21 research outputs found
Viscosity of Molecular Newtonian Liquids
Abstract: An empirical expression based on the general notions of available structural and diffusion theories of viscous flows has been proposed for the viscosity coefficients of molecular liquids. The proposed expression determines the relation between the viscosity coefficient, self-diffusion coefficient, surface tension coefficient, and steric parameter of liquid molecules. The validity of the proposed expression has been confirmed by its applicability to some liquids having different physicochemical characteristics
Hydration, self-diffusion and ionic conductivity of Li<sup>+</sup>, Na<sup>+</sup> and Cs<sup>+</sup> cations in Nafion membrane studied by NMR
Hydration of Nafion 117 perfluorinated sulfonic cation-exchange membrane in alkaline ion forms was investigated by high resolution 1H NMR. Hydration numbers of Li+, Na+ and Cs+ cations were 5 ± 1, 6 ± 1 and 1 ± 0.2, correspondingly for membrane equilibrated with water vapor at 98% RH. As opposed to Li+ and Na+, which form separate ion pair, Cs+ cation directly contacts with membrane sulfonate group. Cation self-diffusion coefficients were measured by pulsed field gradient NMR technique on 7Li, 23Na and 133Cs nuclei for the first time. Self-diffusion coefficients are changed in the next rows Li+ ≤ Na+ > Cs+. Self-diffusion activation energies of Li+ and Na+ cations are about 20 kJ/mol which is close to water self-diffusion activation energy in these membranes, but Cs+ self-diffusion activation energy is distinctly more (25 kJ/mol). Ionic conductivities calculated on the basis of Nernst–Einstein equation from cation self-diffusion coefficients 1.6∙10−2, 2∙10−2, 6∙10−3 S/cm for Li+, Na+, Cs+ cations, correspondingly, are closely approximating to conductivities measured by impedance spectroscopy: 1.3∙10−2, 1.1∙10−2, 2.3∙10−3 S/cm for Li+, Na+, Cs+ cations, correspondingly, but calculated values are appreciably more compared with experimental meanings
New Approach to Analyze 2D Map T <inf>1</inf>–T <inf>2</inf>
© 2020, Springer-Verlag GmbH Austria, part of Springer Nature. Based on the method of two-dimensional (2D) nuclear magnetic resonance (NMR) relaxometry, a technique was developed for determining the joint distribution of the correlation time τc and the Van Vleck second moments Δ ω2. The field of application is the study of slow molecular motions corresponding to the condition of the ratio of nuclear magnetic relaxation times T1/T2 > 1.05 (the relation of spin–lattice relaxation time T1 to spin–spin relaxation time T2). The technique is based on the use of a priori information about the mechanism of nuclear magnetic relaxation in a system. The technique has used this information in the regularization solution of an inverse problem. In contrast to the known method for calculating 2D maps of the joint distribution P2 (T1, T2), the proposed method for constructing a 2D map of the joint distribution Q2(τc, Δ ω2) does not depend on the main characteristic of the NMR relaxometer—the resonance frequency ω. The technique was used to analyze the characteristics of sorbed water in clay rocks–argillite
Molecular and ionic diffusion in ion exchange membranes and biological systems (Cells and proteins) studied by NMR
The results of NMR, and especially pulsed field gradient NMR (PFG NMR) investigations, are summarized. Pulsed field gradient NMR technique makes it possible to investigate directly the partial self-diffusion processes in spatial scales from tenth micron to millimeters. Modern NMR spectrometer diffusive units enable to measure self-diffusion coefficients from 10−13 m2 /s to 10−8 m2 /s in different materials on1 H,2 H,7 Li,13 C,19 F,23 Na,31 P,133 Cs nuclei. PFG NMR became the method of choice for reveals of transport mechanism in polymeric electrolytes for lithium batteries and fuel cells. Second wide field of application this technique is the exchange processes and lateral diffusion in biological cells as well as molecular association of proteins. In this case a permeability, cell size, and associate lifetime could be estimated. The authors have presented the review of their research carried out in Karpov Institute of Physical Chemistry, Moscow, Russia; Institute of Problems of Chemical Physics RAS, Chernogolovka, Russia; Kazan Federal University, Kazan, Russia; Korea University, Seoul, South Korea; Yokohama National University, Yokohama, Japan. The results of water molecule and Li+, Na+, Cs+ cation self-diffusion in Nafion membranes and membranes based on sulfonated polystyrene, water (and water soluble) fullerene derivative permeability in RBC, casein molecule association have being discussed