Temperature dependence of hydrogen bonding in alcohols

Huelsekopf, Markus; Ludwig, Ralf

doi:10.1016/s0167-7322(99)00168-3

Cited by 56 publications

(33 citation statements)

References 28 publications

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“…Evidently, with its growing bulkiness, the contribution to the heat capacity of the OH group increases due to its progressively hampered accessibility to build a hydrogen bridge. This effect has been plausibly explained by Huelsekopf and Ludwig [54], who discovered, upon applying theoretical calculations based on the quantum cluster equilibrium theory (QCE) on two primary (ethanol and benzyl alcohol) and a tertiary alcohol (2,2-dimethyl-3-ethyl-3-pentanol), that primary alcohols on principle form cyclic tetramers and pentamers in the liquid phase, while tertiary alcohols under the same conditions only consist of monomers and dimers. Following this reasoning, the higher liquid heat capacity of secondary and tertiary alcohols over that of their primary counterparts having the same molecular formula is the result of their formation of smaller clusters, which inherently exhibit a higher number of rotational and translational degrees of freedom.…”

Section: Heat Capacity Of Liquidsmentioning

confidence: 92%

Calculation of the Isobaric Heat Capacities of the Liquid and Solid Phase of Organic Compounds at 298.15K by Means of the Group-Additivity Method

Naef

2020

Molecules

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The calculation of the isobaric heat capacities of the liquid and solid phase of molecules at 298.15 K is presented, applying a universal computer algorithm based on the atom-groups additivity method, using refined atom groups. The atom groups are defined as the molecules’ constituting atoms and their immediate neighbourhood. In addition, the hydroxy group of alcohols are further subdivided to take account of the different intermolecular interactions of primary, secondary, and tertiary alcohols. The evaluation of the groups’ contributions has been carried out by solving a matrix of simultaneous linear equations by means of the iterative Gauss–Seidel balancing calculus using experimental data from literature. Plausibility has been tested immediately after each fitting calculation using a 10-fold cross-validation procedure. For the heat capacity of liquids, the respective goodness of fit of the direct (r2) and the cross-validation calculations (q2) of 0.998 and 0.9975, and the respective standard deviations of 8.24 and 9.19 J/mol/K, together with a mean absolute percentage deviation (MAPD) of 2.66%, based on the experimental data of 1111 compounds, proves the excellent predictive applicability of the present method. The statistical values for the heat capacity of solids are only slightly inferior: for r2 and q2, the respective values are 0.9915 and 0.9874, the respective standard deviations are 12.21 and 14.23 J/mol/K, and the MAPD is 4.74%, based on 734 solids. The predicted heat capacities for a series of liquid and solid compounds have been directly compared to those received by a complementary method based on the "true" molecular volume and their deviations have been elucidated.

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Section: Heat Capacity Of Liquidsmentioning

confidence: 92%

Calculation of the Isobaric Heat Capacities of the Liquid and Solid Phase of Organic Compounds at 298.15K by Means of the Group-Additivity Method

Naef

2020

Molecules

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“…other alcohol studies: A comparison of liquid ethanol, benzyl alcohol and 2,2-dimethyl-3-ethyl-3-pentanol was carried out by Huelsekopf and Ludwig [34]. Cyclic tetramer and pentamer structures were observed as the main components of liquid ethanol and benzyl alcohol, whereas only monomers and dimers constituted the 2,2-dimethyl-3-ethyl-3-pentanol liquid [34,35].…”

Section: Introductionmentioning

confidence: 99%

“…Cyclic tetramer and pentamer structures were observed as the main components of liquid ethanol and benzyl alcohol, whereas only monomers and dimers constituted the 2,2-dimethyl-3-ethyl-3-pentanol liquid [34,35]. In a study concerning water, ethanol and methanol, Borowski and coworkers suggested to replace the mean field term by a mean field term per cluster [19].…”

Section: Introductionmentioning

confidence: 99%

What can clusters tell us about the bulk?

Kirchner

Spickermann

Lehmann

et al. 2011

Computer Physics Communications

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“…In an experimental work, Ludwig [17] studied NMR relaxation in alcohol-water mixtures, showing that the reorientational correlation time and the quadrupole coupling constants of water are very sensitive on the concentration of solute. In another work, the behavior of hydrogen bond with temperature has been analyzed by ab initio calculations of liquid alcohols [18]. The magnetic properties such as the isotropic and anisotropic chemical shifts have been used to detect and characterize hydrogen bonds.…”

mentioning

confidence: 99%

Ab initio NMR study of the isomeric hydrogen‐bonded methanol–water complexes

Fileti¹,

Canuto²

2005

Int J of Quantum Chemistry

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Isotropic and anisotropic chemical shifts for all atoms of complexes CH 3 HO . . . H 2 O and CH 3 OH . . . OH 2 have been calculated at the Hartree-Fock, secondorder Møller-Plesset (MP2) and density functional (B3LYP) theoretical levels using the 6-311ϩϩG(2d,2p) basis set. The influence of the hydrogen bond formation on the nuclear magnetic resonance chemical shifts in all atoms is analyzed. The basis set superposition error was taken into account, and its effects were more significant for the anisotropic shieldings on the oxygen atoms of the proton donor CH 3 OH . . . OH 2 and proton acceptor methanol CH 3 HO . . . H 2 O. Using counterpoise correction to the MP2 results, our best estimate for the calculated isotropic and anisotropic shifts of the H atom involved in the hydrogen bond are Ϫ2.98 and 11.95 ppm for CH 3 HO . . . H 2 O and Ϫ2.91 and 11.48 ppm for the CH 3 OH . . . OH 2 isomer, respectively. For the O atom of the OH hydrogen bonded, these calculated shifts are Ϫ5.21 and Ϫ5.35 ppm for CH 3 HO . . . H 2 O and Ϫ6.32 and Ϫ8.75 ppm for CH 3 OH . . . OH 2 . The effect of monomer relaxation was also considered and was found to be appreciable only for the oxygen atom of the proton donor OH due to the distance increase after complex formation.

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Temperature dependence of hydrogen bonding in alcohols

Cited by 56 publications

References 28 publications

Calculation of the Isobaric Heat Capacities of the Liquid and Solid Phase of Organic Compounds at 298.15K by Means of the Group-Additivity Method

Calculation of the Isobaric Heat Capacities of the Liquid and Solid Phase of Organic Compounds at 298.15K by Means of the Group-Additivity Method

What can clusters tell us about the bulk?

Ab initio NMR study of the isomeric hydrogen‐bonded methanol–water complexes

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