Using a two-zone moment analysis
(TZMA) method based
on Brenner’s
generalized dispersion theory for two-dimensional (2D) and three-dimensional
(3D) periodic media, we investigated the mechanisms for dispersion
in particulate media for liquid chromatography. This was done using
a set of plate height data covering an unprecedented wide range of
retention factors, diffusion coefficients, and velocities, all computed
with unequaled accuracy. Applying Giddings’ additivity test,
based on alternatingly making the diffusion coefficient in the mobile
and stationary zones infinitely large, the dispersion data clearly
indicate a lack of additivity. Although this lack could be directly
understood by identifying the existence of multiple parallel mass
transfer paths, the additivity assumption interestingly overestimates
the true C term band broadening (typically by more than 10%, depending
on conditions and dimensionality of the system). However, Giddings
originally asserted the occurrence of parallel paths would always
lead to an underestimation of the dispersion. The origin of the lack
of additivity is analyzed in detail and qualitatively explained. Finally,
we also established a generic framework for the modeling of the effect
of the reduced velocity and the retention coefficient on the C term
in ordered chromatographic media. This led to the introduction of
a new expression for the mobile zone mass transfer term, which, unlike
the currently used literature expression, contains the complete k″ dependency.