The present work focused on the experimental study of the specific features of self-diffusion of tridecane molecules in macroporous kaolinite, which is used as a raw material for the production of chemically inert membranes. The measurements of self-diffusion coefficients by pulsed magnetic field gradient nuclear magnetic resonance (PMFG NMR) revealed an increased translational mobility of tridecane molecules in kaolinite with incomplete filling of the pore space. This effect was accompanied by a sharp change in the slope of the Arrhenius plot of the self-diffusion coefficients of tridecane molecules in kaolinite. An analysis of the diffusion spin echo decay in the tridecane-kaolinite system revealed a discrepancy between the experimental data and the theoretical predictions, considering the effect of the geometry of porous space on molecular mobility. It was shown that the experimental results could be interpreted in terms of a model of two phases of tridecane molecules in the pores of kaolinite, in the gaseous and adsorbed state, coexisting under the fast-exchange conditions. Within the framework of the model, the activation energies of self-diffusion were calculated, which agreed satisfactorily with the experimental data. Additionally, the effects of the internal magnetic field gradients arising in a porous medium loaded with a gas or liquid on the data of the PFG NMR measurements were calculated. It was shown that the effect of magnetic field inhomogeneities on the measured self-diffusion coefficients of tridecane in kaolinite is small and could be neglected.
Keywords: PMFG NMR; activation energy; fast molecular exchange; kaolinite; membrane; porous material; self-diffusion; spin echo; temperature; tridecane; vapor phase.