearns¹,

Back²

1963

Can. J. Chem.

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The photolysis of CF3COOH vapor has been studied a t temperatures between about 90 and 190" C, using light of wavelengths between 2000 and 2200 -4. The major products were C 0 2 and C2F6, with smaller amounts of CO, Hz, and CFaH. A marked reduction in the yields of C o n , CO, and H z with increasing pressure of added isobutane or 1-butene has been interpreted to imply the presence of free COOH radicals in the system, which is supported by the tentative identification of formic and oxalic acids as products of the photolysis. It is thought that the reaction CFaCOOH + hv + CF3 + COOH represents the main primary photolytic process, with the minor processes CF3COOH + hv + CF3 + COz + H and CF3COOH + hv --t CF3 + CO + OH accounting for no more than 27 and 7% respectively of the total a t 165' C.Some tentative conclusions have been drawn about the reactions of COOH radicals. In the present system, the disproportionation reaction, 2COOH -+ COz + HCOOH, appears to predominate, with the decon~position reaction, COOH + COz 4-H, apparently of minor importance a t 165' C.

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Section: Picontrasting

confidence: 61%

The Photolysis of Trifluoroacetic Acid Vapor

Mearns¹,

Back²

1963

Can. J. Chem.

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“…There was no evidence in the mercuryphotosensitization work for reaction (2c) which yields atomic hydrogen. Gorden and Ausloos [20], however, using isotopic labeling and scavenger experiments, were able to show that there is an important free-radical component in both the direct and the mercury-photosensitized photolysis.…”

Section: Mechanisms Of Decomposition Of Acids and Esters Deduced Frommentioning

confidence: 96%

Stopped‐flow studies of the mechanisms of ozone–alkene reactions in the gas phase propene and isobutene

Herron

Huie

1978

Int J of Chemical Kinetics

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The reactions of ozone with propene and isobutene have been studied in the gas phase at 298'K and 530 Pa (4 torr) using a stopped-flow reactor coupled to a photoionization mass spectrometer. Reactant and product concentrations were followed as a function of reaction time. The major reaction products monitored were CH20, CH&HO, COz, and HzO from the propene reaction, and CH20, (CH&CO, COz, and H20 from the isobutene reaction. The observations were interpreted on the basis of the Criegee mechanism for ozonolysis in solution:for which we find k~ N k g . In the gas phase the carbene peroxy radical is postulated to isomerize and decompose into molecular and free-radical products.

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“…The bond lengths of molecules were optimized at the Hartree-Fock level of theory with the 6-31G(d,p) (Hehre, Ditchfield & Pople, 1972;Hariharan & Pople, 1973;Gorden, 1980) or DZP (double-( plus polarization, Dunning & Hay, 1977;Guillermo del Conde, Bagus & Baushlicher, 1977;Poirier, Kari & Csizmadia, 1985) basis sets. The optimized bond lengths are summarized in Table 1.…”

Section: Methodsmentioning

confidence: 99%

Anisotropy of van der Waals radii of atoms in molecules: alkali-metal and halogen atoms

Ishikawa¹,

Ikuta²,

Katada³

et al. 1990

Acta Crystallogr Sect B

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The van der Waals radii of the alkali-metal and halogen atoms in 28 diatomic molecules are estimated theoretically, where the radius is defined as the distance from the nucleus to the surface having a calculated electron density of 0.005a. u. (0.0337 e A-3). The anisotropy of their radii is studied. The electron-correlation effect on the electrondensity distribution in Na + and F-increases slightly (by 0.01-0.02/~) the radii calculated at the HartreeFock level of theory. A large 'polar flattening' is observed for the CI and Br atoms bonded to H or halogen atoms. This can arise from the fact that the Pz electrons of the C1 and Br atoms flow into the bonding region in forming the chemical bond. On the other hand, a small 'polar extension' is observed for the K and Na atoms bonded to halogen atoms. This phenomenon is described with a simple model calculation (Na + .... l e), where the F atom in an NaF molecule is replaced with a negative point charge. The larger repulsion energy of an (HF)2 dimer in a sideways-on contact than in a head-on contact reflects the anisotropy of the electron-density distribution around the F atom in the molecule.

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VAPOR-PHASE PHOTOLYSIS OF FORMIC ACID¹

Cited by 21 publications

References 0 publications

The Photolysis of Trifluoroacetic Acid Vapor

The Photolysis of Trifluoroacetic Acid Vapor

Stopped‐flow studies of the mechanisms of ozone–alkene reactions in the gas phase propene and isobutene

Anisotropy of van der Waals radii of atoms in molecules: alkali-metal and halogen atoms

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VAPOR-PHASE PHOTOLYSIS OF FORMIC ACID1

Cited by 21 publications

References 0 publications

The Photolysis of Trifluoroacetic Acid Vapor

The Photolysis of Trifluoroacetic Acid Vapor

Stopped‐flow studies of the mechanisms of ozone–alkene reactions in the gas phase propene and isobutene

Anisotropy of van der Waals radii of atoms in molecules: alkali-metal and halogen atoms

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VAPOR-PHASE PHOTOLYSIS OF FORMIC ACID¹