Theoretical Plates
The concept of the theoretical plate arose from distillation column theory and was borrowed by A J. P. Martin to develop the first elution curve theory for the chromatography column. Neither in a distillation column, nor in a chromatographic column, does equilibrium exist in any part of the distribution system. This non-equilibrium condition arises from the dynamic nature of the distribution systems as the mobile phase is continually flowing past the stationary phase. The solute does not spend sufficient time at any point in the column for equilibrium to be achieved. To avoid this difficulty in the theoretical treatment of retention, the column is considered to be divided into a number of theoretical plates or cells and each is allotted a finite height (or length) that will allow the solute sufficient theoretical ‘dwell-time’ for equilibrium to take place. It is clear that the faster the equilibrium, the smaller the theoretical plate, and the more theoretical plates there will be in the column. Thus, the more efficient column has more theoretical plates. The plate theory was criticized when first developed, as it was claimed that equilibrium was not achieved in the column and, thus, the theoretical approach was invalid. However, the theoretical plate concept was introduced specifically to attend to this non- equilibrium problem The theory gave rise to the elution equation, the equation for resolution, and the equation used for calculating the column efficiency, all of which, have been exhaustively validated experimentally over many years.
Author: RPW Scott
Book:Extra Column Dispersion
Section:EC-Dispersion Small-Bore-Columns
The column was
10 m long, 1 mm I.D. packed with Partisil Silica Gel 20 mm particle diameter. At the optimum flow rate (i.e., 10 ml/min.) the column gave a quarter of a
million theoretical plates. However, the chromatogram shown in figure 34 was
obtained at a flow rate of 38 ml/min.
and, thus, as it was operated well above its optimum velocity, the column only
gave an efficiency of 160,000 theoretical plates. As the chromatographic data
was acquired and processed by a computer portions of the chromatogram could be
expanded and these are shown as inserts in the figure. It is seen that the
apparently confused peaks at the start of the chromatogram are, in fact, well
EC-Dispersion Small-Bore-Columns
Author: RPW Scott
Book:Plate Theory and Extensions
Section:Plate-Theory Effective-Plate-Number
efficiency, but uses the corrected
retention distance, as opposed to the total retention distance in conjunction
with the peak width. As a consequence, the effective plate number is
significantly smaller than the number of theoretical plates at low (k') values.
The column efficiency and the effective plate number converge to the same value
at high (k') values. It follows, that the effective plate number more nearly
corresponds to the actual resolving power of the column. Although the
theoretical plate, as defined by the plate theory, has a practical significance
and can be used in column design, the concept of the effective plate is
not theoretically unsound and is related directly to the theoretical plate.
The efficiency
of a column (n), in number of theoretical plates, has been shown to be given by
the following equation,
 
Plate-Theory Effective-Plate-Number
Author: RPW Scott
Book:Plate Theory and Extensions
Section:Plate-Theory Column-Efficiency
Column Efficiency
The column
efficiency is defined as the number of theoretical plates in the column. As
discussed in the plate theory, the faster the equilibrium process, the smaller
the plates and thus, the greater the number of plates in the column. It is
therefore important to know how to determine the number of plates a column
possesses and the relationship of the number of theoretical plates in the
column to the properties of the chromatogram.
Starting with
the Poisson form of the elution equation, the peak width at the points of
inflexion (which corresponds to
Plate-Theory Column-Efficiency
Author: RPW Scott
Book:Gas Chromatography
Section:YES Applications Gasoline
. It is clear that open tubular columns are
ideal for this type of separation problem. In fact, it would be impossible to
separate the components of gasoline efficiently with a packed column, even one
that is 50 ft long, and even if the inherent long analysis times could be
tolerated. In addition this type of separation demands the maximum number of
theoretical plates and therefore not only must open tubes be used but tubes of relatively
small diameter to produce the maximum number of theoretical plates. In fact,
several hundred thousand theoretical plates will be necessary and so the column
must also be very long. As has already been discussed, it is necessary to use
small radius open tubular columns with a split injection system. Furthermore,
as a result of the wide range of molecular weight of the components present,
gasoline has a relatively wide boiling range and so will require a temperature
program that will heat the column to 200 ˚C or more. A thermally
YES Applications Gasoline
Author: RPW Scott
Book:Dispersion in Chromatography Columns
Section:Dispersion Van-Deemter-Equation
nbsp;
Figure 12.
Graph of Log. Maximum Efficiency against Particle Diameter
It is seen from
figure 12 that changing the particle diameter from 1 to 20 micron results in an
efficiency change from about 3500 theoretical plates to nearly 1.5 million theoretical plates and furthermore,
this very high efficiency is achieved at an inlet
pressure of only 3000 p.s.i.. It is also seen that the maximum available
efficiency increases as the particle diameter increases. This is because, as
already discussed, if the pressure is limited, in order to increase the column
length to provide more theoretical plates, the permeability of the column must
be increased to allow the optimum mobile phase velocity to be realized. It is
possible to increase the
Dispersion Van-Deemter-Equation
Author: RPW Scott
Book:Plate Theory and Extensions
Section:Plate-Theory Derivation
nbsp;
dXs = KdXm (2)
Consider three
consecutive plates in a column, the (p-1), the (p) and the (p+1) plates and let
there be a total of (n) plates in the column. The three plates are depicted in
Figure 2.
Figure 2. Three Consecutive
Theoretical Plates in a Column
Let the
volumes of mobile phase and stationary phase in each plate be (vm)
and (vs) respectively, and the concentrations of solute in the
mobile and stationary phase in each plate be Xm(p-1), Xs(p-1),
Xm(p), Xs(p), Xm(p+1), and Xs(p+1), respectively.
Let a
Plate-Theory Derivation