Association of methanol in vapor and in n-hexadecane. A model for the association of alcohols

Tucker, Edwin E.; Farnham, Sutton B.; Christian, Sherril D.

doi:10.1021/j100845a042

Cited by 73 publications

(42 citation statements)

References 3 publications

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“…The dissociation energies and dissociation enthalpies for the various clusters at 0 K and at room temperature are given in Table VII. There is good agreement between the calculated dissociation enthalpies and previous theoretical 13 and experimental 43,44 values. From Table VI, we observe that the MP2 interaction energies are consistently improved as the size of the basis set is increased.…”

Section: E Energetics and Cooperativitysupporting

confidence: 81%

Hydrogen bonding and cooperative effects in mixed dimers and trimers of methanol and trifluoromethanol: An ab initio study

Parra

Zeng

1999

The Journal of Chemical Physics

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, "Hydrogen bonding and cooperative effects in mixed dimers and trimers of methanol and trifluoromethanol: An ab initio study" (1999 Ab initio calculations are used to provide information on the mixed dimers and cyclic trimers of the methanol-trifluoromethanol system. In order to better understand the systems, the monomers and their corresponding dimers and trimers are also investigated. Molecular structures and harmonic frequencies are obtained at the B3LYP/6-311ϩϩG(d,p) level. Interaction energies are calculated with the MP2 and B3LYP methods using the 6-311ϩϩG(d,p), 6-311ϩϩG(2d,2p), and 6-311ϩϩG(3d,2p) basis sets for the dimers and heterodimers. The 6-311ϩϩG(d,p) basis set was used to calculate the interaction energies for the trimers and heterotrimers. Because the primary goal of this study is to examine cooperative effects, particular attention is given to parameters such as O...O distances, electronic charge densities at the bond critical points, enhanced dipole moments, shifts in the stretching frequencies of the donor O-H bond, and the length of the donor O-H bond.

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Section: E Energetics and Cooperativitysupporting

confidence: 81%

Hydrogen bonding and cooperative effects in mixed dimers and trimers of methanol and trifluoromethanol: An ab initio study

Parra

Zeng

1999

The Journal of Chemical Physics

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“…(12) for the association of methanol both in its vapour and in hexadecane, although it is at variance with other literature (7,33) which includes the tetramer in twoparameter models.…”

Section: Calculations Ancl Conclirsionscontrasting

confidence: 65%

“…Some infrared data have been interpreted in terms of monomer-dimer equilibria (lo), or monomer-dimer-11-mer (1 1) Lvhen extended to hisher conce~itrations of ethanol. However, recent vapor pressure data for the system methanol-hexadecane were best explained lRevision received August 26, 1976. by a monomer-trimer-octamer model (12). Moreover, combined vapor pressure, infrared, and nmr data on the association of tert-butyl alcohol in C16H34 and in C16D34 led to a monomer-trimer-hexamer being proposed for that system (13).…”

Section: Imtroductionmentioning

confidence: 99%

“…This value was calculated from a value provided by Scheraga and 0wicki2 for the molar energy of vaporization of real water a t 25 "C, t o produce a hypothetical vapor having the same polymeric composition that Scheraga and co-workers (29) Then [Ill, [12], and [13] give 1251 where [261 In eqs. 23-25, XA, xlv.…”

Section: Nmentioning

confidence: 99%

“…Equation 29 allou-s a simple least-squares fit of the distribution data alone to be made. Guided partly by the findings in the literature on alcohol association (7,9,10,12,13,15,31,32) and partly by the shapes of the distribution graphs ( Figs. 1 and 2), various combinations of two, three, and in some cases four a, parameters in [29] were tried.…”

Section: Calculations Ancl Conclirsionsmentioning

confidence: 99%

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Association and hydration of alcohols in low-dielectric solvents. I. n-Butanol

Kirchnerová¹,

Cave²

1976

Can. J. Chem.

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The 347.2 nm Laser Photolysis of Tetranitromethane in Polar, Nonpolar, and Micellar Solutions

Frank¹,

Grätzel²,

Henglein³

1976

Ber Bunsenges Phys Chem

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Tetranitromethane in various solvents (water, ethanol, t‐butanol, acetone, n‐hexane, neo‐pentane, carbon tetrachloride, mixtures of n‐hexane and ethanol, sodium lauryl sulfate and dodecyltrimethylammonium chloride micelles) was photolyzed by a pulsed, frequency‐doubled ruby laser (3.57 eV quantum of energy). The products of the photolysis were monitored in the 10−8 to 10−3 s range by recording the optical absorption and electrical conductivity of the solutions. In polar solvents, the anion of nitroform, C(NO2)3−, is formed during the 20 ns laser pulse. The yields of C(NO2)3− are highest in ethanol and lowest in aqueous solutions. In water, ionic dissociation of tetranitromethane is the main photolytic decomposition mode. In the alcohols and acetone a two step mechanism is proposed involving CN bond rupture to form the trinitromethyl radical which subsequently picks up an electron from the solvent to form C(NO2)3− and an electron deficient solvent state. The latter could optically be detected in the case of acetone. In hydrocarbon solutions, aci‐nitroform is produced via H‐atom abstraction by the trinitromethyl radical. In mixtures of n‐hexane and ethanol (0.1 to 5 vol.%), this radical is only able to abstract an electron from clusters of ethanol molecules and not from free, unassociated ethanol. When tetranitromethane is incorporated in the lipoidic core of ionic micelles, the extent of photolytic decomposition is substantially enhanced relative to that in water. In aqueous solutions containing 0.1 to 3 M sodium chloride, the trinitromethyl radical forms a complex with the chloride anion. Energy considerations involving the formation of electron deficient solvent states are used to explain the observed effects.

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Association of methanol in vapor and in n-hexadecane. A model for the association of alcohols

Cited by 73 publications

References 3 publications

Hydrogen bonding and cooperative effects in mixed dimers and trimers of methanol and trifluoromethanol: An ab initio study

Hydrogen bonding and cooperative effects in mixed dimers and trimers of methanol and trifluoromethanol: An ab initio study

Association and hydration of alcohols in low-dielectric solvents. I. n-Butanol

The 347.2 nm Laser Photolysis of Tetranitromethane in Polar, Nonpolar, and Micellar Solutions

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