Hierarchy of hydrogen bonding among constitutional isomers of hexanol

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F24%3A43929350" target="_blank" >RIV/60461373:22310/24:43929350 - isvavai.cz</a>

Alternative codes found

RIV/60461373:22340/24:43929350

Result on the web

<a href="https://www.sciencedirect.com/science/article/pii/S0167732223026119?via%3Dihub" target="_blank" >https://www.sciencedirect.com/science/article/pii/S0167732223026119?via%3Dihub</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.molliq.2023.123804" target="_blank" >10.1016/j.molliq.2023.123804</a>

Result language

angličtina

Original language name

Hierarchy of hydrogen bonding among constitutional isomers of hexanol

Original language description

The strength and thermal stability of the hydrogen bonding influence the bulk properties of associating liquids, such as higher alcohols. Temperature-induced decay of the hydrogen bonds translates into uncommon trends in the heat capacity of the liquid, frequently exhibiting vast plateaus or distinct maxima. Experimental isobaric heat capacities of sixteen aliphatic hexanols in their liquid phase, resulting from Tian-Calvet calorimetry in the temperature range of 260–340 K, are presented. This temperature range is extended to 380 K with a power-compensation DSC for thirteen compounds. Among the studied compounds, a maximum on the temperature dependence of the heat capacity is explicitly observed below 380 K for six species. Upon derivation of residual heat capacities, this maximum gets amplified and can be recognized for 13 species (below 400 K). Molecular dynamics simulations of pure samples of all hexanol isomers are performed to interpret the observed trends. The hydrogen-bonding hierarchy is established computationally in terms of structural and energetic descriptors of bulk liquids. The strength of the hydrogen bonds is directly related to the extent of steric hindrance imposed on the hydroxyl moieties by the side alkyl chains in the bulk liquid. The hexanol isomers predicted computationally to form the weakest hydrogen bonds in the liquid match those, for which the non-monotonous trends of the heat capacities were observed. The position of the heat capacity maximum is sensitive to a subtle variation of the hydrogen bonding strength and shifts to higher temperatures upon strengthening of the hydrogen bonding for less branched and primary hexanol isomers. © 2023 Elsevier B.V.

Czech name

—

Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

<a href="/en/project/GM23-05476M" target="_blank" >GM23-05476M: Making ab initio modelling possible for disordered molecular semi-conductive materials</a><br>

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2024

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

JOURNAL OF MOLECULAR LIQUIDS

ISSN

0167-7322

e-ISSN

1873-3166

Volume of the periodical

394

Issue of the periodical within the volume

15-01-2024

Country of publishing house

NL - THE KINGDOM OF THE NETHERLANDS

Number of pages

13

Pages from-to

123804

UT code for WoS article

001146460800001

EID of the result in the Scopus database

2-s2.0-85181017627