Dispersion in

Chrom-Ed Book Series
Raymond P. W. Scott
Dispersion in
Chromatography
Columns
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Contents
Introduction to the Rate Theory..............................................................1
The Summation of Variances..................................................................2
The Alternative Axes of a Chromatogram..........................................9
The Random Walk Model.................................................................13
Dispersion Processes that take Place in an LC Column...................22
The Multipath Process...................................................................23
Longitudinal Diffusion..................................................................24
The Diffusion Process...................................................................24
The Resistance to Mass Transfer in The Mobile Phase................29
The Resistance to Mass Transfer in the stationary Phase.............30
Resistance to Mass Transfer Dispersion.......................................31
Diffusion Controlled Dispersion in the Stationary Phase............34
Diffusion Controlled Dispersion in the Mobile Phase.................35
Effect of Mobile Phase Compressibility On the HETP Equation for a
Packed GC Column...........................................................................37
The Van Deemter Equation...............................................................43
Alternative Equations for Peak Dispersion ..........................................55
The Giddings Equation.....................................................................56
The Huber Equation..........................................................................57
The Knox Equation...........................................................................59
The Horvath and Lin Equation..........................................................61
The Golay Equation..........................................................................61
Experimental Validation of the Van Deemter Equation...................66
The Effect of the Function of (k') on Peak Dispersion.....................82
Summary................................................................................................84
References ............................................................................................86
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Introduction to the Rate Theory
The separation of a solute pair in a chromatographic system depends on
moving the peaks apart in the column and constricting their dispersion
so that the two solutes are eluted discretely. The factors that control
retention have been discussed in Book 7 and in this book the processes
of peak dispersion will be considered together with the means by which
peak dispersion can be minimized.
Solute equilibrium between the mobile and stationary phases is never
achieved in the chromatographic column except possibly at the
maximum of a peak. To circumvent this non equilibrium condition and
allow a simple mathematical treatment of the chromatographic process,
Martin and Synge (1) borrowed the plate concept from distillation
theory and considered the column consisted of a series of theoretical
plates in which equilibrium could be assumed to occur. In fact each
plate represented a 'dwell time' for the solute to achieve equilibrium at
that point in the column and the process of distribution could be
considered as incremental. This approach has been discussed in Book
6.
Employing this concept an equation for the elution curve can be easily
obtained and, from that basic equation, others can be developed that
describe the various properties of a chromatogram. Such equations
have permitted the calculation of efficiency, the number of theoretical
plates required to achieve a specific separation and among many
applications, elucidate the function of the heat of absorption detector.
The Plate Theory, however, does little to explain how the efficiency of
a column may be changed or, what causes peak dispersion in a column
in the first place. It does not tell us how dispersion is related to column
geometry, properties of the packing, mobile phase flow-rate, or the
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physical properties of the distribution system. Nevertheless, it was not
so much the limitations of the Plate Theory that provoked Van Deemter
et al (2) (who were chemical engineers and mathematicians) to
develop, what is now termed the Rate Theory for chromatographic
dispersion, but more to explore an alternative mathematical approach to
explain the chromatographic process. Virtually all basic
chromatography theory evolved over the twenty five years between
1940 and 1965 and it was in the middle of this period that Van Deemter
and his colleagues presented their Rate Theory concept in (1956).
Since that time, other Rate Theories have been presented, together with
accompanying dispersion equations and in due course each will be
discussed, but most were very similar in form to that of Van Deemter
et al. It is interesting to note, however, that, even after thirty five years
of chromatography development, the equation that best describes band
dispersion in practice is still the Van Deemter equation. This is
particularly true for columns operated around the mobile phase
optimum velocity where the maximum column efficiency is obtained.
The purpose of the Rate Theory is to help understand the processes that
cause dispersion in a chromatographic column and to identify those
properties of the chromatographic system that control it. Such
information will allow the best column to be designed to effect a given
separation in the most efficient way. However, before discussing the
Rate Theory some basic concepts must be introduced and illustrated.
The Summation of Variances
The width of the band of an eluted solute relative to its proximity to its
nearest neighbor determines whether two solutes are resolved or not.
The ultimate band width as sensed by the detector is the result of a
number of individual dispersion processes taking place in the
chromatographic system, some of which take place in the column itself
and some in the sample valve, connecting tubes and detector (see book
10). In order to determine the ultimate dispersion of the solute band it
is necessary to be able to calculate the final peak variance. This is
achieved by taking into account all the individual dispersion processes
that take place in a chromatographic system. It is not possible to sum
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the band widths (standard deviation or ()) resulting from each
individual dispersion process to obtain the final band width, but it is
possible to sum all the respective variances. However, the summation
of all the variances resulting from each process is only possible if each
process is non-interacting and random in nature. That is to say, the
extent to which one dispersion process progresses is independent of the
development and progress of any other dispersion process.
Thus, assuming there are (n) non-interacting, random dispersive
processes occurring in the chromatographic system, then any process
(p) acting alone will produce a Gaussian curve having a variance
p
2

,
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Hence,
1
2
+ s
2
2
+ s
3
2
+........ + s
n
2
= s
c
2
4
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1
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where, (
c
2
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c
2
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) is the variance of the solute band as sensed by the detector.
The above equation is the algebraic enunciation of the principle of the
summation of variances and is fundamentally important. If the
individual dispersion processes that are taking place in a column can be
identified, and an expression for the variance arising from each
dispersion process evaluated, then the variance of the final band can be
calculated from the sum of all the individual variances. This is how the
Rate Theory provides an equation for the final variance of the peak
leaving the column.
The Alternative Axes of a Chromatogram
An elution curve of a chromatogram can be expressed using parameters
other than the volume flow of mobile phase as the independent variable.
The Plate theory provides an equation that expresses the retention and
standard deviation of a peak in terms volume flow of mobile phase.
However, instead of using milliliters of mobile phase, as the
independent variable, solute concentration in the mobile phase can be
related, time, or distance traveled by the solute band along the column
and proportionally the same chromatogram will be obtained. This is
illustrated in figure (1)
As the curves are describing the same chromatogram, by proportion,
the ratio of the variance to the square of the retention, in the respective
units in which the independent variables are defined, will all be equal.
Consequently,
v
2
V
r
2
x
2
l
2
t
2
t
r
2
where
v
,
x
and
t
are the standard deviations of the elution curves
when related to the volume flow of mobile
phase, the distance traveled by the solute along
the column and time, respectively.
and V
r
, l and t
r
refer to the retention volume, column length
and retention time, respectively.
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2
v
v
2
x
x
2
t
t
F l o w o f M o b i l e P h a s e
i n P l a t e V o l u m e s
R e t e n t i o n T i m e D i s t a n c e T r a v e l l e d
a l o n g C o l u m n
Figure 1 Alternative Axes of a Chromatogram
Now, from the Plate Theory (see book 6) it has been shown that,

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Thus,
v
2
V
r
( )
2
=
n v
m
+ Kv
s
( )
2
n
2
v
m
+ Kv
s
( )
2
=
s
x
2
l
2
10
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1
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and

Therefore,
l
n
x
2
l
The ratio,
(
l
n
)
, (the column length divided by the number of theoretical
plates in the column) has, for obvious reasons, become termed the
Height Equivalent to the Theoretical Plate (HETP) and has been given
the symbol (H). However, it is seen that (H) is numerically equal to,

,
which is, in fact, the variance per unit length of the column. Thus, the
function,

, is the variance that the Rate Theory will provide an explicit
equation to define and can be experimentally calculated for any column
from its length and column efficiency. It follows that the equations that
give a value for, (H), the variance per unit length of the column, have
been termed HETP equations.
To develop an HETP equation it is necessary to first identify the
dispersion processes that occur in a column and then determine the
variance that will result from each process per unit length of column.
The sum of all these variances will be (H), the Height of the
Theoretical Plate, or the total variance per unit column length. There
are a number of methods used to arrive at an expression for the
variance resulting from each dispersion process and these can be
obtained from the various references provided. However, as an
example, the Random-Walk Model introduced by Giddings (3) will be
employed here to illustrate the procedure. The theory of 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
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starting position and will form a Gaussian type distribution curve with
a variance of s
2
.
Now according to the random-walk model,

s p

(1)
Equation (1) can be used in a general way to determine the variance
resulting from the different dispersion processes that occur in an
chromatography column. The application of equation (1) is simple, the
problem that often arises is the identification of the average step and
sometimes the total number of steps associated with the particular
process being considered. As an illustration of its use it will be used to
the problem of obtain an expression for the radial dispersion of a
sample when it is placed on a packed column in the manner of Horne et
al. (5).

When a stream of mobile phase carrying a solute impinges upon a
particle, the stream divides and flows around the particle. Part of the
divided stream then joins other split streams from neighboring
particles, impinges on another and divides again. When a sample is
placed on the column at the center of the packing, initially it is in a
condition of non-radial equilibrium, but as a result of this process the
sample spreads across the column during passage through the column
and eventually achieves radial equilibrium (the concentration of solute
is constant across a cross section of the column. Early work in liquid
chromatography, used relatively low inlet pressures and, thus, samples
could be injected directly onto the column with a syringe through an
appropriate septum device as in gas chromatography. This method of
injection often resulted in radial equilibrium never being achieved by
the solutes before they were eluted. The introduction of the sample
valve, however, aids in establishing radial equilibrium early in the
separation but unless some special spreading device is employed at the
front of the column, it will not necessarily occur at the point of
injection. The stream splitting process is depicted in figure (2). If a
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particular molecule is considered passing round a particle, it will suffer
a lateral movement that can be seen to be given by,
Lateral Movement/Particle =
d
p
2
cos
d p
e
Figure 2. The Mechanism of Radial Dispersion
It follows, that the average lateral step will be,
d
p
2
cos
2
+
d
d
p
Employing the random walk function, the radial variance will be given
by:-
2
Number of Steps
( )
X Step Length
( )
2
(2)
Now assuming one lateral step is taken by a molecule for every
distance (jd
p
) that it moves axially, then, (n) the number of steps is
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given by:-
n =
l
jd
p

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where (l) is the distance traveled axially by the solute band.
Thus, substituting for (n) in equation (2),
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2
=
l
jd
p
d
p
p

2
=
ld
p
j p
2
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1
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In practice the value of (j) will lie between 0.5 and 1.0, but, for
simplicity the value of (j) will be taken as unity. This implies that one
lateral step will be taken by a given molecule for every step traveled
axially equivalent to one particle diameter .
Thus,

or,

(3)
Consider a sample injected precisely at the center of a 4 mm diameter
LC column. Employing equation (3) allows the distance traveled
axially by the solute band before the radial standard deviation of the
sample of solute is numerically equal to the column radius to be
calculated. That is, the band has now spread evenly across the column
and the solute is in radial equilibrium.

For the conditions given above
R
= 0.2.
Thus, substituting this value in equation (3),

or,

l
0 . 2 ( )
2
d
p
(4)
The distance that a solute band must pass along a column before a
sample, injected at the center of the packing, is evenly spread across its
diameter, can be calculated for columns packed with different sized
particles using equation (4). The results are shown as a graph relating
length against particle diameter in figure (3). The particle diameter
range normally employed in liquid chromatography is about 2-25
micron and so from figure 3, it is clear that radial equilibrium would
never be achieved for those column lengths commonly in use in LC.
Despite the lack of radial equilibrium, however, if the column packing
is completely homogeneous throughout the column length, then the
column efficiency should not be impaired. Unfortunately, ideal packing
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conditions are not always achieved and channeling often occurs, under
which circumstances lack of radial equilibrium could result in the
column efficiency being reduced with consequent loss in resolution. To
ensure radial equilibrium, it must either be achieved on injection (using
sample distribution device) or by employing narrow bore columns
where radial equilibrium is more quickly reached. The latter
alternative, however, will depend on the resolution required and the
nature of the sample.
0
5 0 0
1 0 0 0
1 5 0 0
2 0 0 0
2 5 0 0
C
o
l
u
m
n

L
e
n
g
t
h

T
r
a
v
e
r
s
e
d

b
y

S
o
l
u
t
e

(
c
m
)
0 1 0 2 0 3 0
P a r t i c l e D i a m e t e r ( m )
Figure 3. Graph of Column Length Traveled by the Solute Before
Radial Equilibrium is Achieved against Particle Diameter
Dispersion Processes that take Place in an LC Column
There are four basic dispersion processes that can occur in a packed
column that will account for the final band variance. They are,
Multipath dispersion, dispersion from Longitudinal Diffusion,
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dispersion from the Resistance to Mass Transfer in the Mobile Phase
and dispersion from the Resistance to Mass Transfer in the Stationary
Phase. All these processes are random and essentially non-interacting
and, therefore, provide individual contributions of variance that can be
summed to produce the final band variance.
The Multipath Process
In a packed column the solute molecules will describe a tortuous path
through the interstices between the particles and obviously some will
travel shorter paths than the average and some longer paths.
Consequently, some molecules will move ahead of the average and
some will lag behind thus causing band dispersion. The multipath
effect is illustrated in figure (4)
.
d L
Figure 4. Dispersion by the Multipath Effect
The Multipath effect can be applied to the Random Walk Model. The
average path length is equivalent to the mean diameter of the particle
(d
p
) and thus the number of steps will be equivalent to the column
length divided by the average step i.e.

.
Thus, applying equation (1),

or,

Dividing by the column length, (l), the variance per unit length or of
the multipath dispersion will be obtained and, thus, the multipath
contribution (H
M
) to the overall height of the theoretical plate (H),

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In fact, Van Deemter introduced a constant (2) to account for the
inhomogeneity of packing so his expression for the Multipath
contribution became,
H
M
2 d
p
For an ideally packed column (l) will be 0.5, and under which
circumstances the value fro (H
M
) reverts to,

.
Longitudinal Diffusion
If a local concentration of solute is placed at the midpoint of a tube
filled with either a liquid or a gas the solute will slowly diffuse to
either end of the tube. It will first produce a Gaussian distribution with
a maximum concentration at the center and, finally, when the solute
reaches the end of the tube, 'end' effects occur and the solute will
continue to diffuse until there is a constant concentration throughout
the length of the tube. The process is illustrated in Figure 5.
M o b i l e P h a s e
S a m p l e
Figure 5. Longitudinal Diffusion
Before dispersion due to longitudinal dispersion is discussed some
basic principles of diffusion need to be considered.
The Diffusion Process
Diffusion processes play important parts in peak dispersion. The
process not only contributes to dispersion directly (i.e., longitudinal
diffusion), but also helps to reduce the dispersion that results from
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solute transfer between the two phases. Consider the situation depicted
in figure 6.
d x
D
d c
d x
m
x
=
A
B
D
d c
d x
m
x + d x
=
+
D
d c
d x
( )
d
d x
d x
d c
d t
1 c m
1 c m
S a m p l e I n j e c t e d
x
D i f f u s i o n
C
Figure 6. The Diffusion Process
Consider a sample of solute is introduced in plane (A), (plane (A)
having unit cross-sectional area). Solute will diffuse according to
Fick's law in both directions ( x) and, at a point (x) from the sample
point, according, the mass of solute transported across unit area in unit
time (m
x
) according to Fick will be given by,

(5)
where (D
m
) is the Diffusivity of the solute in the fluid.
and

is the concentration gradient at (x).
Now, mass of solute leaving the slice (dx) thick, at (x+dx), i.e.,
(m
x+dx
), is,

Thus, the net change in mass per unit time in the slice (dx) thick will be

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or

Now as

,
then

or,
d c
d t
D
m
d
2
c
d x
2
(6)
Now, this is a standard differential equation and one solution to this
equation, which can be proved by appropriate differentiation, takes the
Gaussian form as follows:

Now, from the Plate Theory (see book 6),

,
where (n) is the variance of the Gaussian curve.
Now, (n) is the volume variance of the Gaussian curve (i.e.,

), then, by
comparison, (2D
m
t) 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 variance given by (2D
m
t).
Thus, if

, the solution of the equation is a Gaussian function, and, for
that equation,
2
2 D
m
t
(7)
Ordinary diffusion is the result of random molecular movement in first
one direction and then another and thus, resembles the Random Walk
Model. Uhlenbeck and Ornstein (8), derived the following expression
for the overall standard deviation () arising from diffusion process,

2 D
m
t ( )
0 . 5
where (t) is the time period over which the process occurs,
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and D
m
is the Diffusivity of the solute in the mobile phase.
Actually, (t) is the time the solute spends in the moving phase and thus,
is given by,

t
l
u
, where (l) and (u) is the length of the column and the
linear mobile phase velocity respectively.
Thus,

and

Therefore, dividing by l to obtain the variance per unit length,

2
l
H
L
2 D
m
u
In the same manner as the constant () introduced by Van Deemter into
the function for multipath dispersion, Van Deemter also introduced a
constant () into the Longitudinal Dispersion contribution to variance
to account for some packing inhomogeneity. As a consequence, the
expression for the Diffusion contribution to the variance per unit length
of the column became,
H
L
2 D
m
u
(8)
To be precise, there should be a second longitudinal diffusion
contribution to the overall variance that would arise from the
stationary phase. The same method of derivation can be used but the
time the solute spends in the stationary phase is now, is now a function
of the capacity ratio of the column, (k').
Thus,

where (t"
o
) is the kinetic dead time, (see book 6)
(k") is the kinetic capacity ratio.
The kinetic dead time and the kinetic capacity factors are calculated
from the kinetic dead volume as opposed to the thermodynamic dead
volume
Then from (7),

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where (D
s
) is now the solute Diffusivity in the stationary phase.
However, in this case, over the time period (t
r
), a fraction of time

is
spent by the solute in the stationary phase and, thus,

Now, again noting that

,

Noting, again that, (H
D(s)
), the contribution to the variance per unit
length, will be

. Then, the contribution to the total variance per unit
length for the column from longitudinal diffusion in the stationary
phase will be

i.e.,

. (9)
Introducing a packing factor the magnitude of which will depend on
the quality of the packing, the contribution to the variance per unit
length from diffusion in the stationary phase (H
L(S)
)is given by,
H
L ( S )
2
2
k ' D
S
u
where, D
S
is the Diffusivity of the solute in the stationary phase
The total contribution to (H) from longitudinal diffusion will thus be:-

or, H
L
2
1
D
m
u
1 + k '
( )
(10)
where,

It is seen from equation (10) that the longitudinal diffusion term is a
function of (k') the capacity factor of the solute. While this could be
significant in an LC capillary column systems, where the film of
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88
stationary phase could be continuous along the length of the column, it
will not be so in a packed column. The stationary phase in a packed
column is broken into segments between each particles and between
each pore in each particle so free continuous diffusion in the stationary
phase would be impossible. It follows that the longitudinal diffusion
term for packed columns should be independent of the k' of the solute
or, very nearly so, and in practice the effect of longitudinal diffusion in
the stationary phase is ignored.
The Resistance to Mass Transfer in The Mobile Phase
As a solute band progresses along a column, the solute molecules are
continually transferring from the mobile phase into the stationary phase
and back from the stationary phase into the mobile phase. This transfer
process is not instantaneous, because a finite time is required for the
molecules to traverse (by diffusion) through the mobile phase in order
to reach, and enter the stationary phase. Thus, those molecules close to
the stationary phase will enter it almost immediately, whereas those
molecules some distance away from the stationary phase will find their
way to it a significant interval of time later. However, as the mobile
phase is moving, during this time interval while they are diffusing
towards the stationary phase boundary, they will be swept along the
column and thus dispersed away from those molecules that were close
and entered it rapidly. The dispersion resulting from the resistance to
mass transfer in the mobile phase is depicted in figure 7.
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1 2
1 2 3 4
5 6
1 2 3 4 5 6
1 2
3
5
3 4
5 6
S t a t i o n a r y P h a s e
4
6
Figure 7. Resistance to Mas Transfer in the Mobile Phase
The diagram shows 6 solute molecules in the mobile phase and those
closest to the surface (1 and 2) enter the stationary phase immediately.
During the period, while molecules 3 and 4 diffuse through the mobile
phase to the interface, the mobile phase moves on. Thus, when
molecules 3 and 4 reach the interface they will enter the stationary
phase some distance ahead of the first two. Finally, while molecules 5
and 6 diffuse to the interface the mobile phase moves even further
down the column until molecules 5 and 6 enter the stationary phase
further ahead of molecules 3 and 4. Thus, the 6 molecules, originally
relatively close together, are now spread out in the stationary phase.
This explanation is a little over-simplified, but gives a correct
description of the mechanism of mass transfer dispersion.
The Resistance to Mass Transfer in the stationary Phase
The resistance to mass transfer in the Stationary phase is depicted in
figure 8.
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94
2 1
4 3 2 1
5 6
1 2 3 4
5 6
3 4 5 6

6 5 4 3 2 1
Figure 8. Resistance to Mass Transfer in the Stationary Phase
The dispersion resulting from the resistance to mass transfer in the
stationary phase can be described in the same way as that in the mobile
phase. Molecules close to the surface of the stationary phase, will leave
and enter the mobile phase before those that have diffused farther into
the stationary phase and, thus, have further to diffuse back to the
surface. Consequently, during the period required for the solute
molecules to diffuse to the stationary phase surface, those molecules
that were close to the surface will be swept along by the moving phase
and dispersed from those molecules still diffusing to the surface. In
figure 6, molecules 1 and 2, (the two closest to the surface) will enter
the mobile phase and begin moving with the mobile phase along the
column. This process will continue while molecules 3 and 4 diffuse to
the interface at which time they, also, will enter the mobile phase and
start following molecules 1 and 2 down the column. All four molecules
will continue their journey down the column while molecules 5 and 6
diffuse to the mobile phase/stationary phase interface. By the time
molecules 5 and 6 enter the mobile phase, the other four molecules will
have been smeared along the column and the original 6 molecules will
have suffered dispersion.
Resistance to Mass Transfer Dispersion
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Both the resistance to mass transfer in the mobile phase and that in the
stationary phase, can be treated quantitatively using the random walk
model. Recalling that if each molecule of a group takes a series of
steplike movements, (positive or negative) the direction being
completely random, then after (p) steps have been taken, each step
having an average 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
2
,
where

or

In the first instance, consider that the distribution is energy controlled
and not diffusion controlled, thus, a solute molecule will desorb from
the stationary phase when it randomly has sufficient kinetic energy to
break its association with a molecule of stationary phase (see book 1).
Similarly, a molecule will be absorbed under the same conditions.
If (k
d
) is the desorption rate constant then the mean desorption time
(t
d
) for the adsorbed molecule will be

. Correspondingly, if the
adsorption rate constant is (k
a
), then the mean adsorption time for a
free molecule in the mobile phase will be

.
Consider a peak moving down a column. During this migration
process, adsorption and desorption steps will constantly and frequently
occur and each occurrence will be a random event. Now a desorption
step will be a random movement forward as it releases a molecule into
the mobile phase. Conversely, an adsorption step will be a random
movement backward, as it is a period of immobility for the molecule
while it resides in the stationary phase and the rest of the zone moves
forward. The total number of random steps, taken as the solute mean
position moves a distance

along the column, is the number of forward
steps plus the number of backward steps. Now the distribution of the
solute is dynamic and is also an equilibrium system, consequently, each
desorption step must be followed by an adsorption step. It follows that
the total number of steps will be twice the number of adsorption steps
that take place in the migration period.
On average, a molecule will remain in the mobile phase a time (t
a
)
before it is adsorbed. During this time, it will be moving at the mean
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100
velocity of the mobile phase (u) and will, thus, move a distance (ut
a
).
Thus, in moving a distance

, the total number of adsorptions will be
and the total number of steps including the adsorption and desorption
steps will be

. It also follows, from the Random Walk Model that,

where

It is now necessary to determine the average step length (s) to obtain an
expression for (H).
The step length is that length moved by the molecule relative to that of
the zone center and, while the molecule has move (vt
a
) during time
(t
a
), the zone center has also moved. Now, it was shown in the Plate
theory that the zone velocity is

where (k") is the dynamic capacity
ratio of the solute.
Consequently,

.
and,

,
i.e.,

In practice, it is more convenient to express (H) in terms of (t
d
) as
opposed to (t
a
). The ratio of the mean phase residence times is the time
the solute spends in the mobile phase divided by the time spent in the
stationary phase,
Thus,

and H
R M T
2 ( k " )
2
1 + k " ( )
2

_
,

u
t
d
k "
2 k "
1 + k " ( )
2
u t
d
(11)
Equation (11), is derived from the approximate random walk theory,
however, it is rigorously correct and applies to heterogeneous surfaces
containing wide variations in properties as well as to perfectly uniform
surfaces. It can also be used as the starting point for the random walk
treatment of diffusion controlled mass transfer similar to that which
takes place in the stationary phase in GC and LC columns.
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Diffusion Controlled Dispersion in the Stationary Phase
The difference between diffusion controlled dispersion and dispersion
resulting from adsorption and desorption processes is that the transfer
process is concentration controlled. Reiterating equation (7),

.
Thus, during solute transfer between the phases, (t) is now the average
diffusion time (t
D
) and () is the mean distance through which the
solute diffuses, i.e., the depth or thickness of the film of stationary
phase (d
f
).
Thus,

or

(12)
where (D
S
) is the Diffusivity of the solute in the stationary phase.
Substituting (t
D
) for (t
d
) from (12) in (11),
H
M T S
q k "
1 + k " ( )
2
d
f
2
D
S
u (13)
where (q) is a configuration factor.
The constant (q) accounts for the precise shape of the 'pool' of
stationary phase which, for a uniformly coated GC capillary column, (q
= 2/3). Diffusion in 'rod' shaped and 'sphere' shaped bodies, (e.g.,
paper chromatography and LC) (q=1/2 and 2/15), respectively (7).
For a GC capillary column,

(14)
and a close approximation for an LC or GC packed column, (H
MTS
)
would be given by
H
M T S
2 k "
1 5 1 + k " ( )
2
d
f
2
D
S
u . (15)
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Diffusion Controlled Dispersion in the Mobile Phase
Dispersion processes in the mobile phase will also be diffusion
controlled, thus, again reiterating equation (7),

While in the mobile phase a solute molecule must traverse from
localities of high velocity (near the center of a capillary column or the
center of an inter-particle channel) to that of low velocity (the interface
between the two phases at the capillary column walls or, in the packed
column, the surface of the particles). Let the "exchange time' between
the two extreme velocities be (t
m
). Now, the distance between the
extremes of velocity will depend on the geometry of the column
system, but in general it can be assumed a molecule must diffuse a
distance (
m
d
m
) to move from one velocity extreme to the other.
Depending on the column (tubular or packed), and on the homogeneity
of the packing, (particle size and shape) the value of (
m
) may range
widely from much less than unity to significantly greater than unity.
Now, from equation (7),
(=
m
d
p
) and (t=t
m
)
Thus,

or t
m
m
2
2 D
m
d
p
2
. (16)
Now, in the equation from the Random walk concept,

or

In addition, = t
m
u and

or

. (17)
Substituting for (t
m
) from (16) in (17)

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Now,

Thus,

H
M T M
2
l
m
2
2 D
m
d
p
2
u (18)
Equation (21) applies to all types of columns each requiring a different
constant (
m
) which is partly determined by the geometry of the
distribution system and partly by the capacity ratio of the solute. A
function for (
m
) has not been developed for packed LC or GC
columns, but due to the geometric simplicity Golay (8) was able to
develop the function for the capillary column ,viz.

and thus, for a capillary column,

H
M T M
1 + 6 k " + 1 1 k "
2
2 4 1 + k "
2

_
,
2
r
2
2 D
m
u
. (19)
The argument used to develop the function describing (t
m
) for a
capillary column is similar to that for the packed column but (r), the
column radius, replaces (dp) the particle diameter.
Due to the varying physical nature of the different packings, it appears
column, but it was suggested by Klinkenberg and Purnell that as no one
has developed a specific function for (

) for a packed columns,
that the function,

(developed by Golay for the capillary column) could also be used for
packed GC and LC columns. However, in a packed column. the flow
patterns in interstices between the particles is very complex and the
eddies and pseudo turbulence that are generated between the particles
greatly increases the effective diffusivity of the solute in the mobile
phase. In fact, the magnitude of equation (18) can be so reduced by the
large increase in (D
m
) that the overall contribution to the peak
dispersion can become small enough to be ignored.
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Summarizing,, the rate theory provides the following equations that
describe the variance per unit length (H) for four different columns.
1. The Open Tubular GC Column,

(20)
2. The Packed GC Column

(21)
This equation is basically that derived by Van Deemter et al. in 1956.
3. The Packed LC Column

(22)
4. The Open Tubular LC Column

(23)
It should be noted that all the equations assume that the mobile phase
is incompressible which will not be true for equations (23) and (24). It
follows that equations (23) and (24) will require modification in order
to be applicable to practical situations.
Effect of Mobile Phase Compressibility On the HETP Equation for a
Packed GC Column
As the pressure falls along the column length, the velocity changes
and, as the solute diffusivity depends on the pressure, the diffusivity of
the solute will also change. The multi-path term, which contains no
velocity or gas pressure dependent parameters, will be unaffected and
the expression that describes it the same. The other terms in the HETP
equation, however, all contain parameters that are affected by gas
pressure (solute diffusivity and mobile phase velocity) and, therefore,
need to be modified to accommodate the compressibility of the mobile
phase.
Reiterating the HETP equation for a packed column,
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115

where f
1
(k") =

and f
2
(k") =

Consider a point (x) along the column,

The HETP equation, as derived by Van Deemter, is seen to apply only
to a particular point distance (x) from the inlet of the column where the
pressure is constant.
Now, applying the gas laws
P
x
u
x
= P
o
u
o
or

where (P
x
) is the pressure at point (x) along the column,
(u
x
) is the linear velocity of the mobile phase at point (x),
(P
o
) is the pressure at the column exit,
and (u
o
) is the linear velocity of the mobile phase at the column
exit.
Now from the kinetic theory of gases, it can be shown that the
diffusivity of a solute in a gas is inversely proportional to the pressure.
Thus, D
x
P
x
= D
o
P
o

or

where (D
o
) is the solute diffusivity at the end of the column at (P
o
)
and (D
x
) is the solute diffusivity at point (x) and pressure (P
x
)
Thus,

and

Substituting for

and

in the HETP equation,

H
x
2 d
p
+
2 D
m ( o )
u
o
+
f
1
( k " ) d
p
2
D
m ( o )
u
o
+
f
2
( k " ) d
f
2
P
0
D
S
P
x
u
o
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118
118
It is now seen that if the mobile phase velocity is taken as that at the
column outlet, only the resistance to the mass transfer term for the
stationary phase is position dependent. All the other terms can be used
as developed by Van Deemter, providing the diffusivities are also
measured at the outlet pressure (atmospheric).
The resistance to the mass transfer term for the stationary phase must
be considered in isolation. The experimentally observed plate height
(variance per unit length) resulting from a particular dispersion process
[e.g., (h
s
), the resistance to mass transfer in the stationary phase] will
be the sum of the local plate height contributions (h'); i.e.,

Consequently, substituting for (h') the expression for the resistance to
mass transfer in the stationary phase will be,

or

(24)
Now, it can be shown that, (see equation 23 Book 6),

or

(25)
Substituting for (P
x
) from equation (25) in equation (24),

(26)
Let w =

Then

or

Furthermore, when x=0, then

and when w = L, then

.
Substituting for

and (dx) in equation (26) and inserting the new limits
and integrating,
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121

or

Thus,

(27)
Thus, the complete HETP equation for a packed GC column, that takes
into account the compressibility of the carrier gas, will be

H 2 d
p
+
2 D
m ( o )
u
o
+
f
1
( k " ) d
p
2
D
m ( o )
u
o
+ 2
f
2
( k " ) d
f
2
D
S
+ 1 ( )
u
o
(28)
Now from D'Arcy's Law

or

Thus,

Integrating from x=0 to x = L and P
x
= P
i
to P
o
,

or

Solving for (),

(29)
Substituting for () in equation (27) from equation (29),

Thus the HETP equation given by equation (28) becomes
H 2 d
p
+
2 D
m ( o )
u
o
+
f
1
( k " ) d
p
2
D
m ( o )
u
o
+ 2
f
2
( k " ) d
f
2
D
S
u
0
L
K P
o
+ 1

_
,

0 . 5
+ 1

_
,

u
o
(30)
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124
Equation (30) gives the variance per unit length of a GC column in
terms of the outlet pressure (atmospheric); the outlet velocity; and
physical and physicochemical properties of the column, packing, and
phases and is independent of the inlet pressure. However, equation (28)
is the recommended form for HETP measurements as the inlet pressure
of a column is usually known, (and consequently (), the inlet/outlet
pressure ratio is also known) and the equation is less complex and
easier to use. The important aspect of this development is that the
resistance to mass transfer in the stationary phase is seen to be a
function of the inlet-outlet pressure ratio ().
Regrettably, the average velocity is the variable that is almost
universally used in constructing HETP curves in both GC and LC. This
is largely because it is simple to calculate from the ratio of the column
length to the dead time. Unfortunately, in GC, the use of the average
velocity provides very erroneous data and, for accurate column
evaluation and column design, the exit velocity must be employed
together in conjunction with the inlet-outlet pressure ratio.
An example of the errors that can occur from the use of the average
velocity, as opposed to the exit velocity, is shown in figure 9 from data
obtained for a capillary column.
H E T P C u r v e E m p l o y i n g
t h e E x i t V e l o c i t y
H E T P C u r v e E m p l o y i n g
t h e A v e r a g e V e l o c i t y
M o b i l e P h a s e V e l o c i t y ( c m / s e c . )
P
l
a
t
e

H
e
i
g
h
t
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127
Figure 9. HETP Curves for the Same Column and Solute Using the
Average Mobile Phase Velocity and the Exit Velocity
The two curves are clearly quite different and, if the results are to be
fitted to the HETP equation, only the data obtained using the exit
velocity will give meaningful values for the exclusive dispersion
processes. This problem is further emphasized in the graphs shown in
figure 10. In figure 10, the individual contributions from the different
dispersion processes are obtained by deconvoluting the HETP curve
obtained using the average velocity data.
It is seen that using the average velocity data, the extracted value for
the multi-path term is negative, which is physically impossible (for a
capillary column should be zero or very close to zero). In contrast, the
values obtained from data involving the exit velocity give small
positive, but realistic values for the multi-path term.
In all aspects of column evaluation and column design in GC, the
compressibility of the mobile phase must be taken into account or
serious errors will be incurred.
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130

L o n g i t u d i n a l D i f f u s i o n B / u
H E T P C u r v e ( H )
R e s i s t a n c e t o
M a s s T r a n s f e r C u
0
M u l t i - p a t h T e r m A
A v e r a g e V e l o c i t y ( c m / s e c . )
H

(
c
m
)
Figure 10. De-Convolution of the HETP Curve Obtained Using the
Average Mobile Phase Velocity
The Van Deemter Equation
The Van Deemter equation (9) was derived as long ago as 1956 and
was the first rate equation to be developed. There are, however, a
number of alternative rate equations that have been reported, but when
subjected to experimental test, the Van Deemter equation has been
shown to be the most appropriate equation for the accurate prediction
of dispersion in chromatographic systems. The Van Deemter equation
is particularly pertinent at mobile phase velocities around the optimum
velocity (a concept that will shortly be explained). Consequently, as all
columns should be operated at, or close to, the optimum velocity for
maximum efficiency, the Van Deemter equation is particularly
important in column design. Restating the Van Deemter equation,

where f
1
(k") =

and f
2
(k") =

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133
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
2 D
m
u
1+ k' ( ) , was
replaced by,
2 D
m
u
. 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,

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,

The form taken by f
2
(k') was considered by Van Deemter to be,

and thus, the complete HETP equation became,

(31)
Equation (31), however, was developed for a GC column and in the
case of an LC column, the resistance to mass transfer in the mobile
phase should be included. Van Deemter et al. did not derive an
expression for f
1
(k') for the mobile phase but Purnell (10) suggested
that the function of (k'), employed by Golay (8) for the resistance to
mass transfer in the mobile phase in his rate equation for capillary
40
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136
columns, would also be appropriate for a packed column. The form of
f
1
(k') derived by Golay was as follows,

Thus, Van Deemter's equation for LC becomes,

(32)
Equation (32 ) can put in a simplified form as follows,

(33)
where, A=2 d
p
, B=2 D
m
and

Equation (33) is a hyperbolic function which has a minimum value of
(H) for a particular value of (u). Thus, a maximum efficiency will
obtained at a particular linear mobile phase velocity.
An example of an HETP curve obtained in practice showing this
hyperbolic relationship is given in figure 11.

-0.000 0.100 0.200 0.300 0.400 0.500 0.600
u ( c m / s e c )
-0.000
0.001
0.002
0.003
C u r v e F i t
M u l t i p a t h T e r m
R e s i s t a n c e t o
M a s s T r a n s f e r
L o n g i t u d i n a l
D i f f u s i o n
41
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139
Figure 11. HETP Curve for Hexamethylbenzene
The HETP curve is the result of a curve fitting procedure to the
experimental points shown. The column was 25 cm long, 9 mm in
diameter and packed with 8.5 micron (nominal 10 micron) Partisil
silica gel. The mobile phase was a solution of 4.8%w/v ethyl acetate in
n-decane. The hyperbolic form of the curve is confirmed, the minimum
is clearly indicated and the fit of the points to the curve is good. From
the curve fitting procedure the values of the Van Deemter constants
could be determined and the separate contributions to the curve from
the multipath dispersion, longitudinal dispersion and the resistance to
mass transfer calculated and included in the figure.
It is seen that the major contribution to dispersion at the optimum
velocity (where the value of (H) is a minimum) is the multipath effect.
Only at much lower velocities, does the longitudinal diffusion effect
become significant. Conversely, the mobile phase velocity must be
increased to about 0.2 cm/sec before the dispersion due to the
resistance to mass transfer begins to become relatively significant
(compared to that of the multipath effect).
The values for the Van Deemter constants were found to be,
A=0.00117
B=0.0000175 cm
2
/sec
and C=0.00250 sec.
If the mean particle size was 0.00085 cm, then as,

A 2 d
p
Then, 0.00117 = 2 0.00085 or, = 0.69
Giddings (11) determined theoretically that, for a well packed column
() should take a value of about 0.5 and thus the column used was
reasonably well packed.
In a similar manner, as B = 2D
m
Then, 0.0000175 = 2gD
m

42
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39
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142
Katz et al (12) determined the diffusivity of hexamethylbenzene in
4.83%w/v ethyl acetate in n-decane and found it to be 1.17x10
-5
cm
2
/sec,
Consequently, = 0.747
Giddings (11) also determined that, for a well packed column, ()
should be about 0.6 so again the dispersion from longitudinal diffusion
as measured. confirms that the column was reasonably well packed.
For a packed column, the particle size has a profound effect on the
minimum value of the HETP of a column and thus the maximum
efficiency attainable. It would also indicate that the highest column
efficiency would be obtained from the smallest particles. However, this
assumes that an unlimited pressure is available and the apparatus can
tolerate such pressures. Within practical limits of pressure, the smaller
the particle diameter, the smaller will be the minimum HETP and thus,
the larger the number of plates per unit length obtainable from the
column. However, the total number of theoretical plates that can be
obtained, will depend on the length of the column which, in turn, must
take into account the available inlet pressure.
The optimum mobile phase velocity can be obtained by differentiating
equation (33) with respect to (u) and equating to zero, thus,

and

Equating to zero
dH
du
0 and consequently,
B
u
2
+ C 0
Thus,

(34)
Substituting for (B) and (C),

and letting D
s
= D
m
,
43
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145

(35)
It is seen from equation (35) that the optimum velocity is, directly
proportional to the diffusivity of the solute in the mobile phase. To a
lesser extent it also appears to be inversely dependent on the particle
diameter of the packing and the film thickness of the stationary phase.
The film thickness of the stationary phase is determined by the physical
form of the packing, that is, in the case of silica gel, the nature of the
surface and in the case of a reverse phase, on the bonding chemistry.
Now, if it is assumed that d
f
<< d
p
(which in practice will always be
true) and () is close to zero (i.e. the diffusivities of the solute in the
two phases is about the same) which for liquid chromatography will
also be true, then,

u
o p t
D
m
d
p
4 8 1 + k ' ( )
2
1 + 6 k ' + 1 1 k '
2
( )

1
]
1
1
1
0 . 5

Furthermore, when k'>> 1, that is, for well retained peaks, and taking
() as 0.6

u
o p t
D
m
d
p
4 . 4 2 [ ]
0 . 5
2 . 1 D
m
d
p

1 . 6 3 D
m
d
p
(36).
Under these circumstances, it is seen that the optimum velocity is
directly proportional to the solute diffusivity in the mobile phase and
inversely proportional to the particle diameter of the packing. The
quality of the packing, also plays some part, but to a very less
significant extent. It is now possible to determine the factors that
control the magnitude of H
min
. Substituting the function for u
opt
from
equation (34) in equation (33) an expression for H
min
is obtained.

and

(37)
Substituting for A, B, and C,

(38)
44
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148
Noting that D
s
= D
m
, and simplifying,

(39)
Again, assuming that, d
f
<< d
p
, and k'>> 1, that is for well retained
peaks,

Bearing in mind the values of () and () for a well packed column are
0.5 and 0.6 respectively,
H
min.
= 1.48d
p
Thus, the approximate value of H
min,
for a well retained solute eluted
from a well packed column and operated at the optimum linear mobile
phase velocity, can be expected to be about 1.48d
p.
Furthermore, to the
first approximation, this value will be independent of the nature of the
solute, mobile phase or stationary phase. For the accurate design of the
optimum columns for a particular separation, however, this
approximation should, in general, not be made, nevertheless, the value
of 1.48 for H
min
is a useful guide for assessing the quality of a column.
From d'Arcy's Law for fluid flow through a packed bed, at the optimum
mobile phase velocity the length of the column is given by,
l
P d
p
2
u
o p t .
where (P) is the inlet pressure to the column,
() is the viscosity of the mobile phase,
() is the d'Arcy's Constant.
Now, l = nH
min
, thus, substituting for l, and rearranging,

. (40)
Substituting for u
opt
and H
min
,

(41)

(42)
45
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151
or, n
P d
p
2
2 . 4 D
m
(43)
It is seen from equation (43) that, if an LC column is operated at its
optimum linear velocity, the maximum efficiency obtainable for well
retained peaks will be directly proportional to the inlet pressure
available (P) and the square of the particle diameter of the packing.
Thus, the larger the particle diameter, the greater efficiency attainable
at a given pressure. This is because, as the particle diameter is
increased the column permeability is also increased allowing a longer
column to be used. The permeability increases as the square of the
particle diameter but the variance per unit length only increases
linearly with the particle diameter. Thus, doubling the particle diameter
will allow a column four times the length to be used but the number of
plates per unit length will be halved. Consequently, the column
efficiency will be increased by a factor of two. It is also seen that the
higher efficiencies will be obtained with mobile phases of low
viscosity and for solutes of low diffusivity. Solvent viscosity and solute
diffusivity tend to be inversely proportional to each other and so the
sensitivity of the maximum obtainable efficiency to either solvent
viscosity or solute diffusivity will generally not be large. The
approximate length of a column that will provide the maximum column
efficiency when operated at optimum velocity is given by, l = nH
min.
Thus,

0 . 6 2 P d
p
3
D
m
(44)
It is seen that the column length varies inversely as the product of the
solute diffusivity in the mobile phase and the mobile phase viscosity in
much the same way as the column efficiency does when operating at
the optimum velocity. As would be expected the column length is
directly proportional to the inlet pressure but, less obviously is also
proportional to the cube of the particle diameter.
The analysis time for a solute mixture in which the last peak is eluted at
a capacity ratio of k'
F
is given by,
46
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154

t (1 + k'
F
)t
0
(1 + k'
F
)
l
u
opt
Substituting for (u
opt
) and (l) from equations (36) and (44),

or, t ( 1 + k '
F
)
0 . 4 9 P d
p
4
D
m
2

_
,

(45)
It is seen from equation (45) that the analysis time is proportional to the
fourth power of the particle diameter and inversely proportional to the
square of the diffusivity in the mobile phase. In a similar manner to
column length, the analysis time is also directly proportional to the
applied inlet pressure and inversely proportional to the mobile phase
viscosity.
Summarizing, if a column is operated at its optimum velocity and the
solute concerned is eluted at a relatively high k' value, and assuming
the film thickness of the stationary phase is small compared with the
particle diameter (a condition that is met in almost all LC separations)
then,

u
o p t
1 . 2 6 D
m
d
p
(36)
H
min
. 1.48dp (46)
n
P d
p
2
2 . 4 D
m
(43)
l
0 . 6 1 7 P d
p
3
D
m
(44)
t (1+ k'
F
)
0 .38 Pd
p
4
D
m
2

_
,

(45)
47
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As already stated, these equations are insufficiently precise to be used
for accurate column design but, they can give a general indication of
the more important performance specifications that could be expected
from an approximately optimized chromatographic system.
It would be of interest to use the equations to calculate the maximum
efficiency, column length and analysis time that would be obtained
from columns packed with particles of different diameter under
conditions that commonly occur in LC analyses.
The diffusivity of solutes having molecular weights ranging from about
60 to 600 vary from about 1x10
-5
to 4x10
-5
cm
2
/sec.(13) Thus, an
average value of 2x10
-5
cm
2
/sec will be taken in the following
calculations. In a similar way a typical viscosity value for the mobile
phase will be assumed as that for acetonitrile (14), i.e. 0.375x10
-2
poises. The inlet pressure taken will be 3,000 p.s.i. or about 200
atmospheres. Many LC pumps available today will operate at 6,000
p.s.i. or even 10,000 p.s.i., however, it is not the pump that determines
the average operating pressure of the chromatograph, but the sample
valve.
Sample valves can, for a limited time, operate very satisfactorily at
very high pressures but their lifetime at maximum pressure is
significantly reduced. Most valves, designed for high pressure
operation will have extensive lifetimes when operated at 3,000 p.s.i.
and so this is the pressure that will be employed in the using the above
equations. The value assumed for the d'Arcy constant,() is 35 when
(P) is measured in p.s.i. and has been determined experimentally (14).
The capacity factor of the last eluted peak was taken as 5 for
calculating the elution time. Employing the above values, equation (16)
was used to calculate maximum efficiency attainable for columns
packed with particles of different diameters. The results obtained are
shown in figure 12. 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..
48
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159
160
160

0 10
20 30
3
4
5
6
7
P a r t i c l e D i a m e t e r ( m i c r o n )
Figure 12. Graph of Log Maximum Efficiency against Particle
Diameter
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 inlet pressure to some extent, but ultimately
the pressure will be limited and the effect of particle diameter will be
the same but at higher efficiency levels. The column lengths necessary
to achieve these efficiencies can be calculated employing equation
(44). The results obtained are shown as curves relating maximum
column length to particle diameter in figure 13.
It is seen from figure 3 that the column length ranges from just under a
centimeter, which provides an efficiency of about 3500 theoretical
plates to nearly 70 meters which provides an efficiency nearly 1.5
million theoretical plates.
49
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163
0 10 20 30
-1
0
1
2
3
4
Figure 13. Graph of Log. Column Length for Maximum Efficiency
against Particle Diameter
Seventy meters is a long column, but not an impractical length. The
question remains is how long will the separation take?
0 10 20 30
-1
0
1
2
3
4
5
Figure 14. Graph of Log. Elution Time against Particle Diameter
50
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166
166
The time taken to achieve these efficiencies when eluting the last peak
at a k' value of 10 can be calculated employing equation (45). The
results obtained are shown in figure 4 where the elution time obtained
from columns of maximum efficiency are plotted against particle
diameter.
On examination of the curve in figure 14, the problem associated with
high efficiencies becomes apparent. The elution time for the short
column having about 3500 theoretical plates is only just about one half
minute. The elution time from the 1.5 million plate column, however, is
about 54 days, a rather long time to wait for a chromatographic
separation. It is also seen that the higher the efficiencies that are
required (the more difficult the separation problem) the longer the
separation time and this is inevitable as a result of practical limits to
the column inlet pressure.
Alternative Equations for Peak Dispersion
The Van Deemter equation remained unquestioned as the established
equation for describing the peak dispersion that took place in a packed
column until about 1961. However, as column performance was
improved, it was found that when experimental data was fitted to the
Van Deemter equation there was often very poor agreement between
theory and experiment (particularly for data measured at high linear
mobile phase velocities).
In retrospect, this poor agreement between theory and experiment
appeared to be due largely to the presence of experimental artifacts
(such as those caused by extra column dispersion, large detector sensor
and detector electronic time constants etc.) than any inadequacies of
the Van Deemter equation. Nevertheless, it was the poor agreement
between theory and experiment at the time, that provoked a number of
workers in the field to develop alternative HETP equations. This work
was carried out in the hope that a more exact relationship between
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169
HETP and linear mobile phase velocity could be obtained that would
be compatible with experimental data.
The Giddings Equation
In 1961, Giddings (16) developed an HETP equation of which the Van
Deemter equation was shown to be a special case. Giddings work was
not provoked by poor agreement between theory and experiment but
because he was dissatisfied with the Van Deemter equation inasmuch
that it predicted a finite contribution to dispersion, independent of the
solute diffusivity, in the limit of zero mobile phase velocity. This
concept, not surprisingly, appeared to him unreasonable and
unacceptable. Giddings developed the following equation to avoid this
irregularity.

H
A
1 +
E
u
+
B
u
+ C u
(46)
It is seen that when u >> E, equation (46) reduces to the Van Deemter
equation,

It is also seen that at very low velocities, where u << E, the first term
tends to zero, thus meeting the requirements that there is no multipath
dispersion at zero mobile phase velocity. Giddings also suggested that
there was a coupling term that accounted for an increase in the
'effective diffusion' of the solute between the particles. The increased
'diffusion' resulted from the tortuous path followed by the molecules as
they twisted and turned through the interstices of the packing. This
process was considered to produced a form of microscopic turbulence
that induced extremely rapid transfer of solute in the inter particulate
spaces. However, again at velocities where u >> E , this mixing effect
could be considered complete and the resistance to mass transfer in the
mobile phase between the particles becomes very small and the
equation again reduces to the Van Deemter equation.
However, on consideration there is a difference between the Giddings
equation and that of Van Deemter as the C term in the Van Deemter
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37
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172
equation would now only describe the resistance to mass transfer in the
mobile phase contained in the pores of the particles, and thus, would
constitute an additional resistance to mass transfer in the stationary
(static mobile) phase. This concept has some indirect experimental
support in the development of the form of f
1
(k') from experimental data
which will be discussed later. The form of f
1
(k') is shown to be closer
to the original form given by Van Deemter for f
2
(k') that is appropriate
for the resistance to mass transfer in the stationary phase. It is not
known for certain, but it is possible and likely, that this was the reason
why Van Deemter et al. did not include a resistance to mass transfer
term for the mobile phase in their original form of the equation.
The Huber Equation
The next HETP equation to be developed was that of Huber and
Hulsman in 1967 (17). These authors introduced a modified multipath
term somewhat similar in form to that of Giddings and a separate term
describing the resistance to mass transfer in the mobile phase contained
between the particles. The form of their equation was as follows:-

H
A
1 +
E
u
1 2
+
B
u
+ C u + D u
1 2
(47)
It is seen that the first term differs from that in the Giddings equation,
in that it now contains the mobile phase velocity to the power of one
half. Nevertheless, again when u
1/2
>> E, the first term reduces to a
constant similar to the Van Deemter equation. The additional term for
the resistance to mass transfer in the mobile phase is an attempt to take
into account the 'turbulent mixing' that takes place between the
particles. Huber's equation implies (but, in fact, was not explicitly
stated by the authors) that the mixing effect between the particles (that
reduces the magnitude of the resistance to mass transfer in the mobile
phase) does not commence until the mobile phase velocity approaches
the optimum velocity (as defined by the Van Deemter equation).
Furthermore, it is not complete until the mobile phase velocity is well
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175
above the optimum velocity. Thus, the shape of the HETP/u curve will
be a little different from that predicted by the Van Deemter equation.
The form of the HETP curve that is produced by the Huber equation is
shown in figure 15.
0.0
0.2
0. 4 0. 6
0. 8
L i n e a r V e l o c i t y ( c m / s e c )
0 . 0 1 2
0 . 0 1 0
0 . 0 0 8
0 . 0 0 6
0 . 0 0 4
0 . 0 0 2
0 . 0
C o m p o s i t e C u r v e
M a s s T r a n f e r i n t h e M o b i l e P h a s e
M a s s T r a n f e r i n t h e S t a t i o n a r y P h a s e
C o u p l i n g T e r m
L o n g i t u d i n a l D i f f u s i o n

Figure 15. H versus U Curves for the Huber Equation
It is seen that the composite curve obtained from the Huber equation is
indeed similar to that obtained from that of Van Deemter but the
individual contributions to the overall variance are different. The
contributions from the resistance to mass transfer in the mobile phase
and longitudinal diffusion are common to both equations. However, the
(A) term from the Huber equation increases with mobile phase flow-
rate and only becomes a constant value, similar to the multipath term in
the Van Deemter equation, when the mobile velocity is sufficiently
large. In practice, however, it would seem that the magnitude of the
mobile velocity where the (A) term gives a constant value, is quite low,
relative to the normal range of operating velocities employed in
practical LC. The portion of the composite curve shown at the higher
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178
velocities is not quite linear due to the non-linear form of the term for
the resistance to mass transfer in the mobile phase and this becomes
more apparent at higher mobile phase velocities. At, and around the
optimum velocity, however, the form of the two curves differ only
slightly.
The Knox Equation
During 1972 and 1973 Knox and his co-workers (18), (19), and (20)
carried out a considerable amount of work on different packing
materials with particular reference to the effect of particle size on the
reduced plate height of a column. The concept of reduced plate height
(h ) and reduced velocity () was introduced by Giddings (21) and (22)
in 1965 in an attempt to form a basis for the comparison of different
columns packed with particles of different diameter. The reduced plate
height is defined as,

(48)
In fact, the reduced plate height merely measures the normal plate
height in units of particle diameters. It is also seen that the reduced
plate height is dimensionless.
The reduced velocity is defined as,

(49)
The reduced velocity compares the mobile phase velocity with the
velocity of the solute diffusion through the pores of the particle. In fact,
the mobile phase velocity is measured in units of the intraparticle
diffusion velocity. As the reduced velocity is a ratio of velocities, like
the reduced plate height, it also is dimensionless.
Employing the reduced parameters the equation of Knox takes the
following form,
h
B
+ A
1 3
+ C (50)
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It should be noted that the constants of the equation were arrived at by
a curve fitting procedure and not derived theoretically from a basic
dispersion model; as a consequence the Knox equation has limited use
in column design. It is, however, extremely valuable in accessing the
quality of the packing. This can be seen from the diagram shown in
figure 16.
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Well Packed
Poorly Packed
L o g . R e d u c e d V e l o c i t y
- 1 . 5
- 0 . 5 0 . 5 1 . 5 2 . 5
Figure 16. Graph of Log. Reduced Plate height against Log.
Reduced Velocity for Poor and Well Packed Columns
The curves represent a plot of Log.(h ),(Reduced Plate height)against
Log.( ), (Reduced Velocity). The lower the Log.(h ) versus the Log.(
) curve the better the column is packed. At low velocities the (B)
term dominates and at high velocities the (C) term dominates as in the
Van Deemter equation. The best column efficiency is achieved when
the minimum is about 2 particle diameters and thus, Log (h ) is about
0.35. The minimum value for (H) as predicted by the Van Deemter
equation has also been shown to be about two particle diameters. The
optimum reduced velocity is in the range of 3 to 5 that is Log.() takes
values between 0.3 and 0.5. The Knox equation is a simple and
effective method of examining the quality of a given column but, as
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stated before, is not nearly so useful in column design due to the
empirical nature of the constants.

The Horvath and Lin Equation
In (1976) Horvath and Lin (23) introduced yet another equation to
describe the value of (H) as a function of the linear mobile phase
velocity (u). Their equation is given as follows,

H
A
1 +
E
u
1 3
+
B
u
+ C u + D u
2 3
(51)
The equation of Horvath and Lin was very similar to that of Huber and
Hulsman and, in fact, only differed in the magnitude of the power
function of (u) in their (A) and (D) terms. These workers were also
trying to address the problem of a zero (A) term at zero velocity and
the fact that some form of "turbulence' between particles aided in the
solute transfer across the voids between the particles.
The Golay Equation
The basic equation describing the dispersion that takes place in an open
tubular column was developed by Golay (8) for GC but is equally, and
directly, applicable to LC. The Golay equation differs in one important
aspect from the equations for packed columns in that, as there is no
packing, there can be no multipath term or coupling factor and thus,
contains only two functions. One function describes the longitudinal
diffusion effect and the other the combined resistance to mass transfer
terms for the mobile and stationary phases. This is the fundamental
difference between the two types of column. The variance from a
packed column is largely determined by the magnitude of the particle
diameter, in contrast, the variance obtained from a capillary or open
tubular column is determined by the magnitude of the radius. The
Golay equation takes the following form:-
H
2 D
m
u
+
1 + 6 k ' + 1 1 k '
2
( )
r
2
2 4 1 + k ' ( )
2
D
m
u +
k '
3
r
2
6 1 + k ' ( )
2
K
2
D
s
u (52)
Where (H) is the variance per unit length of the column for the given
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solute,
(k)' is the capacity factor of the solute,
(K) is the solute distribution coefficient between the two phases,
(D
M)
is the diffusivity of the solute in the mobile phase,
(D
S)
is the diffusivity of the solute in the stationary phase,
(r) is the radius of the column,
and (u) is the linear velocity of the mobile phase.
If the solute is unretained (i.e. k'=0 ) then the Golay equation
reduces to,

(53)
0.00 0.01 0.02 0.03 0.04
0.00
0.01
0.02
0.03
0.04
0.05
0.06
L i n e a r V e l o c i t y ( c m / S e c )
C o m p o s i t e C u r v e
R e i s t a n c e t o M a s s T r a n s f e r
L o n g i t u d i n a l D i f f u s i o n
Figure 17. Graph of H against U for an Uncoated Capillary
Column
Taking a value of 2.5 x10
-5
for D
m
(the diffusivity of benzyl acetate in
n-heptane) equation (52) can be employed to calculate the curve
relating (H) and (u) for an uncoated capillary tube. The results are
shown in figure 17. It is seen that the Golay equation produces a curve
identical to the Van Deemter equation but with no contribution from a
multipath term. It is also seen that the value of (H) is solely dependent
on the diffusivity of the solute in the mobile phase and the linear
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mobile phase velocity. It is clear that the capillary column can,
therefore, provide a simple means of determining the diffusivity of a
solute in any given liquid. The Golay equation (equation (52)) can be
put in a simplified form in a similar manner to the equations for packed
columns:-

(54)
Where,

and

The form of the HETP curve for a capillary column is the same as that
for a packed column and exhibits a minimum value for (H) at an
optimum velocity.

Differentiating equation (54) with respect to (u),

Thus, when H = H
min
, then,

and thus,

(55)
Substituting for (B) and (C) in equation (55)

or,
u
o p t .
D
m
r
4 8 1 + k ' ( )
2
K
2
1 + 6 k ' + 1 1 k '
2
( )
+ 4 k '
3

1
]
1
1
0 . 5
(56)

It is seen that, in a similar manner to the packed column, the optimum
mobile phase velocity is directly proportional to the diffusivity of the
solute in the mobile phase. However, in the capillary column the radius
(r) replaces the particle diameter (d
p
) of the packed column and
consequently, (u
opt
) is inversely proportional to the column radius.
Now,

or,

(57)
Again substituting for (B) and (C),

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H
m i n .
2 r
1 + 6 k ' + 1 1 k '
2
( )
1 2 1 + k ' ( )
2
+
k '
3
3 1 + k ' ( )
2
K
2

_
,

(58)
Equation (58) shows that the minimum value of (H) is solely dependent
on the column radius (r) and the thermodynamic properties of the
solute/phase system. As opposed to the optimum velocity, the
minimum value of (H) is not dependent on the solute diffusivity.
In addition it is seen, from equation (56), that the expression for u
opt
is
very similar to that for a packed column but the expression for H
min.
is
much simpler as it is devoid of the (A) term from the multipath effect.
Due to the relative simple, and precisely defined, geometry of the
capillary column it contains no arbitrary constants involved with the
packing quality of the column such as () and (). As a consequence,
the properties of the capillary column can be explored further in a
relatively straightforward manner. In the following treatment an LC
capillary column will be considered despite, at this time, equipment for
the efficient use of LC capillary columns is not available. From
Poiseuille's Equation, describing the flow of liquid through an open
tube, operating at the optimum velocity,

(59)
Where, (l) is the length of the column,
(P) is the pressure drop across the column,
and () is the viscosity of the flowing liquid.

Now, employing equations (57) and (58),

Thus,

From the Golay equation, B = 2D
m

and n
P r
2
3 2 D
m
(60)
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It is interesting to note from equation (60) that when a capillary
column is run at its optimum velocity, the maximum efficiency
attainable is directly proportional to the inlet pressure and the square of
the radius and inversely proportional to the solvent viscosity and the
diffusivity of the solute in the mobile phase. This means that the
maximum efficiency attainable from a capillary column increases with
the column radius. Consequently, very high efficiencies will be
obtained from relatively large diameter, but very long, columns.
Employing equation (60) it is possible to calculate the range of
efficiencies attainable under operating conditions commonly used for
packed columns. The conditions assumed are as follows,
Inlet Pressure 1000 lb/sq.in.
Viscosity of Mobile Phase 0.00397 Poises
Diffusivity of the Solute in the Mobile Phase 2.5 X 10
-5

cm
2
/sec
The results obtained are shown as a graph relating column efficiency
against column radius in figure 18. It is seen that the 1 micron column
can provided an efficiency of over two hundred thousand plates
whereas the column 100 micron column can provide an efficiency of
over two billion theoretical plates (assuming an inlet pressure of 1000
p.s.i). However, it must be emphasized that the high efficiency column
will be extremely long and have an inordenantly long analysis time. In
addition, the practical limitations of present day chromatography
equipment render the realization of even a modest performance from
LC capillary columns extremely difficult to realize experimentally.
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-0.5 0.5 1.5 2.5
4
5
6
7
8
9
10
L o g . R a d i u s ( R a d i u s i n m i c r o n )
Figure 18. Graph of Log. Efficiency against Log, Radius for an LC
Capillary Column Operated at its Optimum Velocity.
Experimental Validation of the Van Deemter Equation
The different equations were tested against an extensive set of
accurately measured experimental data reported by Katz et al. (24) and,
in order to identify the most pertinent equation, their data and some of
their conclusions will be considered in this chapter. The equations that
were examined, are as follows,
The Van Deemter equation.
The Giddings equation.
The Huber equation.
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The Knox equation.
The Horvath equation.
At first sight, it might appear adequate to apply the above equations to
a number of experimental data sets of (H) and (u) and to identify that
equation that provides the best fit. Unfortunately, this is of little use as,
due to their nature, all five equations would provide an excellent fit to
any given experimentally derived data set, provided the data was
obtained with sufficient precision. However, all the individual terms in
each equation purport to describe a specific dispersive effect. That
being so, if the dispersion effect described is to be physically
significant over the mobile phase velocity range examined, all the
constants for the above equations derived from a curve fitting
procedure must be positive and real. Any equation, that did not
consistently provide positive and real values for all the constants,
would obviously not be an appropriate and explicit equation to
describe the dispersion effects occurring over the range of velocities
examined. However, any equation that does provide a good fit to a
series of experimentally determined data sets and meet the requirement
that all constants were positive and real would still not uniquely
identify the correct equation for column design.
When a satisfactory fit of the experimental data to a particular
equation, is obtained the constants, (A), (B), (C) etc. must then be
replaced by the explicit functions derived from the respective theory
and which incorporate the respective physical properties of solute,
solvent and stationary phase. Those physical properties of solute,
solvent and stationary phase must then be varied in a systematic
manner to change the magnitude of the constants (A), (B),(C) etc. The
changes predicted by the equation under examination must then be
compared with those obtained experimentally. The equation that
satisfies both requirements can then be considered the true equation
that describes band dispersion in a packed column.
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The identification of the pertinent HETP equation must, therefore, be
arrived at from the results of a sequential series of experiments. Firstly,
all the equations must be fitted to a series of (H) and (u) data sets and
those equations that give positive and real values for the constants of
the equations identified. The explicit form of those equations that
satisfy the preliminary data, must then be tested against a series of data
sets that have been obtained from different chromatographic systems.
Such systems might involve columns packed with different size
particles or employ mobile phases or solutes having different but
known physical properties.
Katz, et al. (24) measured the efficiency of two different solutes
(benzyl acetate and hexamethylbenzene) on a silica column 25 cm long
and 9 mm I.D. packed with Partisil 10 (actual mean particle diameter
8.5m) employing six different solvent mixtures. Measurements were
made in triplicate and further replicate measurements made if the mean
of the three differed by more than 3% from the extreme. They
employed a specially designed chromatographic system with low extra
column dead volume to ensure that the contribution of extra column
dispersion to the values of (H) was less than 2%. The properties of the
system are shown in table 1.
Values for k' were obtained using the retention time of
hexamethylbenzene as t
0
. Values for k'
e
(the excluded dead volume)
were obtained employing the retention time of the completely excluded
solute polystyrene (t
(e)0
) (Mol. Wt.83,000). t
(e)0
was also employed for
the measurement of the linear mobile phase velocity.
An example of the results they obtained for the solute benzyl acetate
chromatographed with the solvent mixture 5.4%(w/w) ethyl acetate in
n-hexane is shown in figure 19. The curve through the points is the
fitted curve to the Van Deemter equation and the contributions from
the multipath term, the longitudinal diffusion term and the total
resistance to mass transfer, term derived from the curve fit, are
included.
Table 1. Properties of the Mobile Phase and Solutes
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_________________________________________________________
Mobile Phase Benzyl Acetate Hexamethylbenzene
____________________________
k' k'
e
D
m
(10
-5
cm
2
/sec) D
m
(10
-5
cm
2
/sec)
_________________________________________________________
1/4.6%(w/w)
Et.Ac. in n-C
5
2.05 4.07 3.61 3.51
2/4.9%(w/w) . 1.97 3.94 3.06 2.73
Et.Ac.in n-C
6
3/4.32%(w/w) 2.04 4.06 2.45 2.23
Et.Ac.in n-C
7
4/4.5%(w/w) 2.01 4.01 2.01 1.71
Et.Ac.in n-C
8
5/4.4%(w/w) 2.12 4.20 1.65 1.35
Et.Ac.in n-C
9
6/4.8%(w/w) 2.01 4.01 1.46 1.17
Et.Ac. in n-C
10

Velocity
0.005
0.004
0.003
0.002
0.001
0.000
0.000 0.100 0.200 0.300 0.400 0.500 0.600 0.700
Composite Curve
Multipath Term
Longitudinal
Diffusion
J.Chromatogr.,270(1983)61
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Figure 19. Graph of H versus U for Benzyl Acetate (solvent
5.4%(w/w) ethyl acetate in n-hexane)
It is seen that an excellent fit is obtained with the Van Deemter
equation with an Index of determination of 0.999885. However, the
results from testing all the data to each of the dispersion equations need
to be known in order to identify the equation that, overall, shows the
best fit.
Table 2
Experimental Values for the Dispersion Equation Coefficients
Obtained by a Curve Fitting Procedure
____________________________________________________________
n-pentane n-hexane n-heptane n-octane n-nonane n-decane
4.7%w/w 4.9%w/w 4.3%w/w 4.5w/w 4.4%w/w 4.85w/w
Et.Acet. Et.Acet Et.Acet. Et.Acet. Et.Acet. Et.Acet.
The Van Deemter equation
A 0.001189 0.001144 0.001144 0.001210 0.001208 0.001237
B 0.000108 0.000091 0.000081 0.000065 0.000049 0.000045
C 0.002525 0.003008 0.003362 0.003661 0.004298 0.004786
The Giddings equation
A 0.001189 0.001144 0.001123 0.001210 0.001407 0.001257
B 0.000108 0.000091 0.000086 0.000065 0.000067 0.000053
C 0.002525 0.003008 0.003348 0.003661 0.004001 0.004754
D 0 0 0.005243 0 0.0337 0.008100
The Huber equation
A 0.001455 0.001408 0.000986 0.001196 0.000702 0.1612
B 0.000104 0.000092 0.000084 0.000065 0.000057 0.000056
C 0.003302 0.002728 0.002979 0.003622 0.002769 0.002310
D -0.00092 0.000331 0.000447 0.000046 0.001775 -0.06804
E 0 0 0 0 0 2.13100
The Knox equation
A 0.002509 0.002422 0.002390 0.002545 0.002608 0.002626
B 0.000123 0.000105 0.000096 0.000080 0.000064 0.000061
C 0.008720 0.001407 0.001754 0.002003 0.002518 0.002304
The Horvath equation
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A 0.001366 0.001507 0.001013 0.001197 0.000825 0.005583
B 0.000104 0.000092 0.000083 0.000065 0.000056 0.000051
C 0.003572 0.002495 0.002744 0.003585 0.001948 0.009169
D-0.00110 0.000541 0.000647 0.000080 0.002454 -0.008577
E 0 0 0 0 0 97.30
The value of (H) for each solute was determined in each solvent
mixture over 10 different linear velocities that covered the normal
practical range of velocities used in LC. Measurements at each velocity
were taken in triplicate which resulted in a minimum of 180 values of
(H) being taken for each solute. Each data set, from each solvent
mixture, was fitted to each dispersion equation and the values for the
respective constants (A), (B), (C), etc. calculated, together with the
index of determination for each fitting. It is seen that the data was
sufficient in both quantity, and quality to be able to identify the most
appropriate dispersion equation with some confidence. The results
obtained are shown in table 2. Examination of the results obtained by
Katz et al as given in table 2 show rational fits between the
experimental data and the equations of Van Deemter, Giddings and
Knox. The fit of the data to both the Huber and Horvarth equations
gave alternating positive and negative values for the D constant which
is the coefficient of the term involving a fractional power of (u).
Furthermore, for the Huber equation, the value of coefficient (E) is
consistently zero and for the Horvath equation, is zero for four solvents
mixtures out of six, with an extreme value of 97.3 for one solvent. On
the basis of the irrational fits of the data to the Huber and Horvath
equations, these equations will not be considered to satisfactorily
describe the relationship between (H) and (u). According to Katz et al.
the same irrational behavior of the Huber and Horvath equation was
observed if the data for hexamethylbenzene was also fitted to them.
Although a good fit is obtained to the Giddings equation, the value of
(E) is shown to be numerically equal to zero. This is further evidence
that the Van Deemter equation can be considered to be a special case of
the Giddings equation, where, at the linear velocities employed (i.e.
those normally employed in practical LC), the constant (E) was zero or
tended to zero. It is quite probable, however, that if mobile phase
velocities are considered outside the range studied, the Giddings
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equation would be more appropriate. There does not appear to be
sufficiently precise data available at this time to test this possibility. In
any event, the Van Deemter equation and the Knox equation are the
two that must be further considered as they do describe the
experimental data accurately.
The Van Deemter equation in explicit form is,

(61)

and that of Knox,

(62)
where, (g) and (g') are constants
and the other symbols the meanings previously ascribed to them.
Comparing equations (61) and (62) it is clear that there is a significant
difference between two equations, in that, only the Van Deemter
equations should provide an (A) term that is independent of both the
linear mobile phase velocity and the solute diffusivity. The fit of the
Van Deemter equation to the experimental data confirms the former
condition and the plot of the (A) term against solute diffusivity (the
data taken from tables 1 and 2 and shown in figure 20 confirms the
latter.
Figure 20 demonstrates that the magnitude of the (A) term appears,
within experimental error, independent of the diffusivity of the solute
in the mobile phase. Closer examination, however, indicates that there
might be a slight residual dependence of (A) on diffusivity. This
probably indicates that the velocity range over which the data was
taken was not sufficiently high enough to ensure that the first term of
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220
the Giddings equation was reduced to a constant value as it is in the
simple Van Deemter equation. This can be examined further by
considering the detailed expression for the first term of the Giddings
equation.
0e+0 1e-5 2e-5
3e-5 4e-5
0.000e+0
5.000e-4
1.000e-3
1.500e-3
2.000e-3
2.500e-3
Diffusivity
Figure 20. Graph of A Term against Solute Diffusivity for Benzyl
Acetate
The expanded expression for the first term in the Giddings equation is
as follows:

(63)
From the equation for (A) it is seen that when the value of (u) is
sufficiently large the right hand function in the denominator becomes
negligible and the term simplifies to 2d
p,
the same as the first term in
the Van Deemter equation. However, if (u) takes values, where the
right hand side of the denominator was not quite zero, then the value of
the (A) term would show a slight decrease with increasing values of
D
m
. This effect may well be substantiated by the slight slope of the
straight line in figure 20.
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The curves in figure 21, which is the same plot of the value of the (A)
term against solute diffusivity but this time for hexamethylbenzene
(eluted at the dead volume) gives even stronger confirmation of this
possibility. This indicates that it might be useful to examine the (A)
term more closely.

0e+0 1e-5 2e-5 3e-5
4e-5
0.0000
0.0005
0.0010
0.0015
Diffusivity
y = 0.0012 - 9.607x R = 0.95
Figure 21. Graph of A Term against Solute Diffusivity for
Hexamethylbenzene
Rearranging equation (63)
A
2
+ 2
(64)
Thus, if ud
p
>>>2D
m
, then, A = 2d
p
However, it is now seen that the product of (ud
p
) now determines the
condition for the Giddings equation to simplify to the Van Deemter
equation and, thus, it will depend not only on the mobile phase velocity
but also the particle diameter of the packing. Equation (64) is similar in
form to the Langmuir Adsorption isotherm and it would be interesting
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226
to see the effect of the particle diameter and mobile phase velocity on
the magnitude of A.
0.0E+00
1.0E-03
2.0E-03
3.0E-03
4.0E-03
The (A) Term
0 0.5 1 1.5 2
Mobile Phase Velocity (cm/sec)
Particle Size 10
5
3
Figure 22. Graph of A Term against Mobile Phase Velocity for
Different Particle Sizes
Employing equation (64) curves relating (A) and (u) for different
particle diameters were constructed and are shown in figure 22. For
convenience () is taken as 0.5 (as recommended by Giddings for a
well packed column), () is taken as unity and D
m
taken as 2 x 10
-5
cm
2/
sec. (the diffusivity of benzyl acetate in n-heptane).
Figure 22 discloses, in more detail, the factors that control the
magnitude of the (A) term and the effect of particle diameter on the
mobile phase velocity at which the Giddings equation simplifies to the
Van Deemter equation. For very small particles (e.g. 3 ) the Giddings
equation simplifies to the Van Deemter at a velocity of about 0.2
cm/sec but for the larger particles (e.g., 10 ) it occurs at about 1
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8
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20
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229
cm/sec. However, at the optimum velocity, irrespective of the particle
diameter, the contribution from the coupling term is very small and so
the Van Deemter equation can be used with confidence in column
design.

0e+0 1e-5 2e-5 3e-5 4e-5
-0.0000
0.0000
0.0001
0.0001
Diffusivity
Hexamethylbenzene
Benzyl Acetate
J.Chromatogr.,270(1983)62.
Figure 23. Graph of the (B) Term against Diffusivity
In summary, the Data of Katz et al. shows some slight dependence of
the (A) term on D
m,
(which can be explained on the basis of the
calculations given above). However, as a result of the curve fitting
procedure to the equation it is shown not to be
dependent on (u) and thus, supports the Van Deemter equation as
opposed to the Knox equation. It does, however, also support the idea
that the Van Deemter equation is a special case of the Giddings
equation.
Both the Knox equation and the Van Deemter equation predict a linear
relationship between the value of the (B) term (the longitudinal
diffusion term) and solute diffusivity. A plot of the (B) term against
diffusivity for benzyl acetate and hexamethylbenzene is shown in
72
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7
8
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11
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17
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19
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21
22
231
232
232
figure 23. It is seen that the predicted linear relationship is indeed
realized. However, it can be shown that the values for the (B) term
from the Knox equation curve fit also give a linear relationship with
solute diffusivity so the linear curves shown in figure 23 do not
exclusively support the Van Deemter equation. The stationary phase,
for a silica gel column would consist almost entirely of that portion of
the 'mobile phase' that is 'static' and trapped in the pores of the silica
gel. As a consequence, in equation (49) it would appear reasonable to
assume that,

D
m
= D
s
However, this will be an approximation as, if a binary mixture of
solvents is used for the mobile phase, then a layer of the more polar
solvent would be adsorbed on the surface of the silica gel (25) and the
mean composition of the solvent in the pores of the silica gel would not
be exactly the same as that of the mobile phase. Nevertheless, it would
be reasonable to assume that,

D
m
= D
s
where () is a constant, probably close to unity.
However that there are two ways in which the diffusivity of the solute
in the mobile phase can be changed. It can be modified as a result of
changing the solute which is being eluted, in which case the above
assumptions are valid as (D
s
) is likely to change linearly with (D
m
).
The diffusivity can also be modified by choosing an alternative mobile
phase in which case (D
m)
will be changed but (D
s
) will remain the
same. Under these circumstances the above assumptions are not likely
to be precisely correct. Nevertheless, if the resistance to mass transfer
in the stationary phase makes only a small contribution to the overall
value of (H) due to the magnitude of (d
f
) being much smaller than (d
p
)
the assumption that

D
m
= D
s will still be approximately true.
Assuming that the diffusivity is varied by changing the nature of the
solute and not the mobile phase, then D
s
can be replaced by eD
s
and
equation (1) can be simplified to ,
73
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26
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33
34
35
36
37
38
234
235

(65)
where,

Differentiating with respect to (u), equating to zero and solving for
u
opt.
, it can be seen that,
u
opt.

_
,

0.5
(66)
Further by substituting for (u
opt.)
in equation (65) it can be seen that
the minimum plate height (H
min.)
is given by,

H
min.
2
+ 2 2
(67)
Now, it is seen from equations (66) and (67) that the optimum linear
velocity should be linearly related to the diffusivity of the solute in the
mobile phase, whereas the minimum value of the HETP should be
constant and independent of the solute diffusivity. This, of course, will
only be true for solutes eluted at the same (k').
In table (1) it is seen that the values of (k') and (k'
e
) are approximately
the same for all the mobile phase mixtures employed and if it is
assumed that the contribution of the resistance to mass transfer in the
stationary phase to (H) is small, then equations (66) and (67) can be
tested.
74
236
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24
237
238
238
0e+0 1e-5 2e-5 3e-5 4e-5
0.0000
0.0005
0.0010
0.0015
0.0020
0.0025
Diffusivity
Benzyl Acetate
Hexamethlbenzene
Figure 23. Graph of Minimum (H) against Solute Diffusivity
In figure 23 the values of (H
min.
) are plotted against solute diffusivity
and it is seen that the independence of (H
min.
) on diffusivity is largely
confirmed. Close examination, however, shows that neither of the lines
for the two solutes are completely horizontal with the baseline, but the
dependence of (H
min
) on diffusivity is extremely small for the solute
benzyl acetate. The slight slope of the line for the solute
hexamethylbenzene might well result from the fact that either the (A)
term is not completely independent of the diffusivity (D
m
) as shown by
the results in figure 21, or the resistance to mass transfer in the
stationary phase does make a small but significant contribution to the
value of (H).
The curves relating the optimum velocity with solute diffusivity are
shown in figure 24 and it is seen that the straight lines predicted by the
Van Deemter equation are realized for both solutes. It should be noted
that similar treatment of the Knox equation does not predict that values
of H
min
should be independent of the solute diffusivity neither does it
predict that (u
opt
) should vary linearly with solute diffusivity.

75
239
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21
22
23
240
241
0e+0 1e-5 2e-5 3e-5 4e-5
0.000
0.100
0.200
0.300
Diffusivity
Benzyl Acetate
Hexamethylbenzene
Figure 24. Graph of Optimum Velocity against Solute Diffusivity
This is strong evidence, supporting the validity of the Van Deemter
equation, as opposed to the Knox equation.
Returning to equation (49), it is seen that the Van Deemter equation
predicts that the total resistance to mass transfer term must also be
linearly related to the reciprocal of the solute diffusivity. Furthermore,
it is seen from equation (49), that, if there is a significant contribution
from the resistance to mass transfer in the stationary phase, the curves
will show a positive intercept.

In figure 25. the Resistance to Mass Transfer term (the (C) term from
the Van Deemter curve fit) is plotted against the reciprocal of the
diffusivity for both solutes. It is seen that the expected linear curves are
obtained and that there is a small, but significant, intercept for both
solutes. This indicates that there is a small but, nevertheless, significant
contribution from the resistance to mass transfer in the stationary phase
for these two particular solvent/stationary phase/solute systems.
Overall, however, all the results in figures 23, 24 and 25 support the
Van Deemter equation extremely well.
76
242
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23
243
244
244
0e+0 2e+4 4e+4 6e+4 8e+4
0.000
0.001
0.002
0.003
0.004
0.005
Benzyl
Acetate
1/Diffusivity
Hexamethylbenzene
Figure 25. Graph of (C) Term against the Reciprocal of the Solute
Diffusivity.
Katz et al. (12) also examined the effect of particle diameter on the
value of the overall resistance to mass transfer constant (C). They
employed columns packed with 3.2 , 4.4 , 7.8 , and 17.5 , and
obtained HETP curves for the solute benzyl acetate in 4.3%w/w of
ethyl acetate in n-heptane on each column. The data was curve fitted to
the Van Deemter equation and the values for the A, B and C terms for
all four columns calculated. According to the Van Deemter equation
the (C) term should be linearly related to the square of the particle
diameter. A graph relating the value of the (C) term with the square of
the particle diameter is shown in figure 26.
Figure 26 shows the predicted linear relationship between the
resistance to mass transfer term and the square of the particle diameter.
The linear correlation is extremely good and it is seen that there is,
indeed an intercept on the (C) term axis, at zero particle diameter,
which confirms the existence of a small, but significant, contribution
from the resistance to mass transfer in the stationary phase.
77
245
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23
246
247
0 10 20 30 40
0.000
0.005
0.010
0.015
Particle Diameter Squared (X 0.0000001)

Figure 26. Graph of the (C) Term against the Square of the
Particle Diameter
The Effect of the Function of (k') on Peak Dispersion
Reiterating the Van Deemter equation,

If it is assumed that the column is operated at relatively high velocities,
such that the contribution from longitudinal diffusion is no longer
significant, then,

(68)
Again, assuming that the diffusivity of the solute in the stationary
phase (D
S
) is simply related to the diffusivity in the mobile phase (D
m
),
i.e. D
S
= D
m
78
248
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8
9
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21
249
250
250
Substituting for (D
S
) in equation (7)
(69)
Inserting the expression for f
1
(k') recommended by Purnell (10) and the
expression for f
1
(k') as derived by Van Deemter (2) and rearranging,

(70)
Dividing throughout by

, and rearranging,

(71)
It follows that, if suitable experimental data was available, a graph
relating, , against, ,
should provide a straight line. Katz and Scott (26), in their work
involving the development of a method for the measurement of solute
molecular weight from chromatographic data, generated sufficient data
to test the relationship given in equation (71). Furthermore, the
equation could be tested against the two alternative values for the
capacity factor (k') calculated by employing the fully permeating dead
volume, or (k'
e
) derived by employing the excluded dead volume.
The graph relating,

, to,

should provide a straight line. This graph is
shown in two forms figure 27. It is clear that the upper curve is not a
linear curve and the use of (k') values derived from the fully
permeating dead volume can not be used in the kinetic studies of LC
columns. In contrast, the lower linear curve shown in figure 27, is the
same basic graph but, in this case, the ordinate values were calculated
using (k'
e
) values based on the excluded dead volume. It follows, that
the excluded dead volume must not only be used for measuring mobile
phase velocities in kinetic studies of LC columns and also for LC
79
251
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25
26
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29
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31
32
33
252
253
column design but it must also be employed for the measurement of
capacity factors.
Summary
In summary, it can be said that there are a number of dispersion
processes that take place in a column and for packed columns the
dispersion can be best described by the Giddings equation. This
equation gives the total dispersion as function of the mobile phase
velocity and other pertinent physical properties of the column and
distribution system.
80
254
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7
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9
10
11
255
256
256
0
0.2 0.4 0.6 0.8 1.0
0
0.2 0.4 0.6 0.8 1.0
0
0.3
0.6
0.9
1.2
1.5
0.1
0.2
0.3
0.4
0.5
0
k' Calculated from the retention time
of the fully permeating unretained solute
k'e Calculated from the retention time
of the fully excluded unretained solute
f(1)k'e
f(1)k'
f(2)k'
f(2)k'e
f(1) =

and f(2)=

Figure 27. Graph of

against

for both (k') and (k'
e
)
However, for columns operated in the vicinity of the optimum velocity
(where the best performance is to be realized) the van Deemter
equation is simpler and give equally accurate and precise calculated
data. In GC columns, the compressibility of the mobile phase must be
81
257
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258
259
taken into account and the exit mobile phase velocity (not the mean
velocity) employed in the dispersion function.
In addition, the diffusivity of the solute must be taken at atmospheric
pressure. Only the Van Deemter equation, the Giddings equation and
the Knox equation fit experimental (H) versus (u) data accurately and
only the Van Deemter equation and the Giddings equation correctly
account for other physical properties of the chromatographic system.
The Van Deemter equation appears to be a special case of the Giddings
equation, which simplifies to the Van Deemter equation when the
mobile phase velocity is close to, or around, the optimum mobile phase
velocity. The form of the Van Deemter equation and, in particular, the
individual functions contained in it, are well substantiated by
experiment. The Knox equation is obtained from an empirical fit to
experimental data and the individual functions of other pertinent
variables contained in the equation are not all substantiated by
experiment. The Golay equation accurately described dispersion in
capillary or open tubular columns but in GC the compressibility of the
mobile phase must also be taken into account (Golay in his original
derivation did not accommodate gas compressibility).
It would appear from the data available at this time, that the Van
Deemter equation (for packed columns) or the Golay equation (for
capillary or open tubular columns) would be the most appropriate to
use in column design and in the interpretation of column properties.
References

1. A.J.P.Martin and R.L.M.Synge, Biochem. J .,35(1941)1358.
2. J. J. Van Deemter,F. J. Zuiderweg and A. Klinkenberg, Chem.
Eng. Sci.,5(1956)271
3. J.C.Giddings, " Dynamics of Chromatography Part 1 ",(1965)29
4. W. Feller, " Probability Theory and its Applications", Wiley,New
York, (1950) Chapt.14.
82
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23
24
25
26
27
28
29
30
31
32
33
34
261
262
262
5. (7) D.S.Horne,J.H.Knox and E.McLaren, "Separation Techniques
in Chemistry and Biochemistry ", (Ed.R.A.Keller), Marcel Dekker,
New York,
6.G.E.Uhlenbeck and L.S.Oerstein, Phys. Rev.,36(1930)823.
7. 2. J. C. Giddings, Dynamics of Chromatography, Marcel Dekker
Inc. New York, Chapter 2,(1965).
8. M. J. E.Golay, in "Gas Chromatography 1958 ", (ed. D. H. Desty),
Butterworths, London, (1958)36.
9. 1/J.J.Van Deemter,F.J.Zuiderwg and A.Klinkenberg,Chem.Eng
Sci.,5(1956)271.
10. J.H.Purnell and C.P.Quinn,in "Gas Chromatography 1960" (ed.
R.P.W.Scott), Butterworths London (1960)184.
11.J.C.Giddings,"Dynamics of Chromatography",Marcel Dekker,New
York, (1965) 56.
12.E.Katz,K.L.Ogan and R.P.W.Scott, J.Chromatogr.,270(1983)51.
13.E.D.Katz and R.P.W.Scott,J.Chromatogr. ,270(1983)29.
14.J.A.Riddick and W.B.Bunger,"Oraganic Solvents"Wiley-
Interscience, New York,(1970)399.
15.E.Katz, K.L.Ogan and R.P.W.Scott, J.Chromatogr., 289(1984)65.
16.J. C. Giddings, J. Chromatogr., 5(1961)46.
17. J. F. K. Huber and J. A. R. J. Hulsman, Anal Chim . Acta,
38(1967)305.
18.G. J. Kennedy and J. H. Knox, J. Chromatogr. Sci., 10(1972)606.
19. J. N. Done and J. H. Knox, J.Chromatogr. Sci., 10(1972)606.
20. J. N . Done, G. J. Kennedy and J. H. Knox, in "Gas
Chromatography 1972' "(Ed. S. G. Perry), Applied Science
Publishers, Barking, (1973)145.
83
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26
27
264
265
21. J. C. Giddings, Anal Chem. ,35(1963)1338.
22.J.C.Giddings,"Dynamics of Chromatography", Marcel Dekker,New
York, (1965)125.
23. Cs. Horvath and H.J.Lin, J.Chromatogr., 149(1976)401.
24. E.Katz, K.L.Ogan and R.P.W.Scott, J.Chromatogr . 270(1983)51.
25. R. P. W. Scott and P. Kucera, J. Chromatogr., 149(1978)93.
26.E. D. Katz and R. P. W. Scott, J. Chromatogr. 270(1983)29.
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