Hierarchy of hydrogen bonding among constitutional isomers of hexanol

Kód výsledku v 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>

Nalezeny alternativní kódy

RIV/60461373:22340/24:43929350

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Hierarchy of hydrogen bonding among constitutional isomers of hexanol

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Hierarchy of hydrogen bonding among constitutional isomers of hexanol

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GM23-05476M" target="_blank" >GM23-05476M: Vývoj ab initio modelování pro neuspořádané molekulární polovodiče</a><br>

Návaznosti

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

Rok uplatnění

2024

Kód důvěrnosti údajů

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

Název periodika

JOURNAL OF MOLECULAR LIQUIDS

ISSN

0167-7322

e-ISSN

1873-3166

Svazek periodika

394

Číslo periodika v rámci svazku

15-01-2024

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

13

Strana od-do

123804

Kód UT WoS článku

001146460800001

EID výsledku v databázi Scopus

2-s2.0-85181017627