Gaussian Equation
The Plate theory provides an equation for the concentration of solute eluted from a chromatographic column in terms of the mobile phase and stationary phase volumes, the number of theoretical plates in the column and the volume of mobile phase passed through the column. The expression so obtained is a Poisson function which actually describes an asymmetric distribution curve. However, when the number of theoretical plates is large, which is so in chromatography columns, the Poisson function tends to a Gaussian function which is a symmetrical distribution curve as are most chromatographic peaks. The Gaussian function is the same as a one dimension probability function of the normal distribution (i.e. the normal error function). The variance of the Gaussian curve as derived from the Plate theory is proportional the number of theoretical plates in the column (n) and the standard deviation is thus, proportion to the square root of n. On the chromatogram the retention distance of a solute is proportional to (n) and half the peak width at 0.6065 of the peak height is proportional to the square root of n. Thus, both the variance and the standard deviation can be calculated from measurements made on the chromatogram.
Author: RPW Scott
Book:Plate Theory and Extensions
Section:Plate-Theory Gaussian-Equation
nbsp;
The Gaussian Form of the Elution Equation
To change the
Poisson form of the elution equation to the Gaussian form, it is necessary to
change the position of the origin of the Poisson curve. Consider the elution
curve as shown in Figure 9. The origin of the Poisson curve is the point of
injection, whereas the origin of the Gaussian curve is at the peak maximum,
which will be (n) plate volumes from the injection point.
Now, a point
X, (v) plate volumes from the point of injection will be
(v-n) = w plate volumes from the peak maximum. Consequently, v = (n+w). This
change of origin is depicted in Figure 9.
Now, the Poisson form of the
elution equation is as follows,
 
Plate-Theory Gaussian-Equation
Author: RPW Scott
Book:Plate Theory and Extensions
Section:Plate-Theory Derivation
;
and for the
nth
Plate,
(12)
Equation (12)
is the basic elution curve equation and is, in fact, a Poisson function. In due
course, it will be shown that if (n) is large, the function tends to the normal
Error function or Gaussian function. As in most chromatography systems, (n)
>>100 most peaks will be Gaussian or nearly Gaussian in shape. However,
due to equipment limitations and other factors, the shape of a peak can be
distorted which will also be discussed in due course
Plate-Theory Derivation
Author: RPW Scott
Book:Dispersion in Chromatography Columns
Section:Dispersion Random-Walk-Model
the Random-Walk processes itself can be found in any appropriate
textbook on probability (4) and will not be given here but the consequential
equation will be used.
The Random Walk Model
The
random-walk model consists of a series of step-like movements for each molecule
which may be positive or negative the direction being completely random. After
(p) steps, each step having a length (s) the average of the molecules will have
moved some distance from the starting position and will form a Gaussian type
distribution curve with a variance of s2
.
Now according
to the random-walk model,
 
Dispersion Random-Walk-Model
Author: RPW Scott
Book:Dispersion in Chromatography Columns
Section:Dispersion Dispersion-Processes Diffusion Process
nbsp;
Now,
from the Plate Theory (see
Plate Theory and Extensions),
,
where (n) is
the variance of the Gaussian curve.
Now, (n) is
the volume variance of the Gaussian curve (i.e., ), then, by
comparison, (2Dmt) will be the length variance of the
concentration curve where (t) is the elapsed time. Consequently, if a
differential equation of the form is derived that
describes some form of dispersion that arises from a random diffusion process,
then the solution will be a Gaussian function and, more important from the
point of view of the Rate Theory, the Gaussian curve will have a
Dispersion Dispersion-Processes Diffusion Process
Author: RPW Scott
Book:Plate Theory and Extensions
Section:Plate-Theory Close-Eluting-Peaks
nbsp;
and,
(41)
Equation (41)
is the Gaussian form of the elution curve equation and can be used as an
alternative to the Poisson form in all applications of the Plate Theory.
Retention Measurements on Close Eluting Peaks
The retention
data, are the most important measurements made in any chromatographic analysis.
In addition to providing data for identification (using the capacity ratio or
the separation ratio), retention times are also important in column design. It
will be shown later that the column efficiency needed to ensure resolution of a
pair of
Plate-Theory Close-Eluting-Peaks
Author: RPW Scott
Book:Plate Theory and Extensions
Section:Plate-Theory Inflection-Points
equation
(51) in equation (50),
Now,
Consequently,
the term and those
higher can be
ignored with respect to .
Then,
and
(52)
Equation (52)
shows that the points of inflection occur at 0.6065 of the peak height. It
follows that the peak width, at 0.6065 of the peak height, will be
equivalent to two standard deviations (2s)
of the Poisson or Gaussian curve
Plate-Theory Inflection-Points