RESIDENCE T I M E DISTRIBUTION IN

REAL S Y S T E M S
D A V I D WOLF AND W I L L I A M RESNICK
Chemical Engineering Department, Israel Institute of Technology, H a g a , Israel

The measurement and analysis of residence time distribution i s an important tool in the study of continuous
flow systems. A study of available experimental data shows that the usual assumptions of perfect mixing
or plug flow d o not correspond to the situation existing in real flow systems. The residence time distribution
for real systems can b e represented b y an F-function of the form
F(t) = 1 - exp [- 7) (531 fort 2 E

F(t) = 0 for 0 < t 5 E

This equation results for a number of plausible flow models that include the additional possibilities of dead-
space, short-circuiting, error in average residence time determination, and l a g in response and any com-
bination o f these models. This equation can b e used to describe the experimental results obtained far
single as well as multistage systems.

HE MEASUREMEST and analysis of residence time distribution
Thas become a n important tool in the study of continuous
flow systems. The theoretical analysis is normally based on
the ideal assumption of either plug (or piston) flow or perfect
mixing. Xeither assumption corresponds to the flow situation
existing in most practical cases. A knowledge of the actual
behavior is necessary for the design of reactors, for the evalua-
tion of designs, and to gain a n insight into the physical process.
Representation and Measurement of
Residence Time Distribution
Expressions for residence time distribution have been de-
veloped ( 7 , 6, 7 7 , 72, 75) and applied to various systems. In
the folloLving brief review, the nomenclature adopted by
Danckwerts ( 7 ) \vi11 be used. The fraction of material that
spends less than time t in the system is given by the F-function.
For the case of perfect mixing
F(t) 1 - e-t/o
= (1 1
The function E is the first time derivative of F and the integral
of E d t between limits t l and t~ gives the fraction of material
that has been in the system for a time between t l and tZ-i.e.,
the "age" of the material is between ti and tz. The function C
is the derivative of F with respect to t/B. Its significance is
similar to that of E. For a perfect1)- mixed system,
E(t) =
0 e-/ 8 (2)
straight lines by plotting their data as In (1 - F ) us. t/O. These
straight lines, however, normally possessed slopes different
from -1 and, in addition, did not pass through the origin,
conditions that would have obtained had the systems obeyed
Equation 1, The F-function for real single-stage continuous
flow systems could, therefore, evidently be represented by the
general equation
(I-4
(4)
F(t) = 1 - e-' ; F(t) 3 0
This equation can be obtained for a number of models that
could reasonably be expected to represent such systems and
that have already been proposed in the literature. Some of
these models are considered below. For all cases the analysis
is based on a step change in the forcing function.
Perfect Mixing with Plug Flow. It is assumed that the
system volume consists of two parts, fraction p in which the
material moves in plug flow and fraction (1 - p ) in which
perfect mixing takes place. The transfer function for the
system is
(5)
The inverse transformation after the step change in the
inlet concentration results in

C(tj = e-t/o (3)

Several experimental methods are used for the measurement For p = 0, perfect mixing only, the equation reduces to
of residence time distribution. They are based on the measure- Equation 1. F o r b = 1, plug flow only, the equation reduces to
ment of the s\ stem response to a disturbance (forcing function)
F = O ;t < e
applied to the system inlet. Normally a tracer is added to the
inlet stream and the concentration of the tracer in the outlet F = l ; t > 9
stream is measured as a function of time. The tracer can be
Figure 1 shows the system response for several values of p .
introduced as a pulse. impulse, step change or ramp or as a
Perfect Mixing with Dead Space. The system is assumed
periodic function. The F-function can be obtained directly
to have a perfectly mixed volume (1 - d ) V with dV volume
from the outlet tracer concentration following a step change a t
of dead space. T h e transfer function is identical to that for a
the inlet. The E- and C-functions can be derived directly
first-order system with a n average residence time equal to
from the system response to a n impulse of tracer.
(1 - d)B rather than e. The F-function is, therefore,
Models for Actual Systems-Single Stage -~ 1
(7)
~ ( t =) I - e (l - d)o; ~ ( t>) o
An examination of residence time distribution data of a
number of investigators (2-5.7-70, 73. 74, 77) showed that The system performance for several values of d is shown in
the F-functions for their s) stems could be represrnted by Figure 2.

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 1.0

09

08

07

06

F 05

04

03

02

01

'0 02 04 06 OB 10 12 14 16 18 20 22 24 26
t/e

Figure 1 . Perfect mixing with plug flow Figure 3. Perfect mixing with partial short circuiting

System response to step change System response to step change

10
10
09
09
08
08
07
07
06
06

F05 F 05

04
04
03
03
02
02
01
01
0 6
0'2 O\ 0)5 0'8 Ib 1; 1'4 1'6 1'8 2'0 2'2 2'4 2b
+/e Figure 4. Perfect mixing with error in average residence
Figure 2. Perfect mixing with dead space time
System response to step change System response to step change

Perfect Mixing with Partial Short Circuiting. One Perfect Mixing with Error in Average Residence Time.
model proposed in the literature is that of perfect mixing in a Although only two pieces of information are necessary to
reactor but with part of the entering feed passing to the outlet calculate the average residence time-flow rate and system
with an infinite velocity. It is assumed that (1 - f) is the volume-in many cases, it is difficult to obtain accurate data.
fraction of material moving through perfect mixing and f Flow rates may not be available from direct measurements,
is the fraction moving with an infinite velocity. The transfer especially in the case of data from industrial reactors. True
function for this model would be system volume also may be difficult to determine accurately.
Some of these uncertainties were cited by Danckwerts ( 3 ) . For
CO(S) - (1 -f) +f
(8) this model, it will be assumed that the calculated average
G(S)- 8
residence time is 6 whereas the true residence time is r0. The
F-function would, therefore, be
The F-function obtained upon inverse transformation with
F(t) = 1 - e- t/rO; F(t) > 0 (11)
Ci(S) replaced by AIS is
but the experimental data would be plotted as F as a function
of t / & The results to be expected for this case are shown in
Figure 4.
Equation 9 can be brought to the form Perfect Mixing with Lag in Response. A response lag is
possible and, indeed probable for real systems. This lag
could take the form of a distance-velocity lag in the sampling
system, a measurement lag or any other delay in the system
The graphical representation is illustrated in Figure 3. that would affect its measured response characteristics. The

288 I&EC FUNDAMENTALS

 OO 02 04 06 08 10 12 14 16 18 20 22 24 26
t/8

Figure 5. Perfect mixing with lag in response

System response to step change

r - l i 1 r - -

Figure 6. Combined model-block diagram

transfer function for a single time constant system-i.e., a

perfectly mixed vessel, and a pure time delay is

where L is the time delay.

The inverse transformation for the case of a unit step change in
the input is
F(t) = 0; <L t
/I //
-
-__
(1L) 05 10 15 2R 25 33

~ ( t ) = l - e ' ; t > ~ (13) 110

The response is shown in Figure 5 for several values of LIB. Figure 7. F-Diagram
Combined Model. T h e most general case is obtained by A. Perfect mixing with plug flow and d e a d space
combining all the preceding models to determine the equation 6. Perfect mixing with d e a d space and short circuiting
C. Combined models
for the resulting F-function. In this way, the contribution of
each factor can be shown. T h e system is considered to have a
true average residence time of re. Fraction d of the system
volume is considered to be dead volume whereas the remainder,
(1 - d ) ?represents the effective volume through which the ma-
terial moves. The material moves in plug flow through p
fraction of the effective volume. Subsequently, (1 - f) fraction
of the stream flows through the remainder of the effective
volume which is perfectly mixed, whereas the fraction f short-
Table I. Values of 7 and C/O for Several Models
circuits this section. The combined stream then encounters a
Model v C/O
lag, L. The block diagram is shown in Figure 6.
The transfer function for this general case is Perfect mixing 1 0
with plug flow >1 20
-Pr (1 - d ) with dead space >1 0
UT (1 - d )
es + 1
1 exp (1 - f)
es exp -LS with short circuiting
with error in e
with system lag
<1
?1
1
<O

>O
0

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 1.0,-

n=i c/e:o -
0:0.74 C/B=-OJ ---
experiments: results c

' 4

t/e
5 6 7 8

Figure 8. Experimental and derived F-diagram

A. Denver flototion cell (9) B. MacKintosh flotation cell (91 C. Liquid in fixed bed ( 1 0 ) D. Gas in fluidized bed-1.1 ft. per sec. air velocity ( 1 4 )

The inverse transform for the case of a step forcing function Physical Significance of 7 and E

becomes
F(t) = 1 -
F(t) 2 0
Several combinations are illustrated in Figure 7. Figure
7 , A represents plug flow combined with perfect mixing and
dead space; 7,B represents plug flow, perfect mixing, and some
short-circuiting (infinite velocity) ; and 7,C shows different
combined models as indicated on the figure. The figure
shows that making a decision as to which model represents a
given situation is a difficult if not hopeless task.
All of the models considered, however, are plausible, and
they all result in an F-function of the form
In Table I, the values for 17 and E/O are shown for various
models. The term 7 can be said to be a measure of the effi-
ciency of mixing. For the case of perfect mixing, 7 is equal to
unity, whereas for pure plug flow, 7 tends to infinity. The
(15) presence of dead space in the system also results in 7 assuming
a value greater than unity. Short circuiting results in 7 less
than unity, whereas a n error in the determination of the
average residence time could result in 7 being larger or smaller
than unity depending on the error. Thus. deviations from
unity indicate that perfect mixing is not obtained in the entire
system volume.
The term e is a measure of the phase shift in the system. If
€ 1 0 is greater than zero, the case with plug flow or a system
lag, the system response lags behind that expected for perfect
mixing. Short circuiting would result in a n anticipatory
response-i.e., E assumes negative values.

Applications to Experimental Results

a form which represents the experimental data obtained by
the investigators previously cited. Although the theoretical
model may represent the experimental data quite accurately,
it may not represent the true physical picture. The model
may, however, give some insight into the behavior of the
system.
Published residence time distribution data of the investigators
previously cited were examined to determine the constants 7
and e of Equation 16. Their data were plotted as ln(1 - F ) us.
t / e yielding straight lines. The values of 7 and e/t? were then
determined from the slope and intercept of the line. I n
Table I1 the values obtained for 7 and c/o are summarized.

290 l&EC FUNDAMENTALS

 , *
I
10
for 11 and E depend on the system characteristics, flow pattern,
degree of mixing, etc.
Multistage Systems. T h e model derived for real single-
stage systems can be extended to multistage systems. T h e
07 two cases most likely to be encountered are those in which all
stages are either of equal volume or else of unequal volume.
O6 t The transfer function for a single real stage that behaves
according to the model derived previously is

O't///'
00 05
1
10 15
tlne
I
20 25 30
and the transfer function for n stages would be
n
- 6,:
Figure 9. F-Diagram-perfect mixing in multistage system 1 e i=l

O n the assumption that the values of 7 and e are equal for

each stage, the F-function for n identical stages in series can
be obtained with the substitution of a step forcing function.
I n addition, for each system cited, the system behavior is
described in terms of a n equivalent flow model that was
F(t) = 1 -e
t - ne
+ ...... +
deduced from the calculated values for 7 and C / O . In Figure
8, F-functions calculated from the derived values for 7 and
C / O for several of the cited investigators are shown and com-
(n - l)!
pared with experimental data. If the assumption of 7 and E being equal for each step can
The models deduced do not necessarily represent the true also be made for n unequal stages, the F-function is
physical situation. For example, a model that could be
represented by a combination of perfect mixing, plug flow,
and dead space could also be represented by a combination of
perfect mixing, dead space, and lag or by a combination of all
four. However, a flow model that also has physical significance
3#i
for a particular system could presumably be deduced if suffi-
cient details were known. A plot of ln(1 - F ) as a function of tie will not yield a straight
'The experimental results confirm that real continuous flow line for a multistage system contrary to the situation obtained
systems can be represented by Equation 16 in which the values for a single-stage system.

Table II. Derived Values of q and C/O and Derived Flow Models from Some Experimental Data
Deriued Flow Model
a, P, d, f,
Perfect Plug Dead Short
mixing of Jow of space circuiting
effective effectnue of total of Jow
Figure in Derived Values volume, volume, volume, rate,
Ref. Flea System €/e v
11 /O 70 % 72
8 Turbulent oil in pipe 0 1 0 100 .. ..
6 Laminar in pipe 2.56 0.5 44 56 11 ..
6 Gas fluidized bed 1.74 0.42 58 42 .. ..
8 Gas fluidized bed 77 23
9 Gas fluidized bed 84 16
10 Gas fluidized bed 92 8
14 Gas fixed bed 13 87 3 .. ...
14 Gas in pipe 13.4 0.92 8 92 .. .. ...
2 Gas fluidized bed 1.15 0.17 87 13 .. .. 4
10 Gas spherical stirred reactor 1 .o 0 100 .. .. .. ...
7 Gas fluidized bed 2.12 0.34 58 42 19 .. Indefinable
4 Gas fluidized bed 1.5 0.29 70 30 4 .. ..
5 Gas fluidized bed 2.05 0.25 58 42 20 5 9
4 Liquid Denver flotation cell 1.05 -0.05 100 .. 9 5
5a Liquid Mat flotation cell 1.15 0.06 94 6 7 .. ...
56 Liquid Fagergren flotation cell 1.01 0 100 .. ...
5c Liquid MacKintosh flotation cell 1.19 0 100 .. ...
2 Liquid fixed bed 3.15 0.7 32 68 .. 2
11 Gas fluidized bed 2.2 0.55 45 55 .. ...
1 Gas fluidized bed 0.70 -0.25 100 .. 30 25
1 Gas fluidized bed 0.74 -0.3 100 .. 26 10
1 Gas fluidized bed 0.68 -0.2 100 .. 32 36
5 Solid fluidized bed 1.23 0.1 89 11 ...

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 T-
08

0'41
"F
0.3

OO C

Figure 10. F-Diagram for multistage system

A. 25% Plug flow. B. 25% D e a d space. C. 25% Short circuiting. D. 0.25 0 l a g

The F-functions expected for several cases are shown graphi-

cally for 1, 2, and 5 equal stages in series. Figure 9 represents
perfect mixing in each stage. I n Figures 10,A, 10,B, and
10,C the situation expected for 75% perfectly mixed with 25%
plug flow, dead space, and bypassing, respectively, is shown.
In Figure 1O,D, a response lag of 0.25 0 per stage is assumed.
Application to Multistage Experimental Results. Several
investigators have obtained residence time distribution data
for single-stage and identical multistage units. To test the
multistage model 9 and e/e were calculated from the experi-
mental F-function obtained for the single-stage unit. These
values were then used in Equation 19 to predict the F-function
for the multistage unit. The predicted and experimental
values were then compared. Jowet ( 9 ) obtained residence
time distribution data for a single Denver flotation cell and
for two cells in series. From his experimental data, the value
of 1.05 for 9 and -0.05 for C / O (Table 11) were obtained for
the single cell. The F-function calculated for two cells in
series with these same values of 9 and C / O is shown in Figure 11
along with the experimental results. The agreement is evident.
Overcashier, Todd, and Olney (74) obtained residence time
distribution data for a multistage fluidized bed. The F-func-
tions for four stages in series were calculated from the 7 and C / O
data derived for a single stage a t the three gas flow rates shown
t/2 e in Table 11. The calculated and experimental results are shown
Figure 1 1 . Experimental and derived in Figure 12. Again the agreement is good.
F-diagram for two Denver flotation cells in Some Anomalous Single-Stage Behavior. The data
series ( 9 ) obtained for the Forrester flotation cell ( 9 ) were omitted from

292 l&EC FUNDAMENTALS

 1.o Figure 12. Experimental and derived F-diagram for four
stages of fluidized beds in series ( I 4 )
0.9
A. Air velocity = 0.7 ft. per sec.
E. Air velocity = 1.1 ft. per sec.
0.8 4 C. Air velocity = 1.6 ft. per sec.

0.7
Table I because the experimental results yielded a curved h e
0.6 when plotted as ln(1 -
F ) us. t/O rather than the straight line
expected. The curve obtained is suggestive of the possibility
F 0.5 of multistage behavior, a possibility that should not be dis-
counted for a single-stage system. For example, a plug flow
0.4 reactor can be considered to be composed of a n infinite number
of perfectly mixed reactors in series. Also, the flow pattern
0.3 obtained in a baffled, stirred vessel (16) is suggestive of the
possibility of obtaining a system response equivalent to that
0.2 of a number of vessels in some parallel-series arrangement.
I n the case of anomalous behavior in a real single-stage system
0 .I the appropriate q , €/e, and n values can be calculated with the
aid of a n analog computer in order to avoid a tedious trial and
0
error solution.

Nomenclature
A = concentration in forcing function equation
a = fraction of effective system volume that is perfectly
mixed
C(t) = residence time function
C = concentration
d = fraction of system volume in dead space
E(t) = residence time function
F ( t ) = residence time function
f = fraction of material that moves with infinite velocity
L = lag
rn = lag factor
p = fraction of effective volume in plug flow
r = residence time correction factor
5' = Laplace complex variable
t = time
V = system volume
u = volumetric flow rate
E = system phase shift
q = coefficient of exponent
0 = average residence time
Sub scripts
i = inlet
o = outlet
literature Cited
(1) Danckwerts, P. V., Chem. Eng. Sci.2, 1 1953).
(2) Danckwerts, P. V., Znd. Chemist 30, 102 t1954).
(3) Danckwerts, P. V., Jenkins, J. W., Place, G., Chem. Eng. Sci.
3, 26 (1954).
(4) Gilliland, E. R., Mason, E. A., Znd. Eng. Chem. 44, 218 (1952).
(5) Gilliland, E. R., Mason, E. A., Oliver, R. C., Ibid., 45, 1177
(1953).
(6) Ham, A . , Coe, H. S., Chem. &Met. Eng. 19,663 (1918).
(7) Handlos, A. E., Kunstman, R. W., Schissler, D. O., Znd. Eng.
Chem. 49, 25 (1957).
(8) Huntley, A. R., Glass, W., Heigh, J. J., Zbid., 53, 381 (1961).
(9) Jowet, A., Brit. Chem. Eng. 6, 254 (1961).
(10) Lapidus, L., Znd. Eng. Chem. 49, 1000 (1957).
(11) MacMullin, R. B., Weber, M., Jr., Trans. Am. Inst. Chem.
Eners. 31. 409 11935).
(12) -Mason, R. D., P i k , E. L., Znd. Eng. Chem. 42,817 (1950).
(13) May, G. W., Chem. Eng. Progr. 5 5 , No. 12, 49 (1959).
(14) Overcashier, R. H., Todd, D. B., Olney, R. B., A.Z.Ch.E.J.
5 , 54 (1959).
(15) Resnick, W., Znd. Eng. Chem. 52, 865 (1960).
(16) Rushton, J. H., Oldshue, J. Y . , Chem. Eng. Progr. 49, 161
,-,
",'
I1 q < z \
(17) Tailby, R. S., Cocquerel, M. A. T., Trans. Znst. Chem. Engrs.
(London) 39, 195 (1961).
RECEIVED for review December 17, 1962
ACCEPTED June 26, 1963
This paper is based on work done in partial fulfillment of the
requirements for the D.Sc. degree ofthe Technion-Israel Institute of
Technology.

VOL. 2 NO. 4 NOVEMBER 1 9 6 3 293