Diffusion-Ordered Spectroscopy (DOSY) as a Powerful NMRMethod to Investigate Molecular Mobitiesand IntermolecularInteractions in Complex Oil Mixtures.

Abstract

Studying the characteristics and molecular mechanisms of liquid self-diffusion coefficient and viscosity changes is of great significance for, e.g., chemical and petroleum processing. As an example of a highly complex liquid, asphaltene-free high-acid and high-viscosity crude oil and its extracted fractions were studied by comparing their 1H DOSY diffusion maps. The crude oil exhibited a polydisperse diffusion distribution, including multiple diffusion portions with diffusion coefficients much smaller than that of any single fraction in independent diffusion. The main mechanism that leads to the decreases in the diffusion coefficients of crude oil is attributed to diffusion resistance enhanced by Dynamical Molecular-Interaction Networks (DMINs), rather than by enlargement of the diffusion species caused by molecular aggregation. Constructed through the synergistic interactions of various polar molecules in crude oil, DMINs dynamically bind polar molecules, trap polarizable molecules, and spatially hinder the free motion of non-polar molecules. Overall, this reduces the diffusion coefficients of all molecular. This study demonstrates that DOSY is a powerful NMR method to investigate molecular motion abilities in complex mixtures. In addition, the insights in the influence of the interaction matrix on the molecular mobility also help to understand the contribution of "structural viscosity" to the viscosity of heavy oil.