ABSTRACT

The experiment was constructed to examine the effect of a pulse input and step change input in
a tubular flow reactor. Other than that, the aim of this experiment is to construct a residence
time distribution (RTD) function for the tubular flow reactor. The first step in running this
experiment was opened the valve V9 and switched on pump P1. The flow rate of de-ionized
water into the reactor R1 was controlled to constant at 700 mL/min at Fl-01. The water was
continued to flow until the conductivity of inlet and output were stable a low levels. The value
was 0.0. Then, V9 and P1 were closed and turned off. V11 and P2 were opened. P2 was
adjusted to give a constant flow rate of salt solution into R1 at 700 mL/min at Fl-02. The salt
solution was allowed to flow for one minute. Then, the timer was reset and restarts. This allowed
the time started at the average pulse input. V11 and P2 were closed and quickly opened V9 and
P1. For every 30 s, the conductivity of Q1 and Q2 were recorded until all the readings were
constant and approached the stable low level values. Then, a graph of outlet conductivity values
versus time was plotted to get C(t) curve. From the C(t) curve, graph of E(t) is plotted as the
function of time. This is the residence time distribution (RTD) function for the plug flow reactor.
In experiment 1, the conductivity increased at minute 1.0 at 0.2 ms/cm and reached the peak at
minute 2.0 with conductivity at 2.6 ms/cm. Then, the conductivity decreased as the time
increased until its reading is 0.0 ms/cm. It showed that the reactant was all used up in the
reactor. The time the materials spend in the reactor thus called the residence time. Same steps
as in the first experiment, a graph of conductivity versus time was plotted to find the C(t) curve.
Then, E(t) graph is plotted from the values obtained versus the time. The mean residence time,
tm was 2.128 min, second moment variance, 2 was 25.89 and the third moment skewness, s3
was -0.232. In experiment 2 which is the step change input experiment, the graph of outlet
conductivity values versus time show that the curve start increasing rapidly only at 2.5 min and
constant at 3.5 min with 2.8 conductivity value. The mean residence time, t m was 22.263,
second moment variance, 2 was 1556.452 and the third moment skewness, s3 was -89.222.
The value of E(t) is depends on the value of C(t).

INTRODUCTION
In chemical plant especially in chemical processes, reactor is one vital item needed for raw
materials to undergo a chemical reaction to form desired output or products. Thus, the operation
and design of the reactors play an important role for a success of processes in the industrial.
Depending on the nature of the feed materials and the output, the reactors are appeal in many
forms. Hence, proper approaches of understanding of the nature of the reactors work to handle
the system of reaction. Reactor is divided into two main types which is batch reactors and
continuous flow reactors.
Plug reactor is considered as one of the continuous flow reactors that almost always operated at
steady state (Fogler, 2006). It is also known as tubular reactor with its cylindrical pipe and
mostly used for gas-phase reactions. It also resembles batch reactors in providing initial driving
forces, which diminish as the reactions progress down the tube. The key assumption is that
tubular acts like plug where it mixed in the radial direction but not in the axial direction.
According to Fogler, the reactants are continually consumed as they flow down the length of the
reactor. The systems is said to be in the uniform velocity as in turbulent flow and no radial
variation in reaction rate.

Figure 1. Plug Flow Reactor

As the reactor suggested, there is no mixing of the medium along the length of the reactor since
PFR is an idealized reactor. However, there is no such reactor exist in reality because it is quite
impossible to have no mixing at all during the reaction. At most, the amount of mixing in the
reactor can be minimized.
In PFR, the residence time is the same as for all elements of fluids. However, there is no
interchange of material in the pug with the material in the other leading or following occurs.
2

There is no back mixing in the reactor. The advantages of PFR are that it has a high volumetric
unit conversion, long periods of time in operation without any maintenance. However, it is hard
to control the temperature of the reactors and the maintenance of the reactor is quite costly
compared to CSTR. As it flows down the tubular flow reactor, the residence time of the plug is a
function of it position in the reactor.
In this experiment, the reactor used is BP 101-B that has been designed for students in order to
perform an experiment on chemical reactions in liquid phase under isothermal and adiabatic
conditions. It comes with a jacketed plug flow reactor, individual reactant tank of feed and
pumps, temperature sensors and conductivity measuring sensor. For this purpose,
saponification reaction between ethyl acetate and sodium hydroxide can be performed.
In addition, the injection of a tracer such as salt solution in the reactor feed can perform the
transient behavior in the PFR and the conductivity can be measured at the outlet of the reactor
as it indicate the progression of the tracer throughout the reactor.

OBJECTIVES
1. To examine the effect of a pulse input in a tubular flow reactor.
2. To examine the effect of a step change input in a tubular flow reactor.
3. To construct a residence time distribution (RTD) function for the tubular flow reactor.

THEORY
As fluid flows down the plug flow reactor, the fluid is mixed in the radial direction, but mixing
does not occur in the axial direction each plug of fluid is considered a separate entity as it flows
down the pipe. However, as the plug of fluid flows downstream, time passes. Therefore, there is
implicit time dependence even in steady-state PFR problems. However, because the velocity of
the fluid in the PFR is constant, time and downstream distance are interchangeable.
A given chemical reaction rate can be expresses in several ways either as the rate of
disappearance of the reactants (

r A ) or the rate of formation of products ( r A ). For

instant, in the following reaction,

aA + bB cC + dD
Where;

A = B = reactants
C = D = products
a = b = c = d = stoichiometric coefficients

If the species A is considered as the reaction basis, then the rate of reaction can be represented
by the rate of disappearance of A. The rate of reaction can be also represented by the rate of
disappearance of another species such as rB and the rate of formation of a product such as rC
and rD. They can be related in the following equation,

r A r B r C r D
=
= =
a
b
c d

The rate of chemical reaction is an intensive quantity and depends on temperature and
concentration. One of the most common forms of rate law equation is shown to be:

r A=K A C aA C bB
The saponification of sodium hydroxide and ethyl acetate is represented by the following
stoichiometric equation:
4

C H 3 COO C 2 H 5 + NaOH C H 3 COONa+C 2 H 5 OH

This reaction is found to be second order and practically irreversible. The rate of reaction is
represented in the following:

r=k C A C B Kmol/(m 3 s)
Where:

(E
RT )

k =k 0 e

(Arrhenius law expression)

k 0 =18.6 106 m3 /(kmol . s)

E=4.688 104 J /mol
The reactors residence time is defined as the reactor volume divided by the total feed flow
rates.

V TFR
V0

For a second order equimolar reaction with the same initial reactants concentration

C
( A 0=C B 0) , the rate law is shown to be:

r A=k C A C B=k C2A 0=k C 2A 0 (1 X)2

V TFR =

V0
X
(
)
k C A 0 1X

For Constant PFR volume, flow rate and initial concentrations, the reaction rate constant is
calculated by:

k=

V0
X
(
)
V TFR C A 0 1X

The conversion (or fractional conversion), denoted X, is a frequently used measure of the
degree of reaction. It i s defined as

X=

moles of a species that have reacted

moles of same species iniatially present

In pulse input, an amount of tracer is injected in one shot into the feed stream entering the
reactor in as short time as possible. The outlet concentration is then measured as a function of
time. The effluent concentration versus time curve is referred to as C(t) curve in residence time
distribution analysis.
The residence-time distribution of a reactor is a characteristic of the mixing that occurs in the
chemical reactor. In an ideal plug flow reactor, all the atoms of materials leaving the reactor
have been inside the reactor for exactly the same amount of time. The time the atoms spent in
the reactor is called the residence time of the atoms in the reactor.

By considering an injection of a tracer pulse for a single input and single output system, for a
small time increment, t which is sufficiently small so that the concentration of tracer is
essentially constant during the time period, the amount of tracer C(t) exiting between time t and
t + t is then

N =C ( t ) v t
Dividing by the total amount of material that was injected into the reactor, N0

 N vC (t)
=
t
N0
N0
For a pulse injection,

E (t)=

vC( t)
N0

So that

N
=E ( t ) t
N0
In which E(t) is the residence time distribution function that describes in a quantitative manner
how much time different fluid elements have spent in the reactor. The quantity E(t)dt is the
fraction of the fluid exiting the reactor that has spent time t and t + t inside the reactor.

By differentiation and integration

d N =vC(t )dt

N0 vC ( t ) dt
0

The volumetric flow rate v is constant, so E(t) can be define as

E (t)=

C (t )

C ( t ) dt
0

For step change, a constant rate of tracer addition to a feed that is initiated at time t = 0. Before
this time no tracer was added to the feed. Thus, we have
C0(t) = 0

t<0

C0(t) = C0

t0

Because the inlet concentration is a constant with time, Co, it can be take outside the integral
sign,
t

C out = C
0

E ( t ' ) dt '
0

Dividing by C0 yields

C out
C0

] step =

F ( t )=

[ ]

C out
C0

E ( t ' ) d t ' =F(t )

0

step

We differentiate this expression to obtain the RTD function E(t):

E (t)=

[ ]

d C (t )
dt C 0

step

APPARATUS
1) Soltec Tubular Flow Reactor instrument
2) Solution 0.025M Sodium Chloride and De-ionized water
3) Stopwatch

Figure 2Tubular Flow Reactor (SOLTEQ model :BP 101-B)

PROCEDURES
Operating procedures
General start-up procedures
1.
2.
3.
4.

All the valves are initially except for valve V7.

20 liter of salt solution (NaCl; 0.025M) was prepared.
The feed tank was filled with the NaCl solution.
The power was turn on from the control panel.
9

5. The water de-ionizer was connected to the laboratory water supply. Valve V3 was
opened and filled with the de-ionized water. Then, the valve V3 closed.
6. Valve V2 and V10 was opened before pump P1 switched on. P1 flow controller was
adjusted to obtain a flow rate of approximately 700 ml/min at flow meter FT-01. The
conductivity displays were observed at low value before valves V10 was closed and
pump P1 was switched off.
7. Valves V6 and V12 were opened with pump P2 was switched on. The flow controller was
also adjusted to obtain a flow rate of approximately 700ml/min at flow meter FT-02. After
the flow rate was obtained valves V12 was closed and pump P2 was switched off.

General Shut-Down Procedure

1. Both pump P1, P2 and P3 were switched off and valve V2 and V6 switched off.
2. The heater then switched off.
3. The water keeps circulating through the reactor while the stirrer motor was running to
allow the water jacket to cool down to room temperature.
4. The power control then switched off.

Experiment 1 : Pulse input in a tubular flow reactor

1. Valve V9 was opened and pump P1 was switched on.
2. Pump P1 flow controller was adjusted to give a constant flow rate of de-ionized water
into the reactor R1 at approximately 700 ml/min at FT-01.
3. The de-ionized water was allowed to flow through the reactor until the inlet (QI-01) and
outlet (QI-02) conductivity values are stable at low levels. The conductivity value was
recorded.
4. Valve V9 was closed and pump P1 was switched off.
5. Valve V11 was opened and pump P2 was switched on and the timer start
simultaneously.
6. Pump P2 flow controller was adjusted to give a constant flow rate of salt solution into the
reactor R1 at 700 ml/min at FT-02.
10

7. The salt solution was allowed to flow for 1 minute, then reset and starts the timer. This
will start the time at the average pulse input.
8. Valve V11 was closed and pump P2 was switched off before valve V9 was quickly
opened and pump P1 was switched on.
9. The de-ionized water flow rate was make sure to always maintained at 700 ml/min by
adjusting P1 flow controller.
10. The conductivity value at both inlet (QI-01) and outlet (QI-02) was recorded at regular
intervals of 30 seconds.
11. The conductivity value was recorded until the reading at both inlet and outlet are almost
constant and approach the stable low level values.

Experiment 2 : Step change input in a tubular flow reactor

1. The general start-up procedure was performed.
2. Valve V9 was opened and pump P1 was switched on.
3. Pump P1 flow controller was adjusted to give a constant flow rate of de-ionized water
into the reactor R1 at approximately 700 ml/min at FT-01.
4. The de-ionized water was allowed to flow through the reactor until the inlet (QI-01) and
outlet (QI-02) conductivity values are stable at low levels. The conductivity value was
recorded.
5. Valve V9 was closed and pump P1 was switched off.
6. Valve V11 was opened and pump P2 was switched on and the timer start
simultaneously.
7. The conductivity value at both inlet (QI-01) and outlet (QI-02) was recorded at regular
intervals of 30 seconds.
8. The conductivity value was recorded until the reading at both inlet and outlet are almost
constant.

11

RESULT
Flow rate: 700 mL/min
Experiment 1: Pulse Input in a Tubular Flow Reactor

Time (s)

Time (min)

0.0
30.0
60.0
90.0
120.0
150.0
180.0
210.0
240.0

0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0

Pulse Input
Conductivity (ms/cm)
Input, Q1
Output, Q2
0.0
0.0
0.4
0.0
0.1
0.2
0.1
2.3
0.0
2.6
0.0
0.5
0.0
0.2
0.0
0.1
0.0
0.0

12

Experiment 2: Step Change Input in a Tubular Flow Reactor

Time (s)

Time (min)

0.0
30.0
60.0
90.0
120.0
150.0
180.0
210.0
240.0
270.0
300.0
330.0
360.0
390.0
420.0
450.0

0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5

Step Change Input

Conductivity (ms/cm)
Input, Q1
Output, Q2
0.0
0.0
4.4
0.0
4.7
0.0
4.8
0.0
4.9
0.0
4.9
2.0
4.9
2.0
4.9
2.9
4.9
2.9
4.8
3.0
4.8
3.0
4.8
3.1
4.7
3.1
4.6
3.2
4.6
3.2
4.5
3.2

13

CALCULATIONS
Experiment 1: Pulse Input in a Tubular Flow Reactor

C ( t ) dt
0

= area under the graph of C(t)dt.

4.0

C ( t ) dt= 0. 442 t2 +1.718 t 0.2758 dt

0

0.5

1.0

1.5

2.0

0.442t 2 +1.718 t0.2758 dt+ 0.442t 2+ 1.718t0.2758 dt + 0.442 t 2 +1.718 t0.2758 dt + 0.442
0

0.5

1.0

1.5

0.0584+0.3775+ 0.6445+0.684+ 0.5488+ 0.31550.028 4

2.6003
E (t)=

C (t)

C ( t ) dt

C (t)
2.6003

When C (t) = 0.2

0.2
2.6003

14

= 0.0769

Mean residence time, tm =

2.5

tE ( t ) dt
0

3.0

3.5

4.0

1.328 dt+ 2.000 dt+ 0.481 dt+ 0.231 dt + 0.135dt

2.0

2.5

3.0

3.5

2.0

0.077 dt+
1.5

0.5

1.0

1 .5

t m= 0.0 dt+ 0.0 dt+

0.0

0.5

1 .0

0.000+0.000+0.0385+ 0.664+1.000+0.241+0.116+0.068+ 0.000

2.128 min
2

tt m E ( t ) dt

Second moment, Variance, 2 =

When t = 1.0 ;
2

1.02.128 ( 0.077)
tt m 2 E ( t ) dt=

0.098
2

t t m E ( t ) dt =0+0+0+11.47 +11.19+ 2.81+ 0.36+0.06+0

25.89

15

tt m E ( t ) dt

3
1
Third moment, Skewness, s =

3
2 0

1
(0.055)
4.212

0.232

Time t, (min)

0.000

0.500

1.000

1.500

2.000

2.500

3.000

3.500

4.000

C(t) (ms/cm)

0.000

0.000

0.200

2.300

2.600

0.500

0.200

0.100

0.000

E (t)

0.000

0.000

0.077

0.885

1.000

0.192

0.077

0.038

0.000

tE (t)

0.000

0.000

0.077

1.328

2.000

0.481

0.231

0.135

0.000

tm

0.000

0.000

0.039

0.664

1.000

0.241

0.116

0.068

0.000

(t tm )2

4.528

2.650

1.272

0.394

0.016

0.138

0.760

1.882

3.504

Variance, 2

0.000

0.000

0.049

0.174

0.008

0.013

0.029

0.036

0.000

0.000

0.000

4.212

3.712

37.38

25.97

14.23

12.10

0.000

0.038

0.128

0.363

6.01

3
2

Skewness,s3

0.0

0.0

0.232

0.405

0.000

Experiment 2 : Step change input in a tubular flow reactor

E (t)=

Where

d C (t)
dt C0

( )

C0

= final constant value of outlet conductivity

16

= 3.2

C ( t ) = -0.091t2 + 1.2122t 0.7569

When : t = 0
C (t) = - 0.7569

C (t)
C0

0. 7569
=
3.2

= -0.237

Mean residence time, tm =

0.5

1.0

tE ( t ) dt
0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

0 dt + 0 .027 dt+ 0 .114 dt 0 .402 dt+ 0. 816 dt+ 1.333 dt+ 1.9 3 2 dt+ 2. 594 dt+ 3. 296 dt+
0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

00.014+0.057+ 0.201+ 0.408+0.666+0.966+ 1.297+1.648+2.007+2.368+ 2.714+3.039+3.328+3.577

22.263
2

t t m E ( t ) dt

Second moment, Variance, 2 =

When t = 0.5 ;
2

0.522.263 (0.0 5 4 )
tt m 2 E ( t ) dt =

17

4.5

25.576
2

t t m E ( t ) dt =12.788+25.771+57.768+83.76+104.089+119.483 +130.435+137.418+140.724+141.379+

= 1556.452

tt m 3 E ( t ) dt

3
1
Third moment, Skewness, s =

3
2 0

39.45

3
2

(278.305547.9601199.4311697.23252057.1022301.5892 447.3442509.6532499.677

= -89.222

Time,
t(min)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0

E (t)
-0.237
-0.054
0.114
0.268
0.408
0.533
0.644
0.741
0.824
0.892
0.947
0.987
1.013
1.024
1.022

tm
0.000
-0.135
0.057
0.201
0.408
0.666
0.966
1.297
1.648
2.007
2.368
2.714
3.039
3.328
3.577

tE ( t ) dt
0.000
-0.027
0.114
0.402
0.816
1.333
1.932
2.594
3.296
4.014
4.735
5.429
6.078
6.656
7.154

( t - tm )3

Variance,

Skewness,s3

E(t)
0.000
556.609
-1095.919
-2398.861
-3394.465
-4114.204
-4603.177
-4894.688
-5019.305
-4999.353
-4871.905
-4649.137
-4357.239
-4010.667
-3633.880

2
0.000
-25.576
51.541
115.535
167.520
208.177
238.965
260.869
274.835
281.448
282.217
277.345
267.923
254.436
238.084

0.000
2.246
-4.423
-9.681
-13.699
-16.604
-18.577
-19.754
-20.257
-20.176
-19.662
-18.763
-17.585
-16.186
-14.666
18

7.5

1.005

3.769

7.538

-3233.627

219.036

-13.050

DISCUSSION
The experiment is to examine the effect of a pulse input and step change input in a tubular flow
reactor and to construct a residence time distribution (RTD) function for the tubular flow reactor.
Both inlet and outlet conductivity values was recorded at regular intervals of 30 seconds until all
the reading are almost constant and approach the stable low level values. The de-ionized water
flow rate is maintained at 700 ml/min.

Outlet Conductivity values vs time

1.2
1
0.8
Conductivity (ms/ cm)

0.6
f(x) = - 0.17x^2 + 0.66x - 0.11

0.4
0.2
0
0

0.5

1.5

2.5

3.5

4.5

Time (min)

For the first experiment which is to examine the effect of a pulse input in a tubular flow reactor,
the salt solution was allowed to flow inside the reactor for 1 minute only. According to the graph
above, the outlet conductivity, Q2 value started to rise at minute 1.0 which is 0.2 ms/cm to its
peak at minute 2.0 which is 2.6 ms/cm. Then, it drastically dropped to 0.5 ms/cm at minute 2.5
before decreased uniformly to 0.2, 0.1 and 0.0 ms/cm at 3.0, 3.5 and 4.0 respectively. The
increased show the maximum reaction and the decreased show that the amount of reactant in
the reactor started to decrease until there is no reactant left because it all has been used up in
the reaction.

19

E(t) versus time (min)

1.2
1
0.8
E(t)

0.6
0.4
0.2
0
0

0.5

1.5

2.5

3.5

4.5

time (min)

This graph is plotted to obtained C(t) curve. It is observed that the materials leaving the reactor
spend between 1.5 min to 2.5 min in the reactor. It is also known as the residence time. From
C(t), E(t) curve was obtained which show the residence time distribution (RTD) function for the
plug flow reactor. It describes the fraction of fluid exiting the reactor that has spent between t
and t + dt inside the reactor. The mean residence time, tm was 2.128 min, second moment
variance, 2 was 25.89 and the third moment skewness, s3 was 0.232.

20

For experiment 2 which is experiment to examine the effect of a step change input in a tubular
flow reactor. In this experiment, the conductivity started to rise at minute 2.5. The conductivity
started to rise drastically from 2.0 ms/cm to 2.8 ms/cm before it started to rise uniformly and
constant from minute 3.0 min to 7.5 min at conductivity of 2.8 ms/cm until 3.2 ms/cm. A graph of
conductivity versus time is plotted to obtain the C(t) curve which is the area under the graph as
shown in graph below.

Outlet Conductivity versus time

3.5
f(x) = - 0.09x^2 + 1.21x - 0.76

3
2.5
2
Conductivity, ms/cm

1.5
1
0.5
0
0

time, min

21

After obtained the value of C(t), a graph of E(t) as a function of time is plotted. This is the
residence time distribution (RTD) function for the plug flow reactor.

E(t) versus time

1.2
1
0.8
0.6
E(t)

0.4
0.2
0
-0.2

-0.4
time (min)

The mean residence time is 22.263 min and for the second moment variance, 2 is 1556.452
and the third moment skewness, s3 is -89.222.

CONCLUSION
In experiment 1, based on the graph plotted it is observed that the outlet conductivity value is
the highest in the middle of the time frame which indicated that the reactant leaving the reactor
spent most of it time inside the reactor. As the amounts of the reactants are increases so does
the pulse input is also increases. For experiment 2, the outlet conductivity values shown no
changes until minute 2.5 where the conductivity suddenly rose to 2.0 ms/cm. Then, it increased
steadily until it reached constant value which is 3.2 ms/cm at minute 7.5. Graphs of outlet
conductivity versus time were plotted for both experiments to calculate the C(t) curve which
gave the value of E(t). The E(t) value was then used to calculate the mean residence time, t m,
second moment variance, 2

and third moment skewness, s3 for both experiment. The

objectives of the experiment were achieved.

22

RECOMMENDATIONS
There are few recommendations that can be made to improve the result of the experiment. First,
make sure that the de-ionized water and salt solution flow rate is the same and maintained
throughout the experiment. Make sure the salt solution to flow for 1 minute before the timer is
reset and restart. The valve must be control quickly and properly as this will affect the flow and
time of the reactant in the reactor. Reduce the error in taking the conductivity reading. Do not
run the experiment too long to get the stable values because the solution in the tank will run out.

REFERENCE
Reaction kinetics studies in a plug flow reactor. Background and Theory. Retrieved November
19, 2013 from http://solve.nitk.ac.in/dmdocuments/Chemical/theory_plugflow.pdf
Residence

time

distribution.

Retrieved

November

19,

2013

from

2013

from

http://en.wikipedia.org/wiki/Residence_time_distribution
Chemical

reactors.

Retrieved

from

November

19,

http://www.essentialchemicalindustry.org/processes/chemical-reactors.html
Mole

balances.

Retrieved

November

19,

2013

from

http://ptgmedia.pearsoncmg.com/images/0130473944/samplechapter/0130473944_ch01.pdf
Heterogeneous

And

Homogeneous

Reactors.

Retrieved

November

19,

2013

from

http://www.indiamart.com/ss-fabrication/heterogeneous-and-homogeneous-reactor.html
Fogler, Scott H. Elements of Chemical Reaction Engineering. 4th ed. Englewood Cliffs,
NJ:Prentice-Hall, 2006.

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