On the Hydrogen Bond Contribution to the Heat of Vaporization of Aliphatic Alcohols

Bondì, A.; Simkin, D. J.

doi:10.1063/1.1743102

Cited by 22 publications

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“…where ∆H vap is the vaporization enthalpy and ∆H vap (HB) is the portion of ∆H vap attributed to HBs. Following Bondi, 20 ∆H vap (HB) is calculated by a "replacement method,"…”

Section: Extent Of Intermolecular Hb From Vaporization Enthalpiesmentioning

confidence: 99%

“…For an alcohol, for example, the hydroxyl group OH is replaced by the methyl group CH 3 , on the basis that the two functional groups make similar contributions to the dispersion energy. It was found that the increment ∆H vap (HB) is nearly constant for monoalcohols of different carbon numbers, 20 For non-hydroxyl groups, we use the following replacement scheme: -COOH (carboxylic acid) by -CO-CH 3 (ketone), -NH 2 (primary amine) by -CH 3 , -NH-(secondary amine) by -CH 2 -, -CO-NH 2 (primary amide) by -CO-CH 3 (ketone), and -CO-NH-(secondary amide) by -CO-CH 2 -.…”

Section: Extent Of Intermolecular Hb From Vaporization Enthalpiesmentioning

confidence: 99%

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Effect of molecular size and hydrogen bonding on three surface-facilitated processes in molecular glasses: Surface diffusion, surface crystal growth, and formation of stable glasses by vapor deposition

Chen

Tylinski

et al. 2019

The Journal of Chemical Physics

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Recent work has shown that diffusion and crystal growth can be much faster on the surface of molecular glasses than in the interior and that the enhancement effect varies with molecular size and intermolecular hydrogen bonds (HBs). In a related phenomenon, some molecules form highly stable glasses when vapor-deposited, while others (notably those forming extensive HBs) do not. Here we examine all available data on these phenomena for quantitative structure-property relations. For the systems that form no HBs, the surface diffusion coefficient D s decreases with increasing molecular size d (d = Ω 1/3 , where Ω is the molecular volume); when evaluated at the glass transition temperature T g , D s decreases ∼5 orders of magnitude for 1 nm of increase in d. Assuming that center-of-mass diffusion is limited by the deepest part of the molecule in the surface-mobility gradient, these data indicate a mobility gradient in reasonable agreement with the Elastically Collective Nonlinear Langevin Equation theory prediction for polystyrene as disjointed Kuhn monomers. For systems of similar d, the D s value decreases with the extent of intermolecular HB, x (HB), defined as the fraction of vaporization enthalpy due to HB. For both groups together (hydrogenbonded and otherwise), the D s data collapse when plotted against d/[1 − x(HB)]; this argues that the HB effect on D s can be described as a narrowing of the surface mobility layer by a factor [1 − x(HB)] relative to the van der Waals systems. Essentially the same picture holds for the surface crystal growth rate u s. The kinetic stability of a vapor-deposited glass decreases with x(HB) but is not better organized by the combined variable d/[1 − x(HB)]. These results indicate that surface crystal growth depends strongly on surface diffusion, whereas the formation of stable glasses by vapor deposition may depend on other factors.

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“…where ∆H vap is the vaporization enthalpy and ∆H vap (HB) is the portion of ∆H vap attributed to HBs. Following Bondi, 20 ∆H vap (HB) is calculated by a "replacement method,"…”

Section: Extent Of Intermolecular Hb From Vaporization Enthalpiesmentioning

confidence: 99%

Section: Extent Of Intermolecular Hb From Vaporization Enthalpiesmentioning

confidence: 99%

Effect of molecular size and hydrogen bonding on three surface-facilitated processes in molecular glasses: Surface diffusion, surface crystal growth, and formation of stable glasses by vapor deposition

Chen

Tylinski

et al. 2019

The Journal of Chemical Physics

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“…Instead, the hydrogen bond contribution (i.e. the hydrogen bond increment δOH) to the heat of evaporation is a good measure of hydrogen bond strength [23,24]. Figure 5 shows the standard heat of vaporization of linear alkane, normal alcohols and normal alkylamines, as compiled by the National Institute of Standards and Technology of the United States [25].…”

Section: (D) Effect Of Dispersion Correction On Density Functional Theory Structurementioning

confidence: 99%

Molecular interactions in nanocellulose assembly

Nishiyama¹

2017

Phil. Trans. R. Soc. A.

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The contribution of hydrogen bonds and the London dispersion force in the cohesion of cellulose is discussed in the light of the structure, spectroscopic data, empirical molecular-modelling parameters and thermodynamics data of analogue molecules. The hydrogen bond of cellulose is mainly electrostatic, and the stabilization energy in cellulose for each hydrogen bond is estimated to be between 17 and 30 kJ mol On average, hydroxyl groups of cellulose form hydrogen bonds comparable to those of other simple alcohols. The London dispersion interaction may be estimated from empirical attraction terms in molecular modelling by simple integration over all components. Although this interaction extends to relatively large distances in colloidal systems, the short-range interaction is dominant for the cohesion of cellulose and is equivalent to a compression of 3 GPa. Trends of heat of vaporization of alkyl alcohols and alkanes suggests a stabilization by such hydroxyl group hydrogen bonding to be of the order of 24 kJ mol, whereas the London dispersion force contributes about 0.41 kJ mol Da The simple arithmetic sum of the energy is consistent with the experimental enthalpy of sublimation of small sugars, where the main part of the cohesive energy comes from hydrogen bonds. For cellulose, because of the reduced number of hydroxyl groups, the London dispersion force provides the main contribution to intermolecular cohesion.This article is part of a discussion meeting issue 'New horizons for cellulose nanotechnology'.

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“…6 f 0.5 1.2-1. 9 2.4 f 0 . 3 In surveying the results of this investigation, one is struck by the simplicity of the relationships obtained.…”

Section: Homomorph Compoundmentioning

confidence: 99%

Heats of vaporization of hydrogen‐bonded substances

Bondì

Simkin

1957

AIChE Journal

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A new method is proposed for the calculation of the heat of vaporization of hydroxylated compounds to an accuracy of about k0.5 kcal./mole from no more data than the molecular structure and a boiling point. The older methods, by comparison, achieved an accuracy of about i l kcal./mole with a far greater computational effort, since they required the (usually hypothetical) critical temperature and critical pressure in addition to a boiling point.The method is here applied to aliphatic and aromatic alcohols, to ether-alcohols (e.g., the cellosolves), and to alcohols containing keto or aldehyde groups (e.g., salicylaldehyde) and supersedes previous correlations covering the heats of vaporization of these compounds. The method can also be used to assess the quality of vapor-pressure data of the compounds covered by it.The method is based on the assumption that the heat of vaporization consists of two terms, the dispersion energy and the hydrogen-bond increment (close but not equal to the hydrogen-bond strength). The first term is calculated from a knowledge of the heat of vaporization of the equistructural hydrocarbon, now easily available from the Tables of A.P.I. Research Project 44. The hydrogen-bond term is calculated from a set of rules given in the report.The application of the increment method of this report to other properties and other functional groups is the subject of a continuing investigation. PURPOSE AND SCOPEThe recurrent need for heat-of-vaporization data of increasingly complex synthetic oxygenated compounds and the discovery of some inconsistencies in previous correlations prompted a short inquiry into regularities which could be used as basis for improved calculation. The choice between the direct calculation of the heat of vaporization and the older path of calculating the entropy of vaporization has been resolved in favor of the first route, since it could be shown from basic principles that more information is required to estimate the entropy of vaporization from liquids with strongly Donald J. Simkin is with Rlarquardt Aircraft Company, Van Nuys, California.

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On the Hydrogen Bond Contribution to the Heat of Vaporization of Aliphatic Alcohols

Cited by 22 publications

References 4 publications

Effect of molecular size and hydrogen bonding on three surface-facilitated processes in molecular glasses: Surface diffusion, surface crystal growth, and formation of stable glasses by vapor deposition

Effect of molecular size and hydrogen bonding on three surface-facilitated processes in molecular glasses: Surface diffusion, surface crystal growth, and formation of stable glasses by vapor deposition

Molecular interactions in nanocellulose assembly

Heats of vaporization of hydrogen‐bonded substances

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