Is a dissociation process underlying the molecular origin of the Debye process in monohydroxy alcohols?
Authors:
- Natalia Soszka,
- Barbara Maria Hachuła,
- Magdalena Tarnacka,
- Ewa Kamińska,
- Sebastian Pawlus,
- Kamil Kamiński,
- Marian Paluch
Abstract
Herein, we investigated the molecular dynamics as well as intramolecular interactions in two primary monohydroxy alcohols (MA), 2-ethyl-1-hexanol (2EHOH) and n-butanol (nBOH), by means of broad-band dielectric (BDS) and Fourier transform infrared (FTIR) spectroscopy. The modeling data obtained from dielectric studies within the Rubinstein approach [ Macromolecules 2013, 46, 7525−7541] originally developed to describe the dynamical properties of self-assembling macromolecules allowed us to calculate the energy barrier (Ea) of dissociation from the temperature dependences of relaxation times of Debye and structural processes. We found Ea ∼ 19.4 ± 0.8 and 5.3 ± 0.4 kJ/mol for the former and latter systems, respectively. On the other hand, FTIR data analyzed within the van’t Hoff relationship yielded the energy barriers for dissociation Ea ∼ 20.3 ± 2.1 and 12.4 ± 1.6 kJ/mol for 2EHOH and nBOH, respectively. Hence, there was almost a perfect agreement between the values of Ea estimated from dielectric and FTIR studies for the 2EHOH, while some notable discrepancy was noted for the second alcohol. A quite significant difference in the activation barrier of dissociation indicates that there are probably supramolecular clusters of varying geometry or a ring-chain-like equilibrium is strongly affected in both alcohols. Nevertheless, our analysis showed that the association/dissociation processes undergoing within nanoassociates are one of the main factors underlying the molecular origin of the Debye process, supporting the transient chain model.
- Record ID
- USLca06d7fcd623409c99443b24b1b29653
- Author
- Journal series
- Journal of Physical Chemistry B, ISSN 1520-6106, e-ISSN 1520-5207
- Issue year
- 2021
- Vol
- 125
- No
- 11
- Pages
- 2960-2967
- Publication size in sheets
- 0.40
- Keywords in English
- Debye process, monohydroxy alcohols
- ASJC Classification
- ; ;
- DOI
- DOI:10.1021/acs.jpcb.0c10970 Opening in a new tab
- Handle.net URL
- hdl.handle.net/20.500.12128/19720 Opening in a new tab
- URL
- https://pubs.acs.org/doi/10.1021/acs.jpcb.0c10970 Opening in a new tab
- Language
- eng (en) English
- License
- File
-
- File: 1
- Is a dissociation process underlying the molecular origin of the Debye process in monohydroxy alcohols?, File Soszka_Is_a_dissociation_process_underlying.pdf / 2 MB
- Soszka_Is_a_dissociation_process_underlying.pdf
- publication date: 20-10-2023
- Is a dissociation process underlying the molecular origin of the Debye process in monohydroxy alcohols?, File Soszka_Is_a_dissociation_process_underlying.pdf / 2 MB
-
- Score (nominal)
- 140
- Score source
- journalList
- Score
- = 140.0, 02-04-2024, ArticleFromJournal
- Publication indicators
- Citation count
- 5
- PubMed ID
- 33691402 Opening in a new tab
- Uniform Resource Identifier
- https://opus.us.edu.pl/info/article/USLca06d7fcd623409c99443b24b1b29653/
- URN
urn:uni-kat-prod:USLca06d7fcd623409c99443b24b1b29653
* presented citation count is obtained through Internet information analysis, and it is close to the number calculated by the Publish or PerishOpening in a new tab system.