Revealing complex formation in acetone-nalkane mixtures by MAS PFG NMR diffusion measurement in nanoporous hosts

Magic-angle spinning pulsed field gradient nuclear magnetic resonance (MAS PFG NMR) was applied for selective self-diffusion measurements of acetone -n-alkane (C-6 up to C-9) mixtures in nanoporous silica gel. Two specimens of silica gel with mean pore sizes of about 4 and 10 nm are considered. In the smaller pores, the n-alkane diffusivities are by about one and the acetone diffusivities by about two orders of magnitude smaller than in the larger pores. In addition, the acetone diffusivities in the narrow-pore specimen exhibit a pronounced oscillation with increasing chain length of the solvent n-alkanes: the diffusivities of acetone dissolved in odd-carbon number n-alkanes exceed those of acetone dissolved in even-carbon number n-alkanes by about 50%! These findings reproduce the tendencies observed in previous macroscopic release studies (Phys. Chem. Chem. Phys. 2003, 5, 2476) and suggest the formation of acetone -n-alkane complex-like assemblages in the narrow-pore silica gel.