Determining Residence Time

Distributions in a CSTR
CHE 4112
October 23, 2008

Shelli Schoolcraft
Sarah Wilkes

Executive Summary
The purpose of this experiment was to develop a mathematical model that predicts the ideal
transient concentration and residence time distribution in the unit operations laboratory
continuous stirred tank reactor. Data was collected using aqueous NaCl solutions of varying
concentrations to compare to these ideal models. This experiment provides important
information about the characteristics of the reactor and is useful in predicting the amount of
time a particular solution has spent in the vessel.
The negative step input approach with baffles was employed for this project. Fifteen total tests
were performed with three initial concentrations of 0.45 M, 0.60 M, and 0.75 M. Each
concentration was placed in the reactor tank and allowed to operate at mixing speeds of each
200, 400, 600, 800, and 1000 RPM. Sample solutions were taken from the effluent stream every
twenty seconds and the conductivity was measured and recorded. This data was converted into
concentration data and analyzed against the ideal models.
It was found that by using baffles during the mixing process, the presence of dead zones and bypass streams was greatly reduced. We concluded that the mixing speed shares an inverse
correlation with concentration in that as speed increases, the concentration decreases more
rapidly. By comparing the residence time distributions developed from collected data to the
ideal model, we determined that the 0.60 M solution gave the least deviation. Therefore by
using this initial concentration, the results generated are more predictable by conventional
methods.
We recommend further experimentation to verify these results. A single source of salt should be
used and the reactor should be operated at mixing speeds no lower than 100 RPM. Slower
speeds do not produce enough agitation and therefore a majority of the salt content settles at
the bottom of the tank and is not present in the effluent stream.

Table of Contents
Objective.......................................................................................................................................... 4
Background...................................................................................................................................... 4
Overview.......................................................................................................................................... 4
Experimental Equipment ................................................................................................................. 4
Environmental Health and Safety.................................................................................................... 6
Method of Analysis .......................................................................................................................... 6
Results ............................................................................................................................................. 8
Propagation of Error ...................................................................................................................... 16
Recommendations......................................................................................................................... 16
Appendix: Experimental Data and Sample Calculations ............................................................... 18

Objective
This experiment develops a mathematical model to predict the ideal transient
concentration in a continuous stirred tank reactor (CSTR). By developing this model, the
residence time distribution (RTD) is created and compared to the ideal RTD for multiple
impeller speeds.

Background
A residence time distribution is one of the most informative characterizations for a
reactor. The deviation of the experimental residence time distribution from the ideal
residence time distribution allows engineers in industry to adjust the parameters of the
reactor to provide the maximum desired output. Knowledge of the Bioflow III reactor in
the unit operations laboratory provides a good basis for scale-up industrial reactor
work.

Overview
Varying concentrations of an aqueous sodium chloride solution underwent mixing at
multiple impeller speeds in the Bioflow III CSTR in the unit operations laboratory. Due to
the transient nature of sodium chloride, the Sension 5 conductivity meter was utilized
and the residence time distribution was determined. The results are then compared to
the ideal residence time distribution model and the optimal impeller speed and solution
concentration are established.

Experimental Equipment
The basic experimental setup consists of several components: the reactor, a stopwatch,
three graduated cylinders, three buckets, a balance, baffles, and a conductivity meter.
For this experiment an aqueous salt solution enters from the top of the reactor and is
deflected by a horizontal plate in order to minimize vertical mixing effects. Baffles are
utilized to increase turbulence through agitation and prevent the formation of vertices
and dead zones. The fluid exits the bottom of the reactor where the effluent is collected
for analysis.

Figure 1. Continuous Stirred Tank Reactor[1]

A conductivity meter, Figure 2, is utilized to measure the ion concentration in the

gathered samples and these data are converted into sodium chloride concentrations. A
stopwatch is used to establish amount of time between sample collections.

Figure 2. Conductivity Meter[1]

Environmental Health and Safety

Sodium chloride is the only potential chemical hazard. Protective eyewear should be worn at all
times; however, if ocular exposure occurs, the eyewash station should be utilized. Also, the
sodium chloride solution causes skin irritation and will burn if spilled on an open wound.
Electrical hazards are present due to the use of electricity near liquids, so all valves should be
tightly sealed before the experiment is initiated. The weight of the motor and cover also pose
potential problems. Use caution when moving both.

Method of Analysis
Theory
A mathematical model to predict ideal transient concentration in a CSTR is developed by using
principles of a simple material balance. From the material balance, the ideal residence time
distribution is derived. In order to create the experimental model, a negative step input method
is utilized. This process is used instead of the positive step method due to the difficulty of
keeping an initial tracer concentration in the feed stream.
Accumulation = In Out

Eq. (1)

Since the negative step was used, Co = 0, reducing Eq. 1 to:

dCi
dt

0 QCi

t>0

Eq. (2)

Where,
Ci = Concentration of species i (mol/L)
t = time (sec)
Q = Volumetric flowrate of species i (L/sec)
V = reactor volume (L)
For this model to work, certain assumptions must be made. First, the ideal model assumes
perfect mixing. There are no bypass streams or dead zones and the inlet concentration is
instantly and completely mixed. The fluid stream must also maintain a constant density and
temperature throughout the process. The final assumption is the system operates at steadystate and a single, irreversible reaction takes place. The rate expression follows a first order
reaction.
The integration of Eq. 2 yields the ideal concentration model:

Ci (t )

Co e

t/

Eq. (3)

Where,
Co = Initial concentration of species i (mol/L)

T = V/Q = Space time (sec)

This equation gives the concentration of species i in the outlet stream at any time t.
The residence-time distribution function, E(t), is given by Eq. 4:

C i (t )

E (t )

Eq. (4)

C i (t )dt
0

By substituting Eq. 3 into Eq. 4 and solving, we obtain the following expression which describes
the amount of time a tracer spends in the reactor:

E (t )

t/

Eq. (5)

The ideal cumulative concentration distribution, F(t), is also practical when evaluating the
residence time distribution, providing the percent of material that has a RTD of time t or less[2].

F (t )

Ci ,out
Co

Eq. (6) [2]

step

By definition, E(t) = -dF(t)/dt for a negative step input. Therefore, by differentiating Eq. 6, we
obtain the residence-time distribution function for a non-ideal CSTR.

E (t )

d Ci ,out
dt C o

Eq. (7)
step

Experimental Method
Emergency Shutdown[1]
1. Turn OFF the CSTR ON/OFF switch.
2. Close the water flow valve attached to the CSTR water feed line.
3. Notify professors and students of potential hazards.

Operating Procedure[1]
1. Calibrate conductivity meter.
A. Make aqueous sodium chloride solution using graduated cylinder.
B. Place probe in solution. Avoid probe contact with walls or bottom of container.
C. Press CAL. which creates a reference standard.

2.
3.
4.
5.
6.
7.

8.
9.
10.
11.

D. Scroll to factory calibration settings and press enter.

E. Repeat for multiple standard solutions.
F. Plot concentration versus conductivity to obtain calibration.
Fill tank with known amount of solution.
Set impeller to desired speed.
Allow solution to mix thoroughly.
Place sample collection beaker under the reactor exit nozzle.
Open water control supply valve to begin water flow into CSTR.
Use the beaker and stopwatch method to record conductivity measurements with
respect to time using constant time intervals. To operate the conductivity meter:
A. Place probe into sample, immersing the slot on the end of the probe.
B. Shake the probe for five to ten seconds to remove bubbles.
C. Press COND. to calculate conductivity.
D. Record conductivity and time values.
E. Use the concentration versus conductivity plot to record concentration values
Stop experiment once the conductivity values flat line near water conductivity value
After the run is complete, thoroughly clean the tank to remove any excess salt residue.
Repeat steps 2-9 for additional impeller speeds.
Repeat steps 1-10 for additional sodium chloride solutions.

Shutdown Procedure[1]
1.
2.
3.
4.

Turn the CSTR impeller speed setting to 0 RPM.

Turn OFF the CSTR ON/OFF switch.
Close the water control valve on the wall to the right of the CSTR.
Close the water control regulator on the wall to the right of the CSTR.
5. Close the water flow valve attached to the CSTR feed line.

Data Processing
In order to establish the ideal RTD, concentration curve, and F curve, Eqs. 2 and 4 are evaluated
and plotted as a function of time. Ci is identified by adding a known quantity of NaCl tracer to
the reactor. V is identified by adding a known amount of water into the reactor tank and Q is
identified by the stop watch and beaker method.
Once the base line is established, the experimental concentration curves are created by taking
effluent samples from the outlet at known times and measuring NaCl conductivity. Again Eqs. 2
and 4 are utilized to produce concentration curves with respect to time. Each set of data for a
given sodium chloride solution is compared to the ideal curve.

Results
The initial conductivity readings for each known concentration were used to develop a
conductivity meter calibration chart. The result, Figure 3, was used to convert the conductivity
data into workable concentrations. These concentrations represent the amount of NaCl present
in the reactor at any given time.

Figure 3. Conductivity Meter Calibration

The consequent concentration values were plotted over time for each solution/mixing speed
combination. An ideal curve was also calculated using Eq. 4 and plotted on the same graph.
Sample calculations can be viewed in the Appendix section of this report. In nearly all trials, the
solutions exhibited a faster exponential rate of reduction as the mixing speed was increased.
This is contrary to the findings of a similar study performed by Hamit et. al in which no baffles
were used.[1] The inverse correlation between concentration and mixing speed supports our
predictions, suggesting that baffles help reduce the presence of dead zones and vortices. The
0.60 M solution (150 g NaCl), in particular, generated the results that most closely matched the
ideal curve. These data can be viewed in Figures 4-6.

Figure 4. 0.45 M Concentration Data

10

Figure 5. 0.60 M Concentration Data

11

Figure 6. 0.75 M Concentration Data

In accordance with Eq. 6, the negative derivatives of the best-fit line equations for each mixing
speed were taken to obtain the residence time distribution function, E(t). Time values were
plugged into each equation to calculate the RTD. The E values for nearly every trial are above
the ideal curve until about 200 seconds, and then continue below the curve until it converges at
700 sec. The equations are tabulated in Table 1, while the corresponding RTD graphs are
represented in Figures 7-9.

12

C(t)
Mixing
Speed
(RPM)

Ideal

200

E(t)

0.45
M

0.60
M

0.75
M

e-0.005t

e-0.003t

e-0.004t

Ideal

0.45 M
0.005e0.005t

-0.006t

400
600
800
1000

e
e-0.004t

-0.006t

-0.005t

-0.006t

-0.004t

-0.004t

-0.004t

-0.004t

0.006e

-0.005t

0.006t

-0.005t

-0.006t

-0.006t

0.004e
0.004t

0.60 M
0.003e0.003t

0.004e
0.004t

0.004t

0.005e0.005t

0.006e

0.004e

0.005e-

0.005e-

0.004e-

0.006e-

0.006e-

0.006t

0.005t

0.006e
0.006t

0.75 M
0.004e-

0.004t

0.004t

0.004e
0.004t

0.005t

0.006t

0.006t

Table 1. C(t) and E(t) Equations

Figure 7. 0.45 M RTD

13

Figure 8. 0.60 M RTD

14

Figure 9. 0.75 M RTD

It is obvious that the 0.60 M solution RTD once again gave results closest to the ideal
calculations. The curves are also more consistent at mixing speeds above 200 RPM, which, based
on these findings, leads to more accurate predictability.
One experimental run was performed at a mixing speed of 25 RPM in an attempt to produce a
concentration vs. time curve that had an observably larger difference than any of Figures 4-6.
This mixing speed, however, proved to be too insignificant to obtain any reliable data. There was
not enough agitation to thoroughly mix the amount of salt, and therefore the majority settled at
the bottom of the tank. The salt began to dissolve around 200 seconds. At this point, the NaCl is
distributed more evenly throughout the vessel, leading to more reliable readings. Figure 10
shows the data collected from this trial.

15

Figure 10. 0.45 M Concentration Data at 25 RPM

Propagation of Error
The increase in ideality from the 0.45 M to the 0.60 M mixtures can be justified by the increase
in solution saturation. The 0.75 M mixture, however, does not follow this trend. A possible
explanation is that a different box of salt was used to make this concentration, creating a
significant source of error. There were many other potential sources for error in this
experiment. The liquid level in the tank may have varied slightly for each run, allowing for
differences in initial concentrations. The bucket and stopwatch method, which was used to
calculate flowrates, is inherently inaccurate. Also, the outlet stream is located high on the vessel
so that any NaCl that may have settled near the bottom of the tank will not show up in the
effluent.

Recommendations
We recommend this experiment be performed again with a single a single source of salt. If the
results indicate that higher concentrations more closely mimic ideal conditions, then it can be
concluded the solutions of 0.60 M and higher are optimal to run in this particular CSTR. It should

16

also be noted that unless the outlet location is lowered on the tank, it is not recommended to
operate the CSTR at speeds lower than 100 RPM.

References
[1] Hamit, Josh, Daniel Meysing, and Afshan Samli. Development of a mathematical
model in a Continuous Stirred Tank Reactor. September 18, 2008.
[2] Fogler, H. Scott. Elements of Chemical Reaction Engineering: 4th Edition. P. 869-878
[3] Sodium Chloride MSDS. ScienceLab.
Http://sciencelab.com/msds.php?msdsid=9927593. 29 Oct. 2008

17

Appendix: Experimental Data and Sample Calculations

100 g Concentration (M)
Time
(sec)
0
20
40
60
80
100
120
140
160
180
200
220
240
260
280
300
320
340
360
380
400
420
440
460
480
500
520
540
560
580
600
620
640
660
680
700
720
740
760
780

Ideal
1.000
0.930
0.864
0.803
0.746
0.694
0.645
0.599
0.557
0.518
0.481
0.447
0.416
0.387
0.359
0.334
0.310
0.289
0.268
0.249
0.232
0.215
0.200
0.186
0.173
0.161
0.149
0.139
0.129
0.120
0.112
0.104
0.096
0.090
0.083
0.077
0.072
0.067
0.062
0.058

200 RPM
1.000
0.912
0.817
0.725
0.637
0.571
0.505
0.447
0.395
0.346
0.310
0.275
0.243
0.216
0.192
0.171
0.150
0.135
0.119
0.106
0.095
0.084
0.076
0.068
0.061
0.055
0.050
0.046
0.041
0.040
0.037
0.034
0.031
0.029
0.028
0.025
0.024
0.022
0.021
0.021

400 RPM
1.000
0.856
0.785
0.690
0.611
0.532
0.467
0.414
0.357
0.313
0.276
0.240
0.212
0.187
0.164
0.145
0.128
0.113
0.099
0.089
0.079
0.070
0.063
0.056
0.050
0.045
0.041
0.038
0.036
0.032
0.030
0.028
0.026
0.024
0.023
0.022
0.021
0.020
0.019
0.018

600 RPM
1.001
0.894
0.790
0.697
0.619
0.541
0.475
0.423
0.366
0.321
0.283
0.248
0.218
0.193
0.180
0.149
0.132
0.116
0.103
0.092
0.080
0.072
0.065
0.058
0.052
0.047
0.042
0.040
0.037
0.033
0.031
0.029
0.026
0.025
0.024
0.022
0.021
0.020
0.019
0.018

800 RPM
1.000
0.872
0.761
0.702
0.630
0.562
0.501
0.447
0.403
0.354
0.315
0.283
0.252
0.225
0.202
0.180
0.162
0.144
0.129
0.116
0.104
0.093
0.085
0.076
0.069
0.063
0.057
0.052
0.048
0.044
0.040
0.038
0.036
0.033
0.031
0.029
0.027
0.025
0.024
0.023

1000 RPM
1.000
0.865
0.747
0.626
0.563
0.496
0.425
0.366
0.320
0.278
0.241
0.211
0.183
0.161
0.141
0.123
0.107
0.096
0.084
0.075
0.066
0.059
0.053
0.047
0.042
0.040
0.036
0.033
0.031
0.028
0.026
0.025
0.023
0.022
0.021
0.020
0.020
0.018
0.018
0.017

Table 2. 0.45 M Concentration Data

18

150 g Concentration (M)

Time
(sec)
0
20
40
60
80
100
120
140
160
180
200
220
240
260
280
300
320
340
360
380
400
420
440
460
480
500
520
540
560
580
600
620
640
660
680
700
720
740
760
780

Ideal
1.000
0.930
0.864
0.803
0.746
0.694
0.645
0.599
0.557
0.518
0.481
0.447
0.416
0.387
0.359
0.334
0.310
0.289
0.268
0.249
0.232
0.215
0.200
0.186
0.173
0.161
0.149
0.139
0.129
0.120
0.112
0.104
0.096
0.090
0.083
0.077
0.072
0.067
0.062
0.058

200 RPM
1.001
0.952
0.882
0.822
0.767
0.710
0.662
0.613
0.570
0.530
0.493
0.458
0.428
0.395
0.369
0.341
0.320
0.297
0.279
0.262
0.244
0.229
0.214
0.203
0.191
0.180
0.170
0.160
0.152
0.144
0.138
0.131
0.125
0.120
0.114
0.110
0.106
0.102
0.098
0.095

400 RPM
0.999
0.935
0.870
0.815
0.758
0.691
0.655
0.611
0.565
0.526
0.488
0.456
0.422
0.394
0.364
0.337
0.312
0.290
0.268
0.249
0.230
0.215
0.199
0.185
0.172
0.160
0.149
0.139
0.122
0.117
0.109
0.103
0.097
0.090
0.084
0.078
0.073
0.068
0.064
0.060

600 RPM
1.000
0.921
0.860
0.799
0.745
0.692
0.646
0.598
0.557
0.517
0.480
0.446
0.414
0.383
0.355
0.327
0.304
0.281
0.261
0.241
0.224
0.209
0.193
0.179
0.165
0.153
0.142
0.132
0.122
0.114
0.106
0.098
0.091
0.085
0.079
0.074
0.069
0.064
0.060
0.056

800 RPM
1.001
0.902
0.853
0.791
0.736
0.682
0.632
0.580
0.538
0.497
0.459
0.423
0.390
0.360
0.332
0.306
0.281
0.259
0.239
0.219
0.203
0.188
0.173
0.159
0.148
0.136
0.126
0.117
0.107
0.099
0.092
0.085
0.079
0.073
0.068
0.062
0.058
0.054
0.050
0.047

1000 RPM
0.999
0.922
0.855
0.794
0.734
0.683
0.633
0.584
0.542
0.503
0.465
0.430
0.399
0.369
0.341
0.316
0.291
0.269
0.250
0.230
0.216
0.199
0.183
0.168
0.158
0.146
0.135
0.125
0.116
0.107
0.100
0.092
0.086
0.080
0.074
0.070
0.065
0.060
0.056
0.053

Table 3. 0.60 M Concentration Data

19

Time (sec)
0
20
40
60
80
100
120
140
160
180
200
220
240
260
280
300
320
340
360
380
400
420
440
460
480
500
520
540
560
580
600
620
640
660
680
700
720
740
760
780

Ideal
1.000
0.930
0.864
0.803
0.746
0.694
0.645
0.599
0.557
0.518
0.481
0.447
0.416
0.387
0.359
0.334
0.310
0.289
0.268
0.249
0.232
0.215
0.200
0.186
0.173
0.161
0.149
0.139
0.129
0.120
0.112
0.104
0.096
0.090
0.083
0.077
0.072
0.067
0.062
0.058

200 RPM
0.999
0.919
0.834
0.778
0.718
0.660
0.611
0.561
0.516
0.471
0.432
0.399
0.365
0.332
0.307
0.281
0.255
0.233
0.214
0.197
0.181
0.165
0.152
0.139
0.128
0.117
0.108
0.099
0.091
0.084
0.077
0.068
0.064
0.060
0.055
0.051
0.047
0.044
0.040
0.037

200 g Concentration (M)

400 RPM 600 RPM 800 RPM
1.000
1.000
1.000
0.907
0.910
0.833
0.821
0.825
0.762
0.743
0.737
0.697
0.672
0.664
0.636
0.609
0.603
0.580
0.551
0.545
0.529
0.499
0.492
0.461
0.451
0.441
0.417
0.409
0.399
0.377
0.370
0.360
0.339
0.335
0.325
0.305
0.303
0.294
0.273
0.275
0.267
0.243
0.249
0.240
0.216
0.225
0.215
0.191
0.204
0.194
0.188
0.185
0.175
0.167
0.167
0.157
0.147
0.152
0.142
0.129
0.137
0.127
0.112
0.124
0.114
0.096
0.113
0.103
0.092
0.102
0.092
0.089
0.093
0.083
0.077
0.084
0.074
0.065
0.076
0.066
0.055
0.069
0.059
0.049
0.063
0.053
0.046
0.057
0.049
0.038
0.052
0.044
0.036
0.047
0.039
0.034
0.043
0.035
0.031
0.039
0.031
0.028
0.035
0.029
0.025
0.032
0.026
0.022
0.029
0.023
0.019
0.027
0.021
0.016
0.024
0.020
0.014
0.022
0.018
0.012

1000 RPM
1.000
0.890
0.790
0.701
0.622
0.552
0.490
0.435
0.386
0.343
0.304
0.270
0.240
0.213
0.189
0.168
0.150
0.133
0.118
0.105
0.094
0.083
0.074
0.066
0.059
0.053
0.047
0.042
0.038
0.034
0.030
0.027
0.024
0.022
0.020
0.018
0.016
0.015
0.013
0.012

Table 4. 0.75 M Data

20

Time (sec)
0
20
40
60
80
100
120
140
160
180
200
220
240
260
280
300
320
340
360
380
400
420
440
460
480
500
520
540
560
580
600
620
640
660
680
700
720
740
760
780

Ideal
1.000
0.930
0.864
0.803
0.746
0.694
0.645
0.599
0.557
0.518
0.481
0.447
0.416
0.387
0.359
0.334
0.310
0.289
0.268
0.249
0.232
0.215
0.200
0.186
0.173
0.161
0.149
0.139
0.129
0.120
0.112
0.104
0.096
0.090
0.083
0.077
0.072
0.067
0.062
0.058

100 g
25 RPM
0.102
0.036
0.048
0.053
0.057
0.053
0.059
0.061
0.061
0.062
0.062
0.059
0.057
0.054
0.050
0.046
0.044
0.041
0.040
0.037
0.035
0.033
0.031
0.030
0.029
0.027
0.026
0.025
0.024
0.023
0.022
0.022
0.022
0.021
0.021
0.020
0.020
0.020
0.019
0.019

Table 5. 0.45 M Slower Mixing Speed

21

Sample Calculations

Conductivity to Concentration Conversion:

From calibration chart,

33.856 C
Therefore, for

33.856

= 9.95 mS/cm,

9.95
33.856

0.294 M

Ideal C(t) Curve:

From Eq. 2,

Ci (t )

Co e

t/

Ci (t )
Co

t/

Where,

5700 mL
mL
20.833
s

V /Q

273.6s

Ideal E(t) Curve:

From Eq. 4,

E (t )

t/

Where,

273.6s
And therefore,

E (t )

e t / 273.6
273.6

22