Hydrogen bonding in the gas phase. Part 3.—Infrared spectroscopic investigation of complexes formed by phenol and by 2,2,2-trifluoroethanol

Hussein, Mohammed Ali; Millen, D. J.; Mines, G. W.

doi:10.1039/f29767200686

Cited by 16 publications

(9 citation statements)

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“…20 For comparison, the OH-stretching vibration in ethanol (EtOH) and phenol is red-shifted by 111 and 210 cm −1 , respectively, upon complexation with dimethyl ether (DME) in the gas phase. 38,39 The observed frequency shifts suggest that the sp 2hybridized oxygen atom in DMSO acts as a stronger hydrogen bond acceptor than the sp 3 -hybridized oxygen atom in DME. 40,41 Here the MeOH complex was detected in the gas phase at room temperature.…”

Section: Introductionmentioning

confidence: 99%

“…As different o -methoxyphenols (2-methoxyphenol, 4-methoxyphenol, 2,4-dimethoxyphenol, and 2,6-dimethoxyphenol) were dissolved in CCl 4 and DMSO, the OH-stretching frequency was red-shifted up to ∼1100 cm –1 relative to the OH-stretching vibration of the phenol monomers dissolved in CCl 4 . For comparison, the OH-stretching vibration in ethanol (EtOH) and phenol is red-shifted by 111 and 210 cm –1 , respectively, upon complexation with dimethyl ether (DME) in the gas phase. , The observed frequency shifts suggest that the sp 2 -hybridized oxygen atom in DMSO acts as a stronger hydrogen bond acceptor than the sp 3 -hybridized oxygen atom in DME. , …”

Section: Introductionmentioning

confidence: 99%

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Dimethyl Sulfoxide Complexes Detected at Ambient Conditions

Hansen

Kjaergaard

2017

J. Phys. Chem. A

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Dimethyl sulfoxide (DMSO) is an important intermediate in the atmospheric oxidation of dimethyl sulfide (DMS). DMS, emitted from the ocean, is the main natural sulfur source, and its oxidation products are essential in the formation of sulfate aerosols. The high atmospheric concentration of water makes hydrogen bonding with DMS and its oxidation products likely. Through hydrogen bonding, water can potentially catalyze and affect the steps of the oxidation. We investigate binary hydrogen-bound complexes involving DMSO. Both water·DMSO and methanol·DMSO complexes are identified in an Ar matrix, and at room temperature, a Gibbs free energy of 0.7 kJ/mol for the formation of the methanol·DMSO complex is determined. Assuming a similar Gibbs free energy of the hydrate, it would suggest a relatively high abundance of the DMSO hydrate relative to the monomer in the atmosphere. The effect of changing the atom divalently bound to the hydrogen bond accepting oxygen, from S to C (DMSO to acetone), is found to significantly decrease the equilibrium constant of complex formation.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Dimethyl Sulfoxide Complexes Detected at Ambient Conditions

Hansen

Kjaergaard

2017

J. Phys. Chem. A

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“…The predominance of the anti conformer in EtOH (∼72%) and of the gauche conformer in TFE (∼64%) is obvious and in good agreement with the literature. 17,20 The spectrum of pure BuOH is more complex in this region. The percentage of the anti conformer (estimated as for the shorter alcohols, Table S10) is 42%, which indicates a higher stability of the gauche form, contrarily to that observed in EtOH.…”

Section: The Journal Of Physical Chemistry B Articlementioning

confidence: 99%

“…The predominance of gauche isomers opens the possibility of establishing weak intramolecular OH···F hydrogen bonds in the case of TFE. 20 Alcohols with longer alkyl chains present additional rotational conformations (from all-trans to all-gauche) that will result in different three-dimensional packings. In fluorinated chains, some of the gauche conformers favor intramolecular Hbonding.…”

Section: Introductionmentioning

confidence: 99%

Liquid Mixtures Involving Hydrogenated and Fluorinated Alcohols: Thermodynamics, Spectroscopy, and Simulation

Morgado¹,

García

Ilharco³

et al. 2016

J. Phys. Chem. B

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This article reports a combined thermodynamic, spectroscopic, and computational study on the interactions and structure of binary mixtures of hydrogenated and fluorinated substances that simultaneously interact through strong hydrogen bonding. Four binary mixtures of hydrogenated and fluorinated alcohols have been studied, namely, (ethanol + 2,2,2-trifluoroethanol (TFE)), (ethanol + 2,2,3,3,4,4,4-heptafluoro-1-butanol), (1-butanol (BuOH) + TFE), and (BuOH + 2,2,3,3,4,4,4-heptafluoro-1-butanol). Excess molar volumes and vibrational spectra of all four binary mixtures have been measured as a function of composition at 298 K, and molecular dynamics simulations have been performed. The systems display a complex behavior when compared with mixtures of hydrogenated alcohols and mixtures of alkanes and perfluoroalkanes. The combined analysis of the results from different approaches indicates that this results from a balance between preferential hydrogen bonding between the hydrogenated and fluorinated alcohols and the unfavorable dispersion forces between the hydrogenated and fluorinated chains. As the chain length increases, the contribution of dispersion increases and overcomes the contribution of H-bonds. In terms of the liquid structure, the simulations suggest the possibility of segregation between the hydrogenated and fluorinated segments, a hypothesis corroborated by the spectroscopic results. Furthermore, a quantitative analysis of the infrared spectra reveals that the presence of fluorinated groups induces conformational changes in the hydrogenated chains from the usually preferred all-trans to more globular arrangements involving gauche conformations. Conformational rearrangements at the CCOH dihedral angle upon mixing are also disclosed by the spectra.

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“…Millen et aZ. 23 have shown that, for a given arrangement with fixed pathlength, it will be generally advantageous to raise the temperature of the system. With the knowledge of the spectra of the pure alcohols it becomes possible to anaiyse the spectra of mixtures of an alcohol with hydrogen fluoride.…”

Section: Resultsmentioning

confidence: 99%

Hydrogen bonding in the gas phase. Infrared spectroscopic investigation of hydrogen fluoride alcohol–heterodimers

Legon¹,

Millen²,

Schrems³

1979

J. Chem. Soc., Faraday Trans. 2

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For the first time, an infrared investigation of gas phase hydrogen bonded complexes formed by hydrogen fluoride with alcohols has been made, Evidence has been given for the formation of 1 : 1 heterodimers ROH HF and the vibration wavenumbers Y(F-H) have been estimated. The wavenumber displacements of the HF stretching vibration on H bond formation provide a measure of the electron donating abilities in the free alcohols. The electron donating power of the oxygen atom is increased by increasing methylation at the oxygen atom, as indicated by the constant increase of 75 cm-' in AGF along the series H 2 0 HF, CH30H HF, (CH3)ZO HF. A similar but attenuated increase occurs on increasing methylation of the carbon atom in methanol as indicated by steps of about 25 cm-I in A ~H F for complexes formed by CH30H, CH3CH20H, (CH,),CHOH and (CH&COH. On the other hand, the electron donating ability of the oxygen atom is decreased by the presence of the electron attracting groups CH2Cl, CH2F and CF3. We confirm that where the vapour pressure of a component is a limitation on observing dimer formation in the gas phase, as is the case in most alcohols, it is advantageous to work at higher temperatures.

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Hydrogen bonding in the gas phase. Part 3.—Infrared spectroscopic investigation of complexes formed by phenol and by 2,2,2-trifluoroethanol

Cited by 16 publications

References 0 publications

Dimethyl Sulfoxide Complexes Detected at Ambient Conditions

Dimethyl Sulfoxide Complexes Detected at Ambient Conditions

Liquid Mixtures Involving Hydrogenated and Fluorinated Alcohols: Thermodynamics, Spectroscopy, and Simulation

Hydrogen bonding in the gas phase. Infrared spectroscopic investigation of hydrogen fluoride alcohol–heterodimers

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