Hydrogen‐bond cooperativity in 1‐alkanol + <i>n</i>‐alkane binary mixtures

Gupta, Ram B.; Brinkley, Ray L.

doi:10.1002/aic.690440122

Cited by 79 publications

(99 citation statements)

References 44 publications

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“…7(a). 43 In accord with previous IR investigations this red shift can be interpreted to be due to an increasing degree of hydrogen bond cooperativity: 18,44,45,46 This term means that the formation of a hydrogen bridge enhances the electron density at the lone pairs of the proton donating oxygen atom and therefore increases the ability for proton acceptance. 47 The change in electron density is in turn accompanied by a stretching of the covalent OH bond.…”

Section: Wavelengths Of Maximum Absorbancesupporting

confidence: 61%

Debye relaxation and 250 K anomaly in glass forming monohydroxy alcohols

Bauer

Burlafinger

Gainaru

et al. 2013

The Journal of Chemical Physics

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A previous dielectric, near-infrared (NIR), and nuclear magnetic resonance study on the hydrogen-bonded liquid 2-ethyl-1-hexanol [C. Gainaru et al., Phys. Rev. Lett. 107, 118304 (2011)] revealed anomalous behavior in various static quantities near 250 K. To check whether corresponding observations can be made for other monohydroxy alcohols as well, these experimental methods were applied to such substances with 5, 6, 7, 8, and 10 carbon atoms in their molecular backbone. All studied liquids exhibit a change of behavior near 250 K which is tentatively ascribed to effects of hydrogen bond cooperativity. By analyzing the NIR band intensities, a linear cluster size is derived that agrees with estimates from dielectric spectroscopy. All studied alcohols, except 4-methyl-3-heptanol, display a dominant Debyelike peak. Furthermore, neat 2-ethyl-1-butanol exhibits a well resolved structural relaxation in its dielectric loss spectrum which so far has only been observed for diluted monohydroxy alcohols.

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Section: Wavelengths Of Maximum Absorbancesupporting

confidence: 61%

Debye relaxation and 250 K anomaly in glass forming monohydroxy alcohols

Bauer

Burlafinger

Gainaru

et al. 2013

The Journal of Chemical Physics

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“…ous work Gupta and Brinkley, 1998 on alcohol self-association. The only addition to this apparatus was a cooling coil before the heaterrcontroller so experiments could be performed at subambient temperatures.…”

Section: Experimental Studies Apparatus and Materialsmentioning

confidence: 99%

“…acids Noguchi et al, 1999 , and the intramolecular H-bond-Ž . ing present in glycol ethers Brinkley and Gupta, 1998 . However, H-bonds are largely electrostatic in nature, and therefore other suitable sources of electrons could also act as an acceptor group.…”

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confidence: 99%

Hydrogen bonding with aromatic rings

Brinkley

Gupta

2001

AIChE Journal

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Thermodynamic effects of hydrogen bonding are important in determining the phase behavior in polar fluids. While efforts to understand “strong” donor and “strong” acceptor combinations (H‐bonds involving a formation energy more negative than −20 kJ/mol such as alkanol‐alkanol H‐bonding have been substantial, weak H‐bonds involving double bonds or aromatic rings as proton acceptors) have largely been ignored. Using FTIR spectroscopy H‐bonding between alcohol donor and aromatic ring‐containing acceptor molecules was studied including l‐hexanol and cyclohexanol at low concentrations where self‐association is negligible (strong donors). H‐bonding “weak” acceptors studied include toluene and m‐xylene. Clear spectroscopic evidence existed for the formation of H‐bonds between the alcohol and aromatic molecules, which are much weaker than conventional “strong donor”–“strong acceptor” H‐bonds. Using quantitative FTIR measurements, the percentage of H‐bonded alcohol molecules over a range of aromatic concentrations was determined. Ab initio calculations also showed that alcohol–aromatic H‐bonds are much weaker than alcohol–alcohol H‐bonds. This H‐bonding, though weak, will contribute significantly to the chemical potential of the molecules.

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“…Recent research indicates that association of polymer solutions has an obvious effect not only on solution phase equilibria, but also the extent of association changes with solvent concentration and temperature. 19,20 Heintz and Stephan 21,22 used the UNIQUAC model to predict organic aqueous solubility in a poly(vinyl alcohol) membrane, in which an empirical constant was introduced to account for the hydrogen-bonding effect, by adding a parameter to the canonical formalism. Although this model considered the effect of hydrogen bonding on solubility prediction, it still provided no clear physical picture of association.…”

Section: Introductionmentioning

confidence: 99%