Open AccessIs a Dissociation Process Underlying the Molecular Origin of the Debye Process in Monohydroxy Alcohols?
Author(s) -
Natalia Soszka,
Barbara Hachuła,
Magdalena Tarnacka,
Ewa Kamińska,
S. Pawlus,
Kamil Kamiński,
Marian Paluch
Publication year - 2021
Publication title -
the journal of physical chemistry. b
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.864
H-Index - 392
eISSN - 1520-6106
pISSN - 1520-5207
DOI - 10.1021/acs.jpcb.0c10970
Subject(s) - dissociation (chemistry) , chemistry , fourier transform infrared spectroscopy , activation energy , intramolecular force , dielectric , debye , macromolecule , molecular dynamics , computational chemistry , thermodynamics , materials science , organic chemistry , chemical engineering , biochemistry , physics , optoelectronics , engineering
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 ( n BOH), 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 ( E a ) of dissociation from the temperature dependences of relaxation times of Debye and structural processes. We found E a ∼ 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 E a ∼ 20.3 ± 2.1 and 12.4 ± 1.6 kJ/mol for 2EHOH and n BOH, respectively. Hence, there was almost a perfect agreement between the values of E a 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.