ABSTRACT

This is the experiment of continuous stirred tank reactor 40 L. The reaction to be studied
is the saponification reaction of ethyl acetate Et(Ac) and sodium hydroxide NaOH in the
continuous stirred tank reactor. The calibration curve of conversion vs conductivity is also
perform in this experiment. The objectives of this experiment are to perform saponification
reaction between NaOH and Et(Ac), to determine the reaction rate constant and to study the
effect of residence time on the conversion. This experiment is done by varying the residence time
by manipulating the flow rate of the system. The flow rate of both feeds that is introduced,
Et(Ac) and NaOH is the same and varied from 0.1 L/min to 0.3 mL/min. From the result, the
percentage of conversion of NaOH is increasing with the increase of residence time. When the
residence is 200 mins, the conversion is 98.4%. Then as the total flow rate provided for the
system is increased, the residence time is decreasing and that makes the conversion of NaOH to
decrease as well. When the residence time is 66.6667 mins, the conversion is increasing to
96.4%. The lower flow rate gives a higher residence time and helps increasing the conversion of
the reaction in the CSTR.

INTRODUCTION

Chemical kinetics and reactor design are at the heart of producing almost all
industrial chemicals. The selection of a reaction system that operates in the safest and most
efficient manner can be the key to the success or failure of a chemical plant. The reaction
occurred in a reactor is exothermic or endothermic. A chemical reactor is a vessel where
reactions are carried out purposefully to produce products from reactants by means of one or
more chemical reactions. A chemical reactor may be characterized by the mode operation
according to the flow condition.
Continuous stirred tank reactors (CSTR) are the most basic of the continuous
reactors used in chemical processes. The continuous stirred tank reactor or back mix reactor is a
very common processing unit in chemical and polymer industry. Its names suggest, it is a reactor
in which the contents are well stirred and uniform throughout. The CSTR is normally run at
steady state, and is usually operated so as a to be quite well mixed. The CSTR is generally
modeled as having no spatial variations in concentrations, temperature, or reaction rate
throughout the vessel. Since the temperature and concentration are identical everywhere within
the reaction vessel, they are the same at the exits point as they are elsewhere in the tank.
Continuous stirredtank reactors (CSTRs) are open systems, where material is free
to enter or exit the system that operate on a steadystate basis, where the conditions in the reactor
don't change with time. Reactants are continuously introduced into the reactor, while products
are continuously removed. CSTRs are very well mixed, so the contents have relatively uniform
properties such as temperature, density, etc. throughout. Also, conditions in the reactor's exit
stream are the same as those inside the tank. Continuous stirredtank reactors are most
commonly used in industrial processing, primarily in homogeneous liquidphase flow reactions,
where constant agitation is required. They may be used by themselves, in series, or in a parallel.
The Continuous Stirred Tank Reactor (Model: BP 143) unit is suitable for student
experiments on continuous chemical reactions. The unit consists of a jacketed reaction fitted in
the agitator and condenser. The unit comes complete with vessels for raw materials and product,
feed pumps, and thermostat. . Students will conduct continuous saponification reaction of ethyl
2

acetate and sodium hydroxide. A conductivity measurement is provided and students will relate
the conductivity value to extent of reaction. Students will study the effects of residence time and
reaction temperature on the reaction rate constant.

OBJECTIVE:

To carry out a saponification reaction between NaOH and Et(Ac) in a CSTR

To determine the effect of residence time onto the reaction extent of conversion
To determine the reaction rate constant

THEORY

The behavior of a CSTR is often approximated or modeled by that of a Continuous Ideally

StirredTank Reactor (CISTR). All calculations performed with CISTRs assume perfect mixing.
In a perfectly mixed reactor, the output composition is identical to composition of the material
inside the reactor, which is a function of residence time and rate of reaction. If the residence time
is 5 to 10 times the mixing time, this approximation is valid for engineering purposes. The
CISTR model is often used to simplify engineering calculations and can be used to describe
research reactors. In practice it can only be approached, in particular in industrial size reactors.
Assume:

Perfect or ideal mixing,

Integral mass balance on number of moles Ni of species i in a reactor of volume V;

where Fio is the molar flow rate inlet of species i, Fi the molar flow rate outlet, and stoichiometric
coefficient. The reaction rate, r, is generally dependent on the reactant concentration and the rate
constant (k). The rate constant can be determined by using a known empirical reaction rates that
is adjusted for temperature using the Arrhenius temperature dependence. Generally, as the
temperature increases so does the rate at which the reaction occurs. Residence time, is the
average amount of time a discrete quantity of reagent spends inside the tank.
Assume:

constant density (valid for most liquids; valid for gases only if there is no net change in

the number of moles or drastic temperature change)

isothermal conditions, or constant temperature (k is constant)
steady state
4

single, irreversible reaction (A = 1)

first order reaction (r = kCA)

A products
NA = CA V (where CA is the concentration of species A, V is the volume of the reactor, NA is the
number of moles of species A)

The values of the variables, outlet concentration and residence time, in the equation are major
design criteria. To model systems that do not obey the assumptions of constant temperature and a
single reaction, additional dependent variables must be considered. If the system is considered to
be in unsteady state, a differential equation or a system of coupled differential equations must be
solved. CSTR's are known to be one of the systems which exhibit complex behavior such as
steady state multiplicity, limit cycles and chaos.
Conversion:
One of the reactants is choosed as the basis of calculation and the other species involved is
related in the reaction to this basis. Consider the general equation
aA + bB cC + dD
We will choose A as our basis of calculation.
A+

b
a

c
d
C+ D
a
a

The basis of calculation is most always the limiting reactant. The conversion of species A in a
reaction is equal to the number of moles of A reacted per mole of A fed.

APPARATUS/MATERIALS

tubular flow reactor

deionized water
sodium hydroxide
ethyl acetate

PROCEDURE/METHODOLOGY

General Start-Up Procedures

1. The following solutions are prepared:
a) 40 L of sodium hydroxide, NaOH (0.1M)
b) 40 L of ethyl acetate, Et(Ac) (0.1M)
c) 1 L of hydrochloric acid, HCL (0.25M), for quenching
2. All valves are ensured to be initially closed.
3. The feed vessels are charged as follows:
a) The charge port caps are opened for vessels B1 and B2.
b) The NaOH solution is carefully poured into vessel B1 and the Et(Ac) solution into vessel B2.
c) The charge port caps for both vessels are closed.
4. The power for the control panel is turned on.
5. Water in the thermostat T1 tank is check whether it is sufficient. Refill as necessary.
6. Cooling water valve V13 is opened and the cooling water is let to flow through the condenser
W1. (Only for Experiment 2)
7. The overflow tube is adjusted to give a working volume of 10 L in the reactor R1.
8. Valves V2, V3, V7, V8 and V11 are opened.
9. The unit is now ready for experiment.

General Shut-Down Procedures

1. The cooling water valve V13 is kept open to allow the cooling water to continue flowing.
2. Both pumps P1 and P2 are switched off. Stirrer M1 is switched off.
3. The thermostat T1 is switched off. The liquid in the reaction vessel R1 is let to cool down to
room temperature.
4. Cooling water valve V13 is closed.
5. Valves V2, V3, V7 and V8 is closed. Valves V4, V9 and V12 are opened to drain any liquid
from the unit.
6. The power for the control panel is turned off.

A. Preparation of Calibration Curve for Conversion vs. Conductivity

The reaction to be studied is the saponification reaction of ethyl acetate Et(Ac) and sodium
hydroxide NaOH. Since this is a second order reaction, the rate of reaction depends on both
concentrations of Et(Ac) and NaOH. However, for analysis purposes, the reaction will be carried
out using equimolar feeds of Et(Ac) and NaOH solutions with the same initial concentrations.
This ensures that both concentrations are similar throughout the reaction.
NaOH + Et(Ac) Na(Ac) + EtOH
The following procedures will calibrate the conductivity measurements of conversion values for
the reaction between 0.1 M ethyl acetate and 0.1 M sodium hydroxide:
Procedures:
1. The following solutions is prepared:
a) 1 liter of sodium hydroxide, NaOH (0.1 M)
b) 1 liter of sodium acetate, Na(Ac) (0.1 M)

c) 1 liter of deionised water, H2O

2. The conductivity and NaOH concentration for each conversion values are determined by
mixing the following solutions into 100 ml of deionised water:
a) 0% conversion : 100 ml NaOH
b) 25% conversion : 75 ml NaOH + 25 ml Na(Ac)
c) 50% conversion : 50 ml NaOH + 50 ml Na(Ac)
d) 75% conversion : 25 ml NaOH + 75 ml Na(Ac)
e) 100% conversion : 100 ml Na(Ac)

B. Back Titration Procedures for Manual Conversion Determination

It is advisable to carry out manual conversion determination on experiment samples to verify the
conductivity measurement values. The following procedures will explain the method to carry out
back titration on the samples. It is based on the principle of quenching the sample with excess
acid to stop any further reactions, then back titrating with a base to determine the amount of
unreacted acid.
Procedures:
1. A burette is filled up with 0.1 M NaOH solution.
2. 10 ml of 0.25 M HCl is measured in a flask.
3. A 50 ml sample from the experiment is obtained and immediately added to the HCl in the flask
to quench the saponification reaction.
4. A few drops of pH indicator is added into the mixture.
5. The mixture is titrated with NaOH solution from the burette until the mixture is neutralized.
The amount of NaOH titrated is recorded.

Experiment procedure:
1. The general start-up procedures is performed.
2. Both pumps P1 and P2 is switched on simultaneously and open valves V5 and V10 to obtain
the highest possible flow rate into the reactor.
3. The reactor is filled up with both of the solution until it is just about to overflow.
4. The valves V5 and V10 are readjusted to give a flow rate of about 0.1 L/min. Both flow
rates are made sure to be the same. The flow rate is recorded.
5. The stirrer M1 is switched on and the speed is set to about 200 rpm.
6. The conductivity value at QI-401 is monitored until it does not change over time. This is to
ensure that the reactor has reached steady state.
7. The steady state conductivity value is recorded and the concentration of NaOH in the reactor
and extent of conversion is found from the calibration curve.
8. Sampling valve V12 is opened and a 50 mL sample is collected. A back titration procedure to
is determined manually determine the concentration of NaOH in the reactor and extent of
conversion.
9. The experiment (steps 5 to 9) is repeated for different residence times by adjusting the feed
flow rates of NaOH and Et(Ac) to about 0.15, 0.20, 0.25 and 0.30 L/min. Both flow rates are
made sure to be the same.

10

RESULTS
Table of the preparation of calibration curve.
Conversio
n

Solution Mixtures
0.1M
0.1M
H2O
NaOH

0%
25%
50%
75%
100%

100mL
75mL
50mL
25mL
-

Na(Ac)
25mL
50mL
75mL
100mL

100mL
100mL
100mL
100mL
100mL

Concentratio

Conductivit

n of NaOH

(M)
0.0500
0.0375
0.0250
0.0125
0.0000

(mS/ cm)
10.7
9.7
7.5
5.6
4.0

Table for experiments 1

Reactor volume = 40 L
Concentration of NaOH in feed vessel = 0.1 M
Concentration of Et (Ac) in feed vessel = 0.1 M

Flow

Flow

Total

Residen

Cond

Exit

Convers

Reaction

Reaction

Vol of

rate of

rate of

flow

ce

uctivit

Concent

ion,

rate

rate

NaOH

NaOH

Et(Ac)

rate of

time, t

y, Q

ration of

X (%)

constant,

Titrate

(L/min

(L/min

solutio

(min)

(mS/c

NaOH

ns, V0

m)

(L)

(L /
FT 01
0.10
0.15

FT 02
0.10
0.15

min)
0.2
0.3

200
133.333

3.51
3.17

0.0008
0.0010

98.4
98

3
0.20
0.20
0.4
100
0.25
0.25
0.5
80
0.30
0.30
0.6
66.6667
SAMPLE CALCULATIONS

2.83
2.64
2.52

0.0020
0.0018
0.0018

96
96.4
96.4

384.375
367.5
120
185.957
223.148

2.46 x 10-4
3.68 x 10-4

0.0246
0.0255

4.8 x 10-4
6.03 x 10-4
7.23 x 10-4

0.0260
0.0259
0.0259

Residence Time:
11

Calculation for flow rates of 0.1 L/min:

Total flow rate, Vo

= Flow rate of NaOH + Flow rate of Et(Ac)

= 0.1 L/min NaOH + 0.1 L/min Et(Ac)
= 0.2 L/min

=
Residence Time,

Reactor volume ( L ) ,V
40 L
=
0.2 L/min
L
Total flow rate
, v0
min

( )

= 200 mins

Initial concentration of NaOH entering the reactor:

=

Concentration of NaOH feed

2

0.1
2

= 0.05 M

Conversion:
Calculation for flow rates of 0.1 L/min :
Moles of reacted NaOH, n1
n1
= Concentration NaOH x Volume of NaOH titrated
= 0.1 M x 0.024.6 L
= 0.00246 mole
Moles of unreacted HCl, n2 = Moles of reacted NaOH, n1
n2 = 0.00246 mole

12

Volume of unreacted HCl, V1

V1

n2
concentration HCl quench

0.00246
0.25

= 0.00984 L
Volume of HCl reacted, V2
V2 = Total volume HCl V1
= 0.01 0.00984
= 0.00016 L
Moles of reacted HCl, n3
n3
= Concentration HCl x V2
= 0.25 x 0.00016
= 0.00004 mole
Moles of unreacted NaOH, n4
n4
= n3
= 0.00004 mole
Concentration of unreacted NaOH
CNaOH unreacted

n4
volume sample

0.00004
0.05

= 0.0008 M

Xunreacted
Xunreacted =

Concentration of NaOH unreacted

concentration NaOH

0.0008
= 0.05
= 0.016
Xreacted
Xreacted = 1 - Xunreacted
= 1 - 0.016
= 0.984
Conversion for flow rate 0.1 L/min,
13

0.984 x 100% = 98.4 %

Reaction rate constant, k
k = ( CAo CA) / CA2
= ( 0.05 0.0008) / (200 x 0.00082)
= 384.375 M-1 min -1
Rate of reaction, -rA
-rA = kCA2
= 24.44 x 0.0062
= 8.79 x 10 -4 mol/L.min

14

DISCUSSION

Conversion vs Conductivity
12
10
8
Conductivity (mS/cm)

f(x) = - 0.07x + 11
R = 0.99

6
4
2
0
0 10 20 30 40 50 60 70 80 90 100
Conversion (%)

For the preparation of calibration curve for conversion vs conductivity, the NaOH
solution and Na(Ac) is mixed together in order to give a value of conversion from the 0% which
means a pure NaOH solution to the 100% conversion which means a pure Na(Ac) solution
produced. The conductivity of the solution is then obtained by using a conductivity meter. The
curve obtained is shown in the figure above. The higher the conversion of NaOH, the lower the
conductivity value obtained based on the result. The best fit lined constructed from the result
gives the line of y = -0.07x + 11. Thus, the slope obtained is -0.07 while the y-intercept is at 11
mS/cm.
The CSTR is normally run at steady state, and is usually operated so as a to be quite well
mixed. The conductivity value in the CSTR is assumed as the same anywhere in the reactor.
From the experiment, the conductivity of the reactant decreases as the conversion decreases. The
98.4% conversion gives a conductivity value of 3.51 mS/cmw. The conversion which is 96.4%
gives the lowest conductivity value of 2.52 mS/cm. The decrease in the conductivity value of the
solution is because of the decrease in the ionic activity of a solution in term of its capacity to
transmit current. As the electrical current is transported by the ions in solution the conductivity
increases as the concentration of ions increases. Thus, the higher conversion of the NaOH gives a
15

lower ionic activity for the preparation of the calibration curve result. However, the lower
conversion of the NaOH gives a lower ionic activity from the experiment conducted. The ionic
activity is higher in the higher conversion of NaOH. This is possibly because of the agitation in
CSTR which making the ionic activity still going on in the solution even after the conversion.

Conversion vs Residence Time

100
95
Conversion (%)

90
85
80
60

80

100

120

140

160

180

200

Residence Time (min)

For the experiment of investigating the effect of conversion on residence time, the reaction to be
studied is the saponification reaction of ethyl acetate Et(Ac) and sodium hydroxide NaOH. The
reaction is carried out using equimolar feeds of Et(Ac) and NaOH solutions with the same initial
concentrations. This ensures that both concentrations are similar throughout the reaction. The
introduced flow rate of both feeds also the same throughout the experiment. The flow rate is then
varied from 0.1 L/min to 3.0 L/min for both feeds in order to give variation in the residence time.
The residence time is determined from the equation:
=
Residence Time,

Reactor volume ( L ) ,V
L
Total flow rate
, v0
min

( )

The results obtained from the experiment are shown in the graph above. From the graph,
we can see that the percentage of conversion of NaOH is increasing with the increase of
16

residence time. When the residence is 200 mins, the conversion is 98.4% that is the highest
conversion of NaOH from the experiment. Then as the total flow rate provided for the system is
increased, the residence time is decreased and that makes the conversion of NaOH to decrease as
well. When the residence time is 66.6667 mins, the conversion is decreasing to 96.4%.
The CSTR is normally run at steady state, and is usually operated so as a to be quite well
mixed. From the result, when flowrate is low, it helps the reaction more in the CSTR as
conversion value is higher as shown in the experiment. This is because the reactants have a lot of
time to make contact with each other before exiting the outlet when the flow rate is low. Thus,
the lower flowrate helps the conversion to increase as the contact between the reactant. As for the
reaction rate of the reaction, -rA from the result it is increasing as the residence time is higher
while the rate constant, k is decreasing.

17

CONCLUSION

As a conclusion, the objectives for this experiment are achieved. This is because we get
to perform saponification reaction between NaOH and Et(Ac) by using the continuous stirred
tank reactor 40 liter unit and then determine the reaction rate constant for each reaction which is
different from each flow rate introduced to the system. Besides that we also get to study the
effect of residence time on the conversion which is the lower flow rate gives a higher residence
time and increasing the conversion in the reaction.

RECOMMENDATION

It is recommended that the same experiment is conducted by using other type of reactor
in order to know which reactor will give a better process for the reaction and their
characteristics can be compared.

It is recommended that the flowrate of the feed NaOH and Et(Ac) to be varied and not
the same with each other to know how will it affects the reaction process in the
continuous stirred tank reactor.

It is also recommended to varied the concentration of the feed for example like how
would the reaction process go if the feed introduced into the system is not equimolar.

18

REFERENCES

Amrita Virtual Lab Collaborative Platform. Continous Stirred Tank Reactor. Retrieved on
6th April from http://iitkgp.vlab.co.in/?sub=35&brch=107&sim=1175&cnt=1

Encyclopedia Of Chemical Engineering Equipment. Retrieved on 6th April 2015 from

http://encyclopedia.che.engin.umich.edu/Pages/Reactors/CSTR/CSTR.html

Fogler, H.S (2006). Elements of Chemical Reaction Engineering (3rd Edition). Prentice
Hall.

Levenspiel, O. (1999). Chemical Reaction Engineering (3rd Edition). John Wiley.

Wikipedia. Continuous Stirred Tank Reactor. Retrieved on 6th April from

http://en.wikipedia.org/wiki/Continuous_stirredtank_reactor

19

APPENDIX

20