ABSTRACT/SUMMARY

This experiment is conducted to carry out conversion determination on experiment samples

manually to verity the conductivity measurement values, determine the effect of residence time
onto the reaction extent of conversion and the reaction rate constant. In order to accomplish the
objective, the unit being used to perform this experiment is CSTR 40L. The design of the reactor
is very important to the success of the production. In this experiment sodium hydroxide and ethyl
acetate react in continuous stirred tank reactor. Both of reactants feed to the reactor at equimolar
flow rate for a certain time.
Form graph 1 it shows that conductivity is decrease proportionally with conversion. For the
graph 2 the result shows that, when residence time is increase, conversion also increase by
lowering the flow rate. The higher conversion is 92.4% at 200 min residence time and 0.2
mL/min total flow rate of solution. It can be conclude that the higher the flow rate, the smaller
the reaction rate constant and rate of reaction become highest.

INTRODUCTION
In the industrial chemical process, mostly a reactor is the key part of equipment in which raw
material undergoes a chemical change to form desired product. The design and operation of
chemical reactor is thus crucial to the whole success of the industrial operation. There are many
type of reactor depending on the nature of the feed materials and products.
Reactor is the heart of any process in industry. Reactor can be classified into two types;
continuous stirred tank reactor and a plug flow reactor. Both of this type of reactor can be operate
in a continuous and a batch mode depending on the nature of the reaction. Reactor can be equips
with a heating or cooling coil for heating process or cooling process. It is depending on the
nature of reaction which is exothermic or endothermic. A reactor also can be equip with bed of
catalyst for a better reaction processes.

Reactor is one of the most important parts in industrial sector. Reactor is equipment that changes
the raw material to the product that we want. A good reactor will give a high production and
economical. One of criteria to choose or to design a good reactor is to know the effectiveness of
the reactor itself. There a many types of reactor depending on the nature of the feed materials and
products. One of the most important in the various chemical reactions was the rate of the
reaction.

A stirred tank reactor (STR) may be operated either as a batch reactor or as a steady state flow
reactor (CSTR). The key or main feature of this reactor is that mixing is complete so that
properties such as temperature and concentration of the reaction mixture are uniform in all parts
of the vessel. Material balance of a general chemical reaction described below.
The conservation principle requires that the mass of species A in an element of reactor volume
dV obeys the following statement described below.
(Rate of A into volume element) - (rate of A out of volume element) + (rate of A produced
within volume element) = (rate of A accumulated within vol. element)

OBJECTIVES
1.To verify the conductivity values by manual determination on experimental samples.
2.To determine the effect of residence time onto the reaction extent of conversion.
3.To determine the reaction rate constant

THEORY
Rate of equation and rate law
The rate of reactions or speed of reaction for a reactant and products in particular reaction scan
be defined as how fast or slow the reaction takes place. For examples is about the oxidation
process between iron under the atmospheric is undergoes a slow reaction compare to the
combustion of butane in a fire that can be categories as fast reaction. Consider the chemical
reaction as below:

The lowercase letter which are a,b,p,and q refer to the stoichiometric coefficient while the capital
letter which are A,B,P and Q refer to the reactants and products.
According to the IUPACs Gold Book definition the rate of reaction, r in the chemical reaction is
occur in a closed system which is under a constantvolume conditions, without build up of
reaction intermediates, is defines as:

Where [A], [B], [P] and [Q] are referred to the molarity of the substances. Based on IUPAC the
times must be in second and the rate of reaction is in a positive sign. The mass balance for any
system in general is:
IN - OUT + GENERATION -CONSUMPTION= ACCUMULATION
Mass is a conservative entity, hence given a control volume V the sum of mass flows entering the
system will be equal to the sum exiting minus (plus) the consumed (generated) or accumulated
fractions.

Continuous Stirred Tank Reactors (CSTR)

A stirred-tank reactor (STR) may be operated either as a batch reactor or as a steady-state flow
reactor which is better known as Continuous Stirred-Tank Reactor (CSTR). The key or main
feature of this reactor is that mixing is complete so that properties such as temperature and
concentration of the reaction mixture are uniform in all parts of the vessel.
CSTR is the most basic of the continuous reactors used in chemical process. It is an open system
where material is free to enter or exit the system and runs at steady state with continuous flow of
reactants and products, where the condition in the reactor dont change with time. The reactants
are continuously introduced into the reactor, while product are continuously removed and
assumes a uniform composition throughout the reactor.
CSTRs are very well mixed, so the contents have relatively uniform properties such as
temperature, density, and concentration. Also, conditions in the reactor's exit stream are the same
as those inside the tank.
Systems connecting several CSTRs are used when the reaction is too slow. Multiple CSTRs can
also be used when two immicible liquids or viscous liquids are present and require a high
agitation rate.
General Mole Balance Equation

Assumptions
Steady state, therefore dNA/dt = 0
Well-mixed

therefore

is

the

same

throughout

the

reactor.

Rearranging the generation, V = (FAoFA)/ -rA

In terms of conversion, X = (FAoFA) / FAo
V = (FAoX) / -rA
A calibration curve is a method used in analytical chemistry to determine the concentration of an
unknown sample solution. It is a graph generated by experimental means, with the concentration
of solution plotted on the x-axis and the observable variablefor example, the solutions
absorbanceplotted on the y-axis. The curve is constructed by measuring the concentration and
absorbance of several prepared solutions, called calibration standards. Once the curve has been
plotted, the concentration of the unknown solution can be determined by placing it on the curve
based on its absorbance or other observable variable.

Residence Time
The reactors residence time is defined as the reactor volume divided by the total feed flow rates.

Residence time is a probability distribution function that describes the amount of time
a fluid element could spend inside the reactor. Residence time widely use to characterize the
mixing and flow within reactors and to compare the behavior of real reactors to their ideal
models. This is useful, not only for troubleshooting existing reactors, but in estimating the yield
of a given reaction and designing future reactors.

APPARATUS
1. Continuous stirred tank reactor. Model: BP 143
2. 50 mL burette
3. 200 mL beaker
4. Conical flask
5. Solution :
I-Sodium hydroxide, NaOH (0.1M)
II-Ethyl acetate, Et (Ac) (0.1M)
III-Deionised water
IV-Phenolphthalein
6. Conductivity probe
7. 100 mL measuring cylinder.

OPERATING PROCEDURES
General Start-Up Procedures
1. The following solutions have been prepared for the expirement:
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 the valves was ensured initially closed.
3. The feed vessels was charged as follows:
a) The charge port caps was opened for vessels B1 and B2.
b) NaOH solution was carefully pour into vessel B1 and the Et(Ac) solution into vessel
B2.
c) The charge port caps closed for both vessels.
4. The power was turn on for the control panel.
5. Checked that there is sufficient water in the thermostat T1 tank. Refill if necessary.
6. Opened cooling water valve V13 and let the cooling water flow through the condenser W1.
(Only for
Experiment 2)
7. Adjusted the overflow tube to give a working volume of 10 L in the reactor R1.
8. The valves V2, V3, V7, V8 and V11 was opened.
9. The unit is now ready for experiment.
General Shut-Down Procedures
1. The cooling water valve V13 was open to allow the cooling water to continue flowing.
2. Both pumps P1 and P2 was switch off. Then, switch off stirrer M1.
3. The thermostat T1 was switch off. Let the liquid in the reaction vessel R1 cool down to room
temperature.
4. Closed cooling water valve V13.
5. Closed valves V2, V3, V7 and V8. Valves V4, V9 and V12 was open to drain any liquid from
the unit.
6. The power was turn off for the control panel.
Preparation of Calibration Curve for Conversion vs Conductivity:

1.The following solution were prepared:

i- 1 L of sodium hydroxide, NaOH (0.1M)
ii- 1 L of sodium acetate , Et (Ac) (0.1M)
iii- 1 L of deionised water, H2O.
2. The conductivity and NaOH concentration for each value were determined by mixing the
following solution into 100 mL of deionised water.
i- 0% conversion : 100 mL NaOH
ii- 25% cinversion : 75 mL NaOH + 25 mL Et (Ac)
iii- 50% conversion : 50 mL NaOH + 50 mL Et (Ac)
iv- 75% conversion : 23 mL NaOH + 75 mL Et (Ac)
v- 100% conversion : 100 mL Et (Ac)
Experiment 1: Back Titration Procedures for Manual Conversion Determination:
1.A burette was filled up with 0.1 M NaOH solution.
2.10 mL of 0.25 M HCl was measured in a flask.
3.A 50 mL sample was obtained from the experiment and immediate the sample was added to the
HCl in the flask to quench the saponification reaction.
4.A few drops of pH indicator were added into the mixture.
5.The mixture was titrated with NaOH solution from the burette until the mixture was
neutralized. The amount of NaOH titrated was recorded.

Experiment 2: Effect of Residence Time of The Reaction in a CSTR:

1.The general start-up procedures was performed.
2.Pump 1 and pump 2 were switched on and valves V5 and V10 were opened to obtain the
highest possible flow rate into the reactor.
3.The reactor was filled up with both of the solution until it is just about to overflow.
4.Valves V5 and V10 were readjusted to give a flow rate of about 0.1 L/min. the flow rate for
both valves must be same. The flow rate was recorded into a data.
5. The stirrer M1 was switched on and the speed was set about 200 rpm.
6. The conductivity value at Q1 was started monitoring until it does not change over time. This is
to ensure that the reactor has reached steady state.
7. The steady state conductivity value was recorded and the concentration of NaOH andextent of
conversion in the reactor was found out from the calibration curve.
8. Sampling valve V12 was opened and 100mL of sample was collected. It directly proceed with
the back titration procedures to manually determine the concentration of NaOH in the reactor and
extent of conversion.
9.The experiments was repeated (steps 5-9) for different residence times by adjusting the feed
flow rate of NaOH and Et(Ac) to about 0.15, 0.20, 0.25, and 0.30 L/min. the flow rate for both
must be same.

Results
Table for preparation of calibration curve
Conductivit
Conversion Solution Mixtures
0.1
0%
25%
50%
75%
100%

0.1 M NaOH
100mL
75mL
50mL
25mL

Concentration y
M

Et

(Ac)

H2O
100mL
100mL
100mL
100mL
100mL

25mL
50mL
75mL
100mL

of NaOH (M)
0.0500
0.0375
0.0250
0.0125
0.0000

(ms/cm)
14.48
10.57
7.01
2.31
0.1

Conductivity vs Conversion
20
15
Conductivity (ms/cm)

10

f(x) = - 14.81x + 14.3

R = 0.99

Conductivity (ms/cm)
Linear (Conductivity
(ms/cm))

5
0
0%

50%

100%

150%

Conversion %

Graph 1: Calibration curve for conductivity vs conversion

Back titration for manual conversion determination:

Sample
1
2
3
4
5

Vol. of NaOH (mL)

23.1
21.2
19.4
19.0
18.6

Table of experiment 1 and 2:

Reactor volume = 40 L
Concentration of NaOH in feed vessel = 0.10 M
Concentration of Et(Ac) in feed vessel = 0.10 M
No.

1.
2.
3.
4.
5.

Flow rate of Flow rate of Resisdence

Conductivit

Exit

Conversion

NaOH

Et(Ac)

time,

concentration

, X (%)

(mL/min)

(mL/min)

(min)

(mS/cm)

of NaOH,CNaOH

1.10
2.30
3.21
3.41
3.78

(M)
0.00038
0.00760
0.01120
0.01200
0.01280

0.10
0.15
0.20
0.25
0.30

0.10
0.15
0.20
0.25
0.30

200.00
133.33
100.00
80.00
66.67

Reaction rate constant, k Rate of reaction, -r

(M-1min-1)
15.997
5.507
3.012
3.297

(mol/L.min)
0.000231
0.000318
0.000378
0.000475

92.4
84.8
77.6
76.0
74.4

3.4055

0.000558

Residence time vs Conversion

100
90
80
70
60
Residence time,(min)

Conversion, X (%)

50
40
30
20
10
0
60

80

100

120

140

Graph 2: residence time vs conversion

SAMPLE CALCULATIONS
1) F0= 0.1+0.1 = 0.2 L/min
Known quantities:
Volume of sample, Vs= 50 mL

160

180

200

220

Concentration of NaOH in the feed vessel, CNaOH,f = 0.1 mol/L

Volume of HCL for quenching, VHCl,s= 10 mL
Concentration of HCl in standard solution, CHCls= 0.25 mol/L
Volume of titrated NaOH, V1= 9.8 mL
Concentration of NaOH used for titration, CNaOHs= 0.1 mol/L

I.

Concentration of NaOH that entering the reactor, CNaOHo.

C NaOHo= C NaOHf
= (0.1)
= 0.05 mol/L

ii.

Volume of unreacted quenching HCl,V2

V2= (C NaOHs/ CHCls) x V1
= (0.1/0.25) x 23.1
= 9.24 mL

iii.

Volume of HCl reacted with NaOHin sample, V3

V3= VHCls V2
= 10 9.24
= 0.76

iv.

Moles of HCl reacted with NaOH in sample, n1

n1= (CHCls x V3) / 1000
= 0.25 x 0.76/1000

= 0.00019 mol

v.

Moles of unreacted NaOH in sample, n2

n2= n1
= 0.00019 mol

vi.

Concentration of unreacted NaOH in the reactor, CNaOH

C NaOH= n2/Vs x 1000
= 0.00019/50 x 1000
= 0.0038 mol/L

Vii.

Conversion of NaOH in the reactor, X

X = (1- C NaOH/ C NaOHo) x 100%
= (1 0.0038/0.05) x 100%
= 92.4 %

Viii.

Residence time,
=VCSTR / Fo
= 40 / 0.20
= 200 min

ix.

Reaction rate constant, k

k = ( CAo CA) / CA2
= ( 0.05 0.0038) / (200 x 0.0062)
= 15.997 M-1min-1

x.

Rate of reaction, -r A
-r A= kCA2
= 15.997 x 0.00382

DISCUSSION
According to the experiment that had been conducted, there are three objectives need to achieve
which are to carry out the saponification process between NaOH and Et (Ac) in a CSTR reactor,
to determine the effect of the residence time onto the reaction extent of conversion and lastly to

determine the constant rate of reaction. From the data collected, two graph had been plotted
which are conductivity versus conversion and residence time versus conversion.
From the graph 1, it shows that the conductivity is constantly decreasing which are the line is
inversely proportional until at 50% conversion which is the conductivity is 7.01 mS/cm but then
it suddenly decrease at 60% conversion until 80% conversion which is give a curve on the graph
as shown.
For the second graph which is residence time versus conversion, the graph can be concluded that
the residence time is increase proportionally to the conversion. It can be conclude that residence
is higher if the conversion is higher. But there are certain fluctuated peak which due to the error
that may be affects the result and graph.
As the result for rates of constant is not correspond to the theory, thus there are some errors
occurred during this experiment such as while taking the reading of the burette the position of the
eyes is not at the same level of the meniscus. So, to improve the reading and get the better
results, the positions of the eyes must be parallel to the meniscus. Besides, we have to rinse all
the apparatus before we use it. This is to ensure that all the beakers, or burette is clean so that any
chemical that we put into these apparatus does not react with any others chemicals.by doing all
these precaution, we can get more accurate reading and thus improve the results.
CONCLUSION
Based on the objectives of this experiment, which is to determine the residence time on to the
reaction extent of conversion, the relationship conversion and residence time was directly
proportional. But the reaction rates constant were determined for all varies flow rate. From the
calculated data, the rate constant of reaction is increasing when the conversion is higher. This can
conclude that the experiment was successfully conducted since it give the right and verified
result.
RECOMMENDATIONS
1. Make sure reactor does not have any leaks and valve closed and opened as needed, controlled
the valve carefully and slowly when adjusting the flow rate to obtain 0.10 L/min. It is to make
sure flow rate will stabilize and the experiment will run smoothly.

2. Repeat titrations two or three times because a lot of error comes from titration or use another
method other than titration.
3. Divide into two teams which is the first team in charge of the CSTR 40 liters machine while
the second team would carry out the back titration procedures.
4. Take conductivity reading when the conductivity not changes in time because it can change
rapidly in short of time.
5. Make sure CSTR 40 liters machine is running appropriately, it to prevent harm to the machine
and individual that used the machine.

REFERENCES APPENDICES
(1) http://www.scribd.com/doc/143019471/cstr-40-L#scribd (18/03/2016)
(2) http://www.scribd.com/doc/143019471/cstr-40-L (24/03/2016)
(3) http://www.slideshare.net/errafatiha/experiment-cstr-40l (24/03/2016)

(4) https://en.wikipedia.org/wiki/Continuous_stirred-tank_reactor (24/03/2016)

(5) https://en.wikipedia.org/wiki/Residence_time_distribution (28/03/2016)