Note, this equation
ignores the second order effect of any longitudinal diffusion that might be
present in the stationary phase.In fact, in the original form, the equation was
introduced by Van Deemter for packed GC columns and consequently, the
longitudinal diffusion term for the liquid phase was not included and the
function
, was replaced by,
. This was because the
diffusivity of the solute in a gas is four to five orders of magnitude greater
than in a liquid.
Thus, in the expression for longitudinal diffusion,
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the second
function
would not be significant.
In addition,
Van Deemter considered the resistance to mass transfer in the mobile phase to
be negligible. This was because the eddies that form between the particles
causes a turbulence or secondary flow that greatly increases the diffusivity of
the solute between the pores. As a result, the function,
, was also
not included. Consequently, the equation actually developed by Van Deemter took
the form,
