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Temperature dependence of 1H NMR chemical shifts and diffusivity of confined ethylammonium nitrate ionic liquid
Kazan Federal University, 420008 Kazan, Russia.
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Chemical Engineering. Department of Physics, Warwick University, Coventry CV4 7AL, UK.ORCID iD: 0000-0003-1067-7990
Kazan State Medical University, 420012 Kazan, Russia.
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Chemical Engineering. Kazan State Medical University, 420012 Kazan, Russia.ORCID iD: 0000-0002-6810-1882
2020 (English)In: Magnetic Resonance Imaging, ISSN 0730-725X, E-ISSN 1873-5894, Vol. 74, p. 84-89Article in journal (Refereed) Published
Abstract [en]

Some ionic liquids (ILs) change their dynamic properties when placed in a confinement between polar surfaces (Filippov et al., Phys. Chem. Chem. Phys. 2018, 20, 6316). The diffusivities of ions and NMR relaxation times in these ILs also reversibly change under a strong static magnetic field. The mechanisms of these phenomena are not clear, but it has been suggested that they involve modified hydrogen-bonding networks formed in these ILs in the presence of polar surfaces. To obtain a better understanding of these effects, we performed temperature-dependent measurements of chemical shifts and diffusion coefficients for ethylammonium nitrate (EAN) IL in the bulk phase (IB) and confined in layers with a thickness of ~4 μm between quartz plates unexposed (I phase) and exposed (IMF phase) to a static magnetic field of 9.4 T. It was shown that the NMR chemical shift of NH3 protons of EAN in the I phase is strongly shifted upfield, ~0.0145 ppm/K, which is due to weakening of the hydrogen-bonding network of the confined EAN. Exposure to the magnetic field leads to restitution of the hydrogen-bonding (H-bonding network). The temperature dependences of diffusion coefficients follow the order D(I) > D(IB) > D(IMF) and can be described by a Vogel-Fulcher-Tammann approach with variation of the pre-exponential factor, which is determined by the strength of the H-bonding network. Confinement of EAN between plates (IB → I) is an endothermic process, while processes occurring in a magnetic field, I → IMF and IMF → I, are exothermic and endothermic, respectively.

Place, publisher, year, edition, pages
Elsevier, 2020. Vol. 74, p. 84-89
Keywords [en]
Diffusion, Ion dynamics, Phase transformations, Restricted diffusion, Magnetic field
National Category
Physical Chemistry
Research subject
Chemistry of Interfaces
Identifiers
URN: urn:nbn:se:ltu:diva-80870DOI: 10.1016/j.mri.2020.09.012ISI: 000588632300009PubMedID: 32949669Scopus ID: 2-s2.0-85091392441OAI: oai:DiVA.org:ltu-80870DiVA, id: diva2:1469492
Note

Validerad;2020;Nivå 2;2020-09-22 (alebob)

Available from: 2020-09-22 Created: 2020-09-22 Last updated: 2023-09-05Bibliographically approved

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Antzutkin, Oleg N.Filippov, Andrei

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