Kinetics of Decomposition of HF in Shock Waves

Jacobs, T. A.; Giedt, R. R.; Cohen, N.

doi:10.1063/1.1696537

Cited by 42 publications

(5 citation statements)

References 11 publications

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“…Therefore, it is obvious that the inclusion of the macroscopic solute-solvent interaction to the usual "gas-phase'' quantum-chemical calculations may suggest, in some cases, different reaction mechanisms as the most favored calculated pathways for a given chemical reaction. According to the experimental evidence [23] HF dissociates homolytically in the gas phase. A minimum basis imo SCF CI gives the right dissociation limit for this reaction in the case of the isolated HF molecule.…”

Section: Discussionmentioning

confidence: 97%

Reaction field effects on the electron distribution and chemical reactivity of molecules

Karelson¹,

Katritzky

Zerner

1986

Int. J. Quantum Chem.

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We examine the effects of macroscopic solvation using the self-consistent reaction field technique. On the basis of ah initio, INWSCF, and INW/CI calculations we conclude that the introduction of a dielectric media seems to have little effect on calculated geometries. However, the charge distribution is effected: the presence of dielectric media allows greater local charge to develop. The dissociation of hydrogen fluoride is examined. With electron correlation, HF dissociates homolytically in the "gas" phase, but heterolytically in a "solvent" of dielectric constant of 80.

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Section: Discussionmentioning

confidence: 97%

Reaction field effects on the electron distribution and chemical reactivity of molecules

Karelson¹,

Katritzky

Zerner

1986

Int. J. Quantum Chem.

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“…Appelman and Clyne103 reported on the rapid reaction between F atoms and HOF. The reaction proceeds by H atom abstraction followed by regeneration of F atoms F + HOF -* HF + FO (104) 2FO -»• Oz + 2F (88) Because of extraneous peak interference in the mass spectrograph, the authors were unable to obtain an absolute rate con- slant for reaction 104. However, they report a lower limit of 1.2 X 1014 cm3 mol-1 s-1 for this rate constant.…”

Section: B Reaction With Water and Hydroxyl Radicalmentioning

confidence: 99%

“…-> F + FO +(101) F + F20 -F2 + FO(102) FO + FO -02 + 2F(88) F + F + M-*"F2 + M(97) An activation energy of 14.3 ± 1.5 kcal for reaction 102 was determined from the photochemical investigation,125 while the results of the thermal study126 gave k102 = 5.1 X 101°e xp[-(13.7 ± 1.0) X 103/fi7] cm3 mol-1 s-1.…”

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confidence: 99%

Reactions of fluorine atoms

Jones¹,

Skolnik²

1976

Chem. Rev.

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“…3,4 A pioneering method for the chemical detection of HF uses moisture-sensitive (trifluoromethyl)dialkylaminoboranes. For example, N,N-dimethyl-1,1-bis(trifluoromethyl)boranamine (A) is converted into the corresponding amineborane in Et 2 O in the presence of HF, 5 and the robust H−F bond (135 kcal mol −1 ) 6 of the trapped HF is cleaved. Lewis acid receptors based on boronic acids and esters have been fine-tuned over the past decades for the selective capture of fluoride anion.…”

Section: ■ Introductionmentioning

confidence: 99%

Chemical Detection of Hydrogen Fluoride by the Phosphorus Congener of Cyclobutane-1,3-diyl

2015

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Heteroaryl-substituted air-tolerant 2,4-bis(2,4,6-tri-t-butylphenyl)-1,3-diphosphacyclobutane-2,4-diyls in the open-shell singlet state were synthesized by a sterically promoted regioselective S(N)Ar process. Here we demonstrate that these diyls are effective for capturing hydrogen fluoride (HF) generated by intermediary base-coordinated HF and amine-stabilized HF reagents. The hydrofluorination reaction predominantly occurred on the λ(3)σ(3)-phosphorus atoms to afford the energetically disfavored 1λ(5),3λ(5)-diphosphete. The positively charged t-butyl-substituted phosphorus atom trapped the fluoride anion, and the subsequent protonation was controlled by the steric effect. X-ray crystallographic analysis and an Atoms in Molecule study of the air-stable 1λ(5),3λ(5)-diphosphete bearing P-H and P-F bonds revealed that the delocalized ylidic linkages in the four-membered ring were almost identical, in contrast to the nonsymmetrically substituted 2,4-bis(2,4,6-tri-t-butylphenyl)-1,3-diphosphacyclobutane-2,4-diyl. Hydrofluorination efficiently induced a remarkable exchange of visible photoabsorption. The charge-transfer-type transition from highest occupied molecular orbital to lowest unoccupied molecular orbital was highly tuned, which is advantageous for the facile identification of HF. In contrast to hitherto known trapping reagents for HF based on cleavage of the H-F bond, several hydrofluorinated P-heterocycles were reconverted into the 1,3-diphosphacyclobutane-2,4-diyl by treatment with sodium hydride. However, in the hydrofluorination of the benzoyl-substituted 1,3-diphosphacyclobutane-2,4-diyl, fluorination and protonation occurred at the t-butyl-substituted phosphorus atom and the skeletal carbon atom, respectively, and the energetically preferable 1λ(5),3λ(3)-dihydrodiphosphete was isolated as a purple-blue crystalline compound. These findings are promising not only for the practical detection of HF but also for the development of fluorine technology based on the chemistry of phosphorus heterocycles.

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Kinetics of Decomposition of HF in Shock Waves

Cited by 42 publications

References 11 publications

Reaction field effects on the electron distribution and chemical reactivity of molecules

Reaction field effects on the electron distribution and chemical reactivity of molecules

Reactions of fluorine atoms

Chemical Detection of Hydrogen Fluoride by the Phosphorus Congener of Cyclobutane-1,3-diyl

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