In this study the zero length column (ZLC) technique is extended to the case where the decay of the adsorbed phase concentration is observed directly by nuclear magnetic resonance (NMR). An adsorption-desorption apparatus compatible with a 400-MHz NMR spectrometer was developed. It operates with nitrogen or helium as the inert purge gas. The column of the adsorbent material is placed in the sensitive region of the superconducting magnet and the rf coil of the NMR spectrometer. The time scales of the adsorption and desorption processes depend on concentration, temperature and crystal shape and are found to be in the range of 1-10 min. From the desorption branch, the non-equilibrium ZLC-NMR measurements yield intracrystalline diffusion coefficients in the range of 10(-13) to 10(-11) m2/s for different alkanes in silicalite-1. These values are always found to be smaller than the values measured by pulsed field gradient NMR under equilibrium condition indicating that there must be additional transport resistance at the external surface of these silicalite-1 zeolite crystals.