Study of Dispersion in Packed Chromatographic Columns by Pulsed Field Gradient Nuclear Magnetic Resonance

Abstract

Pulsed field gradient nuclear magnetic resonance (PFGNMR) allows the direct determination of the average value of the axial and transverse apparent dispersion coefficient in a packed bed over a certain volume of this bed. From these data, the dependence of the local value of the height equivalent to a theoretical plate (HETP) of a chromatographic column on the fluid velocity can be measured accurately. The results are shown to be exactly accounted for by the Giddings equation. The PFGNMR measurements are made over a very short period of time. Hence they give the value of the HETP averaged over a limited volume of packing and a short time. This value is markedly smaller than the one afforded by the classical methods of chromatography and which is derived from the width of the distribution of the residence time of a small sample. The difference is explained by systematic variations of the local mobile-phase velocity across the column. PFGNMR techniques also allow the determination of the tortuosity of the column packing in the absence of flow. Their results confirm that the apparent dispersion experienced by a molecule is a function of the duration of the observation, until the tortuosity of the packing is completely felt. The values obtained agree very well with those derived from classical chromatography determinations.