Diluting the hydrogen bonds in viscous solutions of n-butanol with n-bromobutane: a dielectric study

The Journal of Chemical Physics
T El Goresy, Roland Böhmer

Abstract

Glass-forming monohydroxy alcohols exhibit not only a structural relaxation but also a slower, single-exponential Debye-type relaxation process which already freezes in the liquid phase. By using dielectric spectroscopy, we study how these relaxations evolve when the aprotic alkyl halide n-bromobutane is added to n-butanol, thereby diluting the hydrogen-bond network. The structural relaxation times smoothly vary over the concentration range of this completely miscible binary system. The Debye process remains unaffected by the dilution of the OH groups up to n-bromobutane mole fractions of about 50%. For larger hydroxy dilutions, it turns rather abruptly into a feature which develops significant spectral broadening and it becomes faster. In the dilute limit, the decoupling between the time scale of the Debye process and that of the structural relaxation amounts to almost 6 decades when extrapolated to the glass transition temperature. This relatively large, strongly concentration dependent decoupling is interpreted in analogy to normal modes in polymers. The present results suggest that the structural and the Debye-like responses of monohydroxy alcohols are unrelated.

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Citations

Oct 15, 2013·The Journal of Chemical Physics·S BauerR Böhmer
Apr 5, 2014·The Journal of Chemical Physics·P SillrénR Böhmer
Nov 11, 2011·The Journal of Chemical Physics·Catalin GainaruRoland Böhmer
Nov 5, 2013·The Journal of Chemical Physics·Yanqin GaoLi-Min Wang
Mar 15, 2013·The Journal of Chemical Physics·S BauerR Böhmer
Feb 2, 2010·The Journal of Chemical Physics·Rikard BergmanJan Swenson
Jul 19, 2013·The Journal of Chemical Physics·Yanqin GaoLi-Min Wang
Mar 17, 2011·The Journal of Chemical Physics·Helén Jansson, Jan Swenson
Feb 2, 2011·The Journal of Chemical Physics·G PowerG P Johari
Nov 29, 2014·The Journal of Chemical Physics·Leila HennousAziz Ghoufi
Nov 26, 2015·The Journal of Physical Chemistry. B·Catalin P GainaruR Böhmer
May 24, 2013·The Journal of Physical Chemistry. B·Khalid ElaminJan Swenson
Nov 2, 2015·The Journal of Chemical Physics·M T Ottou AbeF Affouard
Nov 7, 2018·Physical Chemistry Chemical Physics : PCCP·Marzena Rams-BaronMarian Paluch
Apr 7, 2010·Physical Review Letters·Helén JanssonJan Swenson
Nov 22, 2020·The Journal of Chemical Physics·C A ThomannC Gainaru
Mar 17, 2021·The Journal of Chemical Physics·Florent GoujonPatrice Malfreyt
Nov 9, 2011·Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics·Sebastian PawlusMarzena Dzida
Aug 17, 2010·The Journal of Physical Chemistry. B·F Affouard, Natália T Correia

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Methods Mentioned

BETA
nuclear magnetic resonance
NMR

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