Molecular Association of Methanol Vapor

Inskeep, Richard G.; Kelliher, James M.; McMahon, Paul; Somers, B. G.

doi:10.1063/1.1744340

Cited by 55 publications

(20 citation statements)

References 11 publications

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“…We have not performed a full vibrational analysis and therefore the computation of the 0-H frequency on the basis of,fo,, alone would be premature. We note, however, that the vapor phase frequency of vo, is 3682 cm-' (53). Matrix isolation of (CH,OH)l yielded values of 3490-3528 cm-' dependent on the type of matrix used (24) whereas the lowest OH-frequency in the solid is 3187 cm-' (9).…”

Section: Results and Discussion I (Ch$oh)mentioning

confidence: 99%

Abinitio studies on hydrogen bonded chains. V. The structure of infinite chains of methanol and water molecules

Karpfen¹,

Schuster²

1985

Can. J. Chem.

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Infinitely extended, periodic, bent chains of methanol and water molecules have been investigated with the aid of the abinitio crystal orbital method. Results on equilibrium geometries, stabilization energies, and other ground state properties are compared with the corresponding data obtained on monomers and homodimers. We also confront our computed results with experimental vapor phase and solid state data. Deviations from additivity of intermolecular interactions and the change of molecular properties from vapor phase monomer to molecules embedded in a periodic lattice are pointed out and compared to analogous effects as observed in other hydrogen bonded polymers. A few remarks on the evaluation of effective molecular dipole moments in molecular crystals are included as well.

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Section: Results and Discussion I (Ch$oh)mentioning

confidence: 99%

Abinitio studies on hydrogen bonded chains. V. The structure of infinite chains of methanol and water molecules

Karpfen¹,

Schuster²

1985

Can. J. Chem.

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“…In other words, why are isovolume compositions so effective in breaking up ring structures? In an effort to answer this question let us follow arguments supposing that ring structures are present predominantly in the form of dimers [30], trimers [31], or tetramers [32].…”

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confidence: 99%

Supramolecular x-ray signature of susceptibility amplification in hydrogen-bonded liquids

et al. 2014

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Mixing two nonconducting hydrogen-bonded liquids, each exhibiting a low dielectric relaxation strength, can result in a highly electrically absorbing fluid. This susceptibility amplification effect is demonstrated for mixtures of monohydroxy alcohols. Whereas in the pure liquids a tendency to form ringlike low-dipole moment clusters prevails, in the mixtures such supramolecular structures are disfavored leading to an up to tenfold enhancement of the dielectric loss. The compositional evolution of density and mean cluster-cluster separation is traced using x-ray scattering and indicates deviations from ideal mixing with decreased C-C but simultaneously increased O-O correlation lengths. Thus, the variation in the supramolecular absorption strength could be tracked using a static scattering technique. These observations are in harmony with volume exclusion and ring open effects that predict an optimized susceptibility amplification for mixtures in which the two components occupy equal volume fractions as experimentally observed.

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“…The spectrum shape and its peak positions were essentially identical to those known for ϳ10 Ϫ4 mol/l methanol vapor at an ambient temperature. 24,4,25,26 There were also weak absorptions between 1900 and 2600 cm Ϫ1 associated with phonon bands of the diamond windows and a C-O stretch overtone. 27 We stress here the good quality of our IR spectra obtained at such a high temperature.…”

Section: Methodsmentioning

confidence: 99%

“…3 Around the same time, the first IR studies of hydrogen-bonding interactions in pure methanol vapor showed the existence of equilibria between methanol monomer, dimer, and tetramer forms as a function of vapor density. 4 Nowadays, a huge number of different experimental and theoretical studies devoted to the hydrogen-bonded structure of methanol in different phases can be found in the literature. Summarizing the accumulated theoretical and experimental knowledge, the models of the hydrogen bonding between methanol molecules in different phases can be represented as follows.…”

Section: Introductionmentioning

confidence: 99%

“…Below 373 K, methanol monomer-dimer-tetramer equilibria have been measured as a function of vapor density and temperature. 4,7 However, until recent advances in high-temperature and pressure techniques, direct spectroscopic investigations were limited to the subcritical region due to the comparatively high critical temperature of methanol. ͑Note that methanol critical temperature, T c , critical pressure, P c , and critical density, c , are 512.6 K, 8.1035 MPa, and 8.60 mol/l, respectively.…”

Section: Introductionmentioning

confidence: 99%

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Hydrogen bonding in supercritical methanol studied by infrared spectroscopy

Bulgarevich

Otake

Sako

et al. 2002

The Journal of Chemical Physics

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Articles you may be interested inCommunication: The highest frequency hydrogen bond vibration and an experimental value for the dissociation energy of formic acid dimer J. Chem. Phys. 136, 151101 (2012); 10.1063/1.4704827 Association structures of ionic liquid/DMSO mixtures studied by high-pressure infrared spectroscopy J. Chem. Phys. 134, 044506 (2011); 10.1063/1.3526485 Infrared spectroscopy of methanol-hexane liquid mixtures. II. The strength of hydrogen bonding Infrared cavity ringdown spectroscopy of methanol clusters: Single donor hydrogen bondingWe report the first Fourier transform infrared spectroscopic studies of the hydrogen-bonding interactions in supercritical methanol and methanol/methanol-d1 mixtures. At 523 K and below ϳ0.3 mol/l, methanol chiefly existed in a monomeric form. However, at 523 K and between ϳ0.3 and 2 mol/l, in the regions of O-H, C-O, and C-H stretching vibrations, there were clear indications of methanol monomer-dimer equilibrium. The effect of temperature on the equilibrium constant was also investigated. As a result, the partial molar volume difference and enthalpy of the dimerization were estimated and correlated with the behavior of the methanol isothermal compressibility. It was also concluded that at 523 K and density higher than ϳ15 mol/l, the hydrogen-bonding equilibrium started to shift toward larger aggregates.

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Molecular Association of Methanol Vapor

Cited by 55 publications

References 11 publications

Abinitio studies on hydrogen bonded chains. V. The structure of infinite chains of methanol and water molecules

Abinitio studies on hydrogen bonded chains. V. The structure of infinite chains of methanol and water molecules

Supramolecular x-ray signature of susceptibility amplification in hydrogen-bonded liquids

Hydrogen bonding in supercritical methanol studied by infrared spectroscopy

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