CHE424

Chemical Reaction Engineering II

Notes 3: Models; Dispersion
 Dispersion Model
Choice of Models
• In this Section we shall deal with models with
small deviation from plug flow. There are two
models for this: the dispersion model and the
tanks-in-series model. Use the one you are
comfortable with. They are almost equivalent.
These models apply to turbulent flow in pipes,
laminar flow in very long tubes, flow in packed
beds, shaft kilns, long channels, screw
conveyers, etc.
• These models may not apply to laminar flows in
short tubes or laminar flows of viscous materials;
it may be that the parabolic velocity profile is the
main cause of deviation from plug flow. This
situation is called pure convection model which
shall be treated later.
• If you are unsure which model to use there are
charts in literature which can tell you which
model should be used to represent your setup to
be seen later.
Axial Dispersion

• Suppose an ideal pulse of tracer is introduced

into the fluid entering a vessel, the pulse spreads
as it passes through the vessel, we assume a
diffusion-like process superimposed on plug flow.
This is called dispersion or longitudinal dispersion
to distinguish it from molecular diffusion. The
dispersion coefficient D (m2/s) represents this
spreading process.
• Large D means rapid spreading of the tracer curve
• Small D means slow spreading
• D = 0 means no spreading, hence plug flow
• And is a dimensionless group that characterizes
the spread in the whole vessel.
• Figure 1. denotes the spreading of tracer
according to the dispersion model.
• We evaluate D or D/L by recording the shape
of the tracer curve as it passes the exit of the
vessel.

Figure 1: Spreading of tracer in dispersion model

• In particular we measure;

• These measured are directly linked by theory

to D and D/L. The mean, for continuous or discrete
data, is defined as;

(1)
• The variance is defined as:

(2)

• Or
(3)

• The variance represents the square of the spread of

the distribution as it passes the vessel exit and has
units of (time)2. It is particularly useful for matching
experimental curves to one of a family of theoretical
curves.
• Consider plug flow of a fluid, on top of which is
superimposed some degree of back-mixing, the
magnitude of which is independent of position
within the vessel. This condition implies that there
exist no stagnant pockets and no gross bypassing
or short-circuiting of fluid in the vessel.
• This is called the dispersed plug flow model, or
simply the dispersion model. Note that with
varying intensities of turbulence or intermixing the
predictions of this model should range from plug
flow at one extreme to mixed flow at the other. As
a result the reactor volume for this model will lie
between those calculated for plug and mixed flow.
• Since the mixing process involves a shuffling or
redistribution of material either by slippage or eddies,
and it is repeated many times during the flow of fluid
through the vessel, we can consider these
disturbances to be statistical in nature like in
molecular diffusion. For molecular diffusion in the x-
direction the governing differential equation is given
by Fick's law: (4)
• Where , the coefficient of molecular diffusion is
a parameter that uniquely characterizes the
process.
• Analogously we may consider all the
contributions to intermixing of fluids flowing in
the x-direction to be described by a similar
expression;
(5)
• Where D, the longitudinal or axial dispersion
coefficient uniquely characterizes the degree of
back-mixing during flow.
• The term longitudinal or axial are used to
distinguish the mixing in the direction of the flow
from mixing in the lateral or radial direction
which is not of our primary concern here. In
streamline flow of fluid through pipes, axial
mixing is mainly due to fluid velocity gradient
while radial mixing is due to molecular diffusion.
• The basic differential equation representing this
dispersion model is;
(6)
• Where;
• The dimensionless group , called the vessel
dispersion number is the parameter that
measures the extent of axial dispersion, therefore
• This model usually represents quite satisfactorily
flows that do not deviate too greatly from plug
flow, thus real packed beds and long tubes with
streamline flows.
• Fitting Dispersion model for small dispersion,
• < 0.01
• If we impose an idealized pulse onto the flowing
fluid then dispersion modifies this pulse as shown
in the figure 2.
Figure 2: Relationship between D/L and EΘ
For small dispersion, the tracer curve does not
change in shape during the time it is measured.
Under these conditions, eqn. (6) gives curve of fig. 2
(7)
• This represents a family of Gaussian curves also
called error or normal curves. The equations
representing this family are:

(8)
 Figure 3: Additive ppty. of means and variances of the E curves of vessels a,b…….n

• Figure 2 shows various ways to evaluate the

parameter D/L from and experimental curve by
calculating its variance, by measuring its
maximum height or width at the point of
inflection or by finding that width which includes
68% of the area. Also note how the tracer
spreads as it moves down the vessel. From the
variance expression of eq. (8), we find that
 For small extents of dispersion, numerous
simplifications and approximations in the analysis of
tracer curves are possible.
First, the shape of the tracer curve is insensitive to the
boundary condition imposed on the vessel, whether
closed or open. So for both closed and open vessels

• For a series of vessels the of the individual

vessels are additive, as in Figure 3. Thus;
 (9)

• And (10)

• This additive property of variance allows us to

treat any one shot tracer input (no matter the
shape) and to extract the variance of the E
curve of the vessel from it. So we can have;
(11)
• According to the figure, the increase of variance is
the same in both cases or
• Aris (1959) showed that for small extent dispersion;

(12)

• Meaning that the value for a vessel can be

found no matter what the shape of the input curve is
• The goodness of fit can only be evaluated by
comparison with the more exact solution.
• From such a comparison we find that the
maximum error in estimating is given by;
• Large deviation from Plug Flow; D/L > 0.01
• Here the pulse response is broad and it passes the
measurement point slowly enough that it changes
shape-it spreads-as it is being measured. This gives a
non-symmetrical E curve.
• An additional complication enters the picture for large
D/L; What happens right at the entrance and exit of
the vessel strongly affects the shape of the tracer
curve as well as the relationship between the
parameters of the curve and D/L.
• We consider two types of boundary conditions;
• (i) either the flow is undisturbed as it passes the
entrance and the exit boundaries (this is called
the open boundary condition) or
• (ii) you have plug flow outside the vessel up to
the boundaries (this is closed boundary
condition). This leads to 3 combinations of b.c.;
close-close, open-open and mixed.
• The figure below illustrates the closed and
open extremes whose RTD curves are
designated as Ecc and Eoo

Figure 4: Boundary conditions used with dispersion model

• For all other boundary conditions you do not get
a proper RTD. In all cases you can evaluate D/L
from the parameters of the tracer curves but
each curve has its own mathematics. Let us look
at tracer curve for close vessel: Here an analytical
expression for the E curve is not available but we
can construct the curve by numerical method (fig.
5) or evaluate its mean and variance exactly;
thus;
(13)
Figure 5: Tracer response curves for closed vessels and large deviations
• Open Vessel
• This represents a convenient and commonly used
section of a long pipe. It is a physical situation
where the analytical expression for the E curve is
not too complex. The results are given in the
response curve shown in Figure 6 by these
equations derived by Levenspiel;
(14)
Figure 6: Tracer response curve for open vessels having large deviations from plug flow
• Notes:

(15)

1)- For small D/L all curves for different

boundary conditions approach the curve of
eq. (8). For “small deviation”. At large
deviations the curves differ more from each
other.
2)- To evaluate D/L, either match the measured
tracer curve or the measured 2 to theory.
3)- If the flow deviates greatly from plug (D/L
large), chances are that the real vessel does not
meet the assumption of the model. It becomes
questionable whether the model should even be
used.
4)- Always ask whether the model should be used.
Match 2 values if the shape looks wrong, don’t
use the model. Wrong shapes here
5)- For large D/L literature is conflicting due to
unclear assumptions about what is happening
at the vessel boundaries. The mathematical
treatment is questionable. Due to these facts
one needs to be very careful in using
dispersion model where back-mixing is large,
particularly in open systems.
Step input of tracers
The output F curve is S-shaped and is obtained
by integrating the corresponding E curve
• Thus at any time t or Θ; (16)

• The shape of F curve depends on D/L and the

boundary conditions of the vessel. Analytical
expressions are not available for any of the F
curves; but their graphs can be constructed. Two
typical cases are as displayed below;
• For small deviation from plug flow (D/L<0.01)
from eqns. (8) and (16) we can find the curves of
Figure 7.
• For this small deviation, we can find D/L directly
by plotting the experimental data on the
probability graph paper as seen of Fig. 8.

Figure 7: Step response curves for small deviations

• Plot on probability graph paper from which
you can find D/L

Figure 8: Probability plot of response signal.

• For large deviation, the problems of boundary
conditions must be considered. The resulting S-
shape response curve are not symmetrical, their
equations are not available, and they are best
analyzed by first differentiating them to give the
corresponding Cpulse curve. Figure 9 shows an
example of this family of curves.
• Step response for large deviation, D/L

Figure 9: Step response curves for large deviations in closed vessels

• Notes:
• 1)- One direct commercial application of the step
experiment is to find the zone of intermixing- the
contaminated width between two fluids of
somewhat similar properties flowing one after
the other in a long pipe. Given D/L we can find
this from the probability plot of fig. 8. Design
charts to ease calculations are given by
Levenspiel (1958a).
• 2)- Sometimes one type of experiment is more
convenient for many reasons, when you have a
choice, the pulse experiment is preferred.
Example 1: D/L from a Cpulse curve
• On the assumption that the closed vessel of
example 1 of Note 1. is well represented by the
dispersion model, calculate the vessel dispersion
number D/L. the C versus t tracer response of
this vessel is;
Solution

• Since the c curve for this vessel is broad and

unsymmetrical, let us guess that dispersion is too
large (we cannot use small dispersion curves).
• We start with the variance matching procedure.
The mean and variance of a continuous
distribution measured at a finite number of
equidistant locations is given by;
• And
• Using the original tracer concentration-time data
we find;

• Therefore;
and
• For a closed vessel eq. (13) relates the variance to
D/L.
• Ignoring the 2nd term on the right, our first
approximation becomes;
• Now correcting for the term ignored we find by
trial and error;
• This value of D/L is beyond the limit where
Gaussian approximation should be used so the
guess was right.
Example 2: D/L from an F curve

• Von Rosenberg(1956) studied the displacement of

benzene by n-butyrate in a 38 mm diameter
packed column 1219 mm long, measuring the
fraction of n-butyrate in the exit stream by
refractive index methods. When graphed, the
fraction of n-butyrate versus time was found to be
S-shaped. This is the F curve for von Rosenberg’s
run at the lowest flow rate where  = 0.0067 mm/s
which is about 0.5 m/day. Find the vessel
dispersion number of this system.
• The F curve is given below.
Solution:
• Instead of using slopes of F curve to give E curve
and determining the spread of this curve, we use
the probability paper method; plotting the data
on this paper gives close to a straight line
• To find the variance and D/L from the
probability chart, follow the procedure in Figure
8. so our figure here shows that;

• This time interval represents 2, therefore the

standard deviation is;
• This standard deviation is needed in
dimensionless time unit in order to find D.
• Therefore the variance is;
• And from eq (8);
• This is well below 0.01 which justifies the use of
Gaussian approximation.