The Van Deemter Equation by Fahad
The Van Deemter Equation by Fahad
The Van Deemter Equation by Fahad
Where
H = height equivalent to a theoretical plate, a measure of the resolving power of
the column [m]
A = Eddy-diffusion parameter, related to channelling through a non-ideal
packing [m]
B = diffusion coefficient of the eluting particles in the longitudinal direction,
resulting in dispersion [m2 s1]
C = Resistance to mass transfer coefficient of the analyte between mobile and
stationary phase [s]
u = Linear Velocity [m s1]
The van Deemter equation evaluates efficiency (expressed as H) as a function of linear velocity
(u) or flow rate. The H called plate height, or height of a theoretical plate is determined by
dividing the column length (L) by the calculated number of theoretical plates. The goal is to
get a small plate height.
The plate theory was first introduced to partition chromatography by James and Martin
in 1952. This concept is borrowed from the performance description of distillation columns. It
divides the continuous separation process in a number of discrete individual steps. Thus, the
column consists of many consecutive segments, called theoretical plates, and for each plate an
equilibrium between the solute in the stationary and mobile phase is assumed. The smaller a
segment or the height of theoretical plate, the more plates are available per column meter.
Consequently, more distribution steps can be performed resulting in less relative band
broadening in relation to the column length. The number of theoretical plates N and the height
of a plate H are derived from the chromatogram using the retention time of a test solute and a
measure for the peak width:
The conversion between the different peak heights assumes a Gaussian peak. The plate height
(H) is obtained by dividing the column length (L) by the plate number (N):
The plate height is also often called the height equivalent to one theoretical plate
(HETP). The plate height is an important criterion to judge the efficiency of a column and can
be used to compare columns. High-quality columns are characterized by a high N and a low H.
However, both values depend on the column temperature, the average carrier gas velocity, and
the solute, which should always be specified. Keep in mind, N and H are determined under
isothermal conditions (validity of the plate theory). While the plate theory delivers a value to
judge the efficiency of a column, it does not explain peak broadening. This was first achieved
with the rate theory by van Deemter.
A term
The A term refers to band broadening caused by dispersion (multi-pathway) effects, the socalled Eddy diffusion:
= correction factor for the irregularity of the column packing
dp = average particle diameter
The transport of the mobile phase through the column packing can occur via different
flow channels. In simple terms, molecules belonging to one solute can take different flow paths
around the particles resulting in different pathway lengths and consequently broader peaks.
This effect is termed Eddy diffusion. It depends on the particle size and shape as well as the
irregularity of the column packing. The higher the diameter and irregularity of the particles the
stronger is the dispersion. Consequently, the A term can be minimized using small regular
particles and a uniform column packing, but at the cost of a higher backpressure. In addition,
at the laminar flow conditions present in chromatography, the flow rate is higher in the middle
of the flow channels and lower at the edges.
B term
The B term represents band broadening by longitudinal diffusion, the molecular diffusion both
in and against the flow direction
C term
The C term refers to band broadening caused by solute delay due to the mass transfer:
k = retention factor
dL = average film thickness of the stationary phase on the support material
DL = diffusion coefficient of the analyte in the liquid stationary phase
The C terms refers to the mass transfer between stationary and mobile phase. It is also
termed resistance against the mass transport. Chromatography is a dynamic process. A nearly
complete partition equilibrium is only reached at very low carrier gas flow rates. Thus, the C
term linearly increases with the carrier gas velocity. It takes a finite time to reach equilibrium
conditions that include the transport through the mobile phase to the phase interface, the phase
transfer (solutes entering the stationary phase), and the transport of the solutes into the liquid
stationary phase and back to the phase interface. These transport processes are determined by
axial diffusion (perpendicular to the flow direction of the mobile phase). Therefore, the C term
is determined by the diffusion coefficients of the solute in mobile and stationary phase and the
transport distances, most importantly the thickness of the liquid stationary phase. In contrast to
the B term, a fast mass transfer requires high values for the diffusion coefficient. Low
molecular weight carrier gases are advantageous for a fast diffusion. As diffusion in liquids is
slow, thin films of the liquid stationary phase are beneficial. As initially mentioned, the van
Deemter equation was developed for packed columns with liquid stationary phases under
isothermal conditions. Later on, it was modified and refined by several researchers (Golay,
Huber, Guiochon, Knox, Giddings, and others) taking the specific conditions and requirements
of capillary columns, solid stationary phases, and liquid chromatography into consideration.
Furthermore,
the
compressibility
of
the
Figure 2. Graphical representation of the A, B, and C terms of the van Deemter equation
carrier