1.

0 INTRODUCTION

In the majority of industrial chemical processes, the reactor is the key equipment in which
raw materials undergo a chemical change to form desired products. The design and
operation of chemical reactors is thus crucial to the whole success of an industrial process.
Reactors can take a widely varying form, depending on the nature of the feed materials and
the products. Understanding the behaviour of how reactors function is necessary for the
proper control and handling of a reaction system. Basically, there are two main groups of
reactors, batch reactors and continuous flow reactors.

One of continuous flow reactors used very commonly in industrial processing is continuous
stirred tank reactor (CSTR). The CSTR is normally run at steady state and is usually operated
so as to be quite well mixed. As a result of mixing, the CSTR is generally modeled as having
no spatial variations in concentration, 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 exit point as they are elsewhere in the tank. Thus, the temperature
and concentration in the exit stream are modeled as being the same as those inside the
reactor.

The designed equation of CSTR is obtained from the mole balance equation and was
presented as below.

where V is denoted for the volume of CSTR; FA0 and FA represent the inlet and outlet
molar flowrate of species A , respectively; and -rA is the rate of reaction for species A.

Normally, conversion increases with the time the reactants spend in the reactor. For
continuous flow systems, this time usually increases with increasing reactor volume.
Consequently, the design equation is further derived into the following form, where the
conversion X is a function of reactor volume V.

Since the exit composition from the reactor is identical to the composition inside the reactor,
the rate of reaction is evaluated at the exit condition.

In current experiment, the effects of residence time and reaction temperature towards the
conversion, and hence the reaction rate will be investigated in the CSTR.
2.0 Safety Considerations

1. The unit must be operated under the supervision of an authorized staff who
has been properly trained to handle the unit.
2. All operating instructions supplied with the unit must be carefully read and
understood before attempting to operate the unit.
3. Feed stock which severely affect PTFE, PFA and borosilicate glass are not to
be used.
4. The system should not be subjected to shock, sudden impact, vibration,
additional load, or permanent external action of aggressive vapours.
5. Always check and rectify any leak.
6. Do not touch the hot components of the unit.
7. Be extremely careful when handling hazardous, flammable or polluting
materials.
8. Restore the system to operating conditions after any repair job.
9. Make sure the system is sufficiently ventilated when working at atmospheric
pressure.
10. Only a properly trained staff shall be allowed to carry out any servicing.
Manufacturer's manual must always be observed.
11. Before any servicing, shut down the whole operation and let the system to cool
down and be properly ventilated.
12. Do not use any coarse or abrasive cleaners on glass components.
13. Leaking couplings or fittings should be carefully retightened. Replace any
gaskets or seals if necessary.
14. Please fill the reactor with water before switch on the heater.

2.4 Maintenance

1. After each experiment, drain off any liquids from the reactor and make sure that
the reactor and tubings are cleaned properly. Flush the system with de-ionized
water until no traces of salt are detected.
2. Dispose all liquids immediately after each experiment. Do not leave any
solution or waste in the tanks over a long period of time.
3. Wipe off any spillage from the unit immediately.
3.0 OPERATING PROCEDURES

3.1 General Start-Up Procedures

1. Prepare the following solutions:

a) 30 liter of sodium hydroxide, NaOH (0.1 M)
b) 30 liter of ethyl acetate, Et(Ac) (0.1 M)
c) 1 liter of hydrochloric acid, HCl (0.25 M), for quenching
2. Ensure that all valves are initially closed except valve V12.
3. Fill feed tank B1 with the NaOH solution and feed tank B2 with the Et(Ac)
solution.
4. Turn on the power for the control panel.
5. Adjust the overflow tube to give the desired working volume in the reactor R1.
6. Open valves V2 and V4.
7. The unit is now ready for experiment.

3.2 General Shut-Down Procedures

1. Keep the cooling water cooling water continue flowing into the reactor, by
opening valve V5 and V6.
2. Switch off both pumps P1 and P2. Switch off the stirrer M1.
3. Switch off the heater. Let the liquid in the reaction vessel R1 to cool down to
room temperature.
4. Close the cooling water supply, by closing the valve V5 and V6.
5. Turn off the power for the control panel.
6. Open valves V1 and V3 to drain all solutions from feed tanks B1 and B2.
Otherwise, keep the solutions for subsequent experiment.
7. Open valves V8 to drain any liquid from the reactor R1 into waste tank B3.
Open valve V9 to drain all solutions from waste tank B3.
SOLTEQ® LIQUID PHASED STIRRED TANK REACTOR (Model: BP 100)

4.0 EXPERIMENTAL PROCEDURES

4.1 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. Prepare the following solutions:
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. Determine the conductivity and NaOH concentration for each conversion
values 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)

ANALYSIS AND DISCUSSION:

1. Record all data in the table.
2. Plot the calibration curve of conductivity vs conversion. Determine the slope
and y-axis intercept.

12
SOLTEQ® LIQUID PHASED STIRRED TANK REACTOR (Model: BP 100)

4.2 Back Titration Procedures for Manual Conversion Determination

It is recommended 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. Fill up a burette with 0.1 M NaOH solution.
2. Measure 10 ml of 0.25 M HCl in a flask.
3. Obtain a 50 ml sample from the experiment and immediately add the sample
to the HCl in the flask to quench the saponification reaction.
4. Add a few drops of pH indicator into the mixture.
5. Titrate the mixture with NaOH solution from the burette until the mixture is
neutralized. Record the amount of NaOH titrated.

ANALYSIS AND DISCUSSION:

→
NaOH + HCl NaCl + H2O
Unknown quantity:
Concentration of NaOH in the reactor = CNaOH mol/L

Known quantities:
Volume of sample = Vs ml
Concentration of NaOH in the feed vessel = CNaOH,f mol/L
Volume of HCl for quenching = VHCl,s ml
Concentration of HCl in standard solution = CHCl,s mol/L
Volume of titrated NaOH = V1 ml
Concentration of NaOH used for titration = CNaOH,s mol/L

Calculations:
Conc. of NaOH entering the reactor, CNaOH,0 = (CNaOH,f)/2 mol/L
C
Volume of unreacted quenching HCl, V2 = NaOH, s × V1 ml
CHCl, s
Vol. of HCl reacted with NaOH in sample, V3 = VHCl,s – V2 ml
Moles of HCl reacted with NaOH in sample, n1 = CHCl,s × V3 mol
Moles of unreacted NaOH in sample, n2 = n1 mol
Conc. of unreacted NaOH in the reactor, CNaOH = n2 / (Vs × 1000) mol/L

CNaOH
Conversion of NaOH in the reactor, X = ( 1 – CNaOH,0 ) × 100%

13
4.3 EXPERIMENT 1: Effect of Residence Time on the Reaction in a CSTR

OBJECTIVE:
To determine the effect of residence time on the extent of conversion.
To determine the reaction rate constant.

PROCEDURES:
1. Perform the general start-up procedures
2. Switch on both pumps P1 and P2 simultaneously and open valves V2 and V4
to obtain the highest possible flow rate into the reactor.
3. Let the reactor fill up with both the solution until it is just about to overflow. Adjust
the overflow tube to achieve level of the mixture solution ¾ reactor height .
Record the volume of the solution.
4. Adjust knob on the peristaltic pump P1 and P2 to give a flow rate of about 0.10
l/min (refer calibration curve of pump). Make sure that both flow rates are the
same. Record the flow rates.
5. Switch on the stirrer M1 and set the speed to about 200 rpm.
6. Start monitoring the conductivity value at QT101 until it does not change over
time. This is to ensure that the reactor has reached steady state.
7. Record the steady state conductivity value and find the concentration of NaOH
in the reactor and extent of conversion from the calibration curve.
8. Repeat the experiment (steps 5 to 8) for different residence times by adjusting
the feed flow rates of NaOH and Et(Ac) to 0.15, 0.20, 0.25 and 0.30 l/min. Make
sure that both feed flow rates are the same.

ANALYSIS AND DISCUSSION:

1. Plot a graph of conversion vs. residence time.
3. For a second order equimolar reaction with the same initial reactants’
concentration ( CA0 = CB 0 ), the rate law is shown to be:
− rA = kCACB = kCA2
For different reactor residence times, calculate the value of the reaction rate
constant, k and the rate of reaction, -rA.
 4.4 EXPERIMENT 2: Effect of Temperature on the Reaction in a CSTR

OBJECTIVE:
To determine the effect of temperature on the extent of conversion.
To determine the value of the reaction’s activation energy.

PROCEDURES:
1. Perform the general start-up procedures as in Section 4.1.
2. Switch on both pumps P1 and P2 simultaneously and open valves V2 and V4
to obtain the highest possible flow rate into the reactor.
3. Let the reactor fill up with both solution until it is just about to overflow.
4. Adjust knob on the peristaltic pump to give a flow rate of 0.10 l/min (refer
calibration curve of pump). Make sure that both flow rates are the same.
5. Switch on the stirrer M1 and set the speed at about 200 rpm.
6. Switch on the heater on the control panel. Set the temperature setpoint on the
TIC01 to 40 °C. Allow the liquid temperature to rise to the setpoint and remains
constant.
7. Start monitoring the conductivity value at QT101 until it doesn’t change over
time. This is to ensure that the reactor has reached steady state.
8. Record the steady state conductivity and temperature values and find the
concentration of NaOH in the reactor and extent of conversion from the
calibration curve.
9. Repeat the experiment (steps 7 to 9) for different reactor temperatures by
setting the temperature setpoint to 50, 60, 70 and 80 °C. Make sure that the
flow rates of both solutions are maintained at 0.1 l/min.

ANALYSIS AND DISCUSSION:

1. Plot a graph of conversion, X vs. reaction temperature.

2. Calculate the activation energy, E and Arrhenius constant, A by plotting graph.
Given that

where E = activation energy [J/mol]

A = Arrhenius constant
R = universal gas constant = 8.314 J/mol.K
T = absolute temperature [K]

5.0 REFERENCES

1. Levenspiel O., “Chemical Reaction Engineering”, John Wiley (USA), 1972.

2. Fogler H.S., “Elements of Chemical Reaction Engineering, 3rd Ed.”, Prentice Hall
(USA), 1999.
TABLE FOR PREPARATION OF CALIBRATION CURVE

Solution Mixtures
Concentration Conductivity
Conversion
0.1 M NaOH 0.1 M Na(Ac) H2O of NaOH (M) (mS/cm)

0% 100 mL – 100 mL
25% 75 mL 25 mL 100 mL
50% 50 mL 50 mL 100 mL
75% 25 mL 75 mL 100 mL
100% – 100 mL 100 mL
TABLE FOR EXPERIMENTS 1 : Effect of residence time on the reaction in CSTR
Reactor volume = _____ L
Concentration of NaOH in feed vessel = _____ M
Concentration of Et(Ac) in feed vessel = _____ M

Reaction
Et(Ac) feed NaOH feed Total feed Residence Rate of reaction,
Conductivity Conversion Concentration rate
flowrate flowrate flowrate, time, τ -rA
(mS/cm) (%) (mol/L) constant, k
(L/min) (L/min) (L/min) (min) (mol/ml.min)
(mL/mol.min)

TABLE FOR EXPERIMENTS 2 : Effect of temperature on the reaction in a CSTR

Et(Ac) feed flowrate = _____ L/min
NaOH feed flowrate = _____ L/min
Total feed flowrate = _____ L/min

Residance Reaction
Conductivity Conversion Concentration
Temperature (K) time, τ rate ln k 1/T
(mS/cm) (%) (M)
(min) constant,k
APPENDIX

PHYSICAL PROPERTIES OF COMPONENTS

Property Ethyl Acetate Sodium Hydroxide

Formula CH3COOCH2CH3 NaOH

Appearance clear liquid white solid

Molecular weight 88.11 g/mol 40.00 g/mol

Normal boiling point 77.1°C 1390° C

Normal melting point -84.0°C 323°C

Density 0.8945 g/mL @ 25°C 2.1 g/mL

Refractive index 1.3274 @ 20°C –