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INTRODUCTION


Reactor design and operation are the heart of almost all chemical producing plant and
plays an important role in determining the success or failure of a chemical plant. The ability of
the engineer in charge in choosing the most efficient method of operation for the reactor is vital
in ensuring the reactor is always operated in the most optimized manner. However, since real
reactors are subject to non-ideality, their design equation and characterization is different than
those of ideal reactors. Understanding non-steady behavior of real reactor is necessary for the
design and operation of the reactor.
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In the majority of industrial chemical process, a reactor is the key item of equi pment
i n whi ch r aw mat er i al s under go a chemi cal change t o f or m desired product.
The design and operation of chemical reactors is thus crucial to the whole success of the
industrial operation. Reactors can widely form, depending on the nature of the feed materials and
the products. Understanding non-steady behavior of process equipment is necessary for design
and operation of automatic control systems. One particular type of process equipment is the
continuous stirred tank reactor. In this reactor, it is important to determine the system response to
a change in concentration. This response of concentration versus time is an indication of the
ideality of the system.
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 Bio flow III reactor in the unit operations
laboratory provides a good basis for scale-up industrial reactor work.





What is resident time distribution (RTD)?
Residence time distribution (RTD) refers to the characteristic of the mixing that occurs in
a chemical reactor. Real reactors are subject to non-ideal flow pattern. For example, in tubular
reactor, by assuming that the flow inside the reactor is of plug flow type and no axial mixing
exists, the design equation of the tubular reactor was simplified to those of plug flow reactor
(PFR). However, the actual flow inside a real tubular reactor, especially if packing are used
inside the reactor, is no longer of plug flow type and some degree of axial mixing does exist
inside the reactor. Hence, the mixing characteristic of real reactors will be different than ideal
reactors and this is reflected in the RTD of the reactor. In short, information on RTD for a given
reactor yields distinctive clues to the type of mixing occurring within the reactor.
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What is the use of RTD?

RTD is mainly used to account for the non-ideality inside a reactor. Non-ideality inside a
reactor leads to the existence of dead zone, stagnant zone and actual conversion that is
less than those predicted by ideal reactors. On the micro scale level, the analyst will be
able to predict the conversion inside a non-ideal reactor should the reactor is to be used for
some other reaction

How does one measures RTD?

The RTD is determined experimentally by injection an inert chemical, molecule, or atom,
called a tracer, into the reactor at some time t = 0 and then measuring the tracer
concentration, C, in the effluent stream as a function of time. A tracer should be non
reactive, easily detectable, have physical properties similar to those of the reacting
mixture and completely soluble in the mixture. It should not adsorb on the walls or other
surfaces in the reactor. The two most used methods of injection are pulse input and step
input.



OBJECTIVE:


1. To carry out a saponification reaction between NaOH and Et(Ac) in a CSTR
2. To determine the effect of residence time onto the reaction extent of conversion
3. To determine the reaction rate constant






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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.

Ideal stirred-tank reactor
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A stirred- tank reactor (STR) may be operated either as a batch reactor or as a steady-
state flow reactor. The reactor can completely mix where the temperature and concentration of
the reaction mixture are uniform in all parts of the vessel.
The conservation principle requires that the mass of species A in an element of reactor
volume V obey the following statement:

Rate of A Rate of A Rate of A Rate of A
Into _ out of + produced = accumulated ...(1)
volume volume within volume within volume
element element element element


Batch stirred-tank reactor (BSTR)
In batch reactions, there are no feeds or exit streams and therefore equation (1) can be simplified
into:
Rate of A Rate of A
produced = accumulated (2)
within volume within volume
element element


The rate of reaction of component A is defined as:

reaction by
A
A
dt
dN
V
r

|
.
|

\
|
=
1
.(3)

When A is a reaction product, the rate is positive while when reactant is consumed, the rate is
negative. Rearranging equation (3);
( )
dt
dX
N V r
A
AO A
= .(4)
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Integrate equation (4);

( )
}

=
V r
dX
N t
A
A
AO
(5)
where t is the time required to achieve a conversion X
A
for either isothermal or non-isothermal
operation.


Steady state mixed flow reactor

Figure 1: Components of mixed flow

From figure 1, if F
A0
= v
0
C
A0
is the molar feed rate of the component A to the reactor, then
considering the reactor as a whole we have,
Input of A (moles/time) = F
A0
(1 X
A0
) = F
A0

Output of A (moles/time) = F
A
= F
A0
(1 X
A
)
Disappearance of A by reaction (moles/time) = (-r
A
)V
Replacing equation (1) with mathematical formula above,

F
A0
X
A
= (-r
A
)V ...(6)
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Which on arranging, will form the performance equation for mixed flow reactors,

A
A
AO AO
r
X
C F
V

A
= =
t

A
A AO
AO
AO
O
r
X C
F
VC
v
V
s
= = = =
1
t (7)



In mixed flow reactors, X
A
= X
AF
and C
A
= C
AF
. In a constant density system,
X
A
= 1 (C
A
/C
A0
)

The performance equation can be rewritten in terms of concentration, or

) (
A AO
A AO
A
A
AO
r C
C C
r
X
F
V

=
) (
A
A AO
r
X C
v
V

= = t (8)
Reaction Rate in Mixed Reactor

First order reaction (Unimolecular Type)
A Product
Suppose the reaction rate is the following type:
A
A
A
kC
dt
dC
r = = ..(9)
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kt
C
C
A
A
=
0
ln .(10)

Plot of ln(C
A
/C
A0
) versus t will produce a straight line with a slope equals to rate constant, k

Figure 2: Plot of ln(C
A
/C
A0
) versus time





Irreversible Second-order Reaction (Bimolecular Type)
A + B Products
The rate equation can be written as:

B A
B A
A
C kC
dt
dC
dt
dC
r = = = .(11)

Plot of ln (C
B
/C
A
) versus t (time) will produce a straight line with slope equals (C
B0
C
A0
)k.

-ln C
A0
C
A

t
Slope = k
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Figure 3 : Plot of ln (C
B
/C
A
) versus t

For second order reaction with equal initial concentrations of A and B, the rate equation can be
written based on only one component:

2 2 2
) 1 (
A AO A
A
A
X kC kC
dt
dC
r = = = .(12)





A plot of 1 / C
A
versus t will produce a straight line with slope equals to k.

-ln C
B
C
A

t
slope = (C
B0
-C
A0
)k
Intercept = ln C
B0
/C
A0


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Figure 4: Plot of 1/C
A
versus t













PROCEDURE

General Start-Up Procedures

1. Prepare the following solutions:
1/C
A

t
slope = k
Intercept = 1/C
A0

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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. Ensure that all valves are initially closed.

3. Charge the feed vessels as follows:
a) Open the charge port caps for vessels B1 and B2.
b) Carefully pour the NaOH solution into vessel B1 and the Et(Ac) solution into vessel B2.
c) Close the charge port caps for both vessels.

4. Turn on the power for the control panel.

5. Check that there is sufficient water in the thermostat T1 tank. Refill as necessary.

6. Open cooling water valve V13 and let the cooling water flow through the condenser W1.
(Only for Experiment 2)

7. Adjust the overflow tube to give a working volume of 10 L in the reactor R1.

8. Open valves V2, V3, V7, V8 and V11.

9. The unit is now ready for experiment.





General Shut-Down Procedures

1. Keep the cooling water valve V13 open to allow the cooling water to continue flowing.
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2. Switch off both pumps P1 and P2. Switch off stirrer M1.

3. Switch off the thermostat T1. Let the liquid in the reaction vessel R1 cool down to room
temperature.

4. Close cooling water valve V13.

5. Close valves V2, V3, V7 and V8. Open valves V4, V9 and V12 to drain any liquid from
the unit.

6. Turn off the power for the control panel.

EXPERIMENT 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 V5 and V10 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.

4. Readjust the valves V5 and V10 to give a flow rate of about 0.1 L/min. Make sure that
both flow rates are the same. Record the flow rate.

5. Switch on the stirrer M1 and set the speed to about 200 rpm.



6. Start monitoring the conductivity value at QI-401until it does not change over time. This is
to ensure that the reactor has reached steady state.

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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. Open sampling valve V12 and collect a 50 mL sample. Carry out a back titration
procedure to manually determine the concentration of NaOH in the reactor and extent of
conversion (Section 5.2).

9. Repeat the experiment (steps 5 to 9) 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. Make sure that
both flow rates are the same.


















APPARATUS


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1. Distillation water
2. Sodium Chloride
3. Continuous reactor in series
4. Stirrer system
5. Feed tanks
6. Waste tank
7. Dead time coil
8. Computerize system
9. Stop watch
10. 1 liter of sodium hydroxide, NaOH (0.1 M)
11. 1 liter of sodium acetate, Et(Ac) (0.1 M)
12. 1 liter of deionised water, H2O












RESULTS
Reactor volume = 40L
Concentration of NaOH in feed vessel = 0.1 M
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Concentration of Et (Ac) in feed vessel = 0.1 M
Temperatu
re
(
o
C)
Flow
rate of
NaOH
(ml/mi
n)
Flow
rate of
Et, Ac
(ml/mi
n)
Total
flow
rate of
solutio
n
F
o

(ml/mi
n)
Residen
ce
Time,
(min)
Conductivi
ty
(ms/cm)
Exit
concentrati
on
Of NaOH,
C
NaOH
(M)
Conversio
n,
X (%)
27.0 0.10 0.10 0.20 5 4.26 0.0499 0.2
27.4 0.15 0.15 0.30 5 4.10 0.0376 24.8
27.6 0.2 0.20 0.40 5 4.26 0.0240 52.0
27.7 0.25 0.25 0.50 5 4.56 0.0134 73.2
27.8 0.30 0.30 0.60 5 4.96 0.0001 99.8



Figure 10: Graph 1/C
A
versus time, t for experiment A

Experiment 2
y = 1.0013x + 27.157
R = 0.9893
1
/
C
A

Time, t
Plot of 1/CA versus time
Conversion

Solution
mixture

Concentration Conductivity
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Graph conductivity vs conversion




SAMPLE OF CALCULATION
0
2
4
6
8
10
12
14
0.00 0.20 0.40 0.60 0.80 1.00 1.20
c
o
n
d
u
c
t
i
v
i
t
y

conversion

0.1 M NaOH 0.1 M Et(Ac) H
2
O of NaOH (Ms/cm)
0% 100ml - 100ml 0.0500 12.22
25% 75ml 25ml 100ml 0.0375 7.90
50% 50ml 50ml 100ml 0.0250 3.52
75% 25ml 75ml 100ml 0.0125 1.28
100% - 100ml 100ml 0.0000 0.12
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Concentration of NaOH
()

Entering the reactor, C
NaOH,0

()

Volume of unreacted quenching HCl, V
2

()


Volume of HCl reacted with NaOH in

Sample, V
3

\


Moles of HCl reacted with NaOH in
(

Sample , n
1

()

Moles of unreacted NaOH in the reactor, n
2
= n
1



Concentration of unreacted NaOH in the reactor, C
NaOH

)

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()




Conversion of NaOH in the reactor, X (

)
(

)

Concentration of NaOH reacted with Ethyl Acetate (moles/litre) (I)
) (
,
G C
o NaOH
=

0352 . 0 1 . 0 =
= 0.0648 moles/litre

Moles of NaOH reacted with Ethyl Acetate in Sample (J)
s
V I = ) (

05 . 0 0648 . 0 =
= 0.00324 mole

Concentration of Ethyl Acetate = Concentration of NaOH reacted with
Reacted with NaOH(moles/litre) (K) Ethyl Acetate (moles/litre) (I)

Concentration of Ethyl Acetate unreacted (moles/litre), C
B
(L)
) (
,
K C
o EA
=

0648 . 0 1 . 0 =
= 0.0352 moles/litre
1 / C
A
= 1 / (G)
= 1 / 0.0352
= 28.41 litre / moles



DISCUSSION

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Based on results, increase of dosing pump, increases the conductivity of the mixture
solution. This is because increasing the dosing pumps increases the flow rate of raw reactants
into the CSTR, and hence the residence time of reactants in the reactor is lesser. The reactant
does not have sufficient time to react and transform into product before being over flow to the
tank drain where the conductivity of mixture is measured. So, the amount
of NaOH remained in the fluid coming out from the CSTR is higher. Therefore, the conductivity
is high due to the large amount of hydroxide ion (from NaOH) remaining in the outlet stream.

Increase of dosing pump, increases the conductivity of the mixture solution. The percenta
ge conversion of the saponification reaction is dependent on the conductivity measured from the
product. Therefore, the percentage conversion is high at low percentage dosing pump. As the
percentage dosing pump or flow rate increases, the resulting percentage conversion of NaOH
decreases. This is due to less residence time of reactants in the CSTR, which does not give ample
time for the saponification reaction to take place. Hence, lower percentage conversion of NaOH
results. In short, the conversion of NaOH is inversely proportional to the percentage of dosing
pump. The results proved that this theory applies on this experiment.The residence time of a
chemical reactor is the average amount of time a particle spends inside the reactor, with the
general formula of

=VQ

where,

= residence time,

V = volume of fluid in reactor, m3

Q = volumetric flow rate, m3/min




To calculate the residence time in a CSTR, first the volume of the CSTR has to be
determined. Since the volume of CSTR in this experiment is set to be constant (the amount of
fluid is maintained at a per-determined level by a level adjustor in the CSTR),so we can assume
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that the volume of fluid is around 20% of the volume of reactor. To get the volumetric flow rate
of fluid into the reactor, multiply the dosing pump percentage to the total flow rate as the dosing
peristaltic pumps are fitted with speed control to adjust the feeding rate. Therefore, for this
experiment, the higher the dosing pump, the higher the volumetric flow rate and hence lower the
residence time (as the volume of fluid is constant).By referring to the equation below,

V=F
AO
X
A
- r
A


where,
V = volume of reactor

FA0 = initial feed rate of A

XA = extent of conversion of A

rA = rate of reaction

We know that as the volume of a CSTR increases, the conversion of reactant A increases
as well. To be more precise, with higher volume of reactant fluid in the reactor and fixed
volumetric flow rate, the residence time of the reactant in the reactor increases. Therefore, the
reactant has more time to react in the reactor and hence the conversion will be higher.

It is important to note that adding catalyst will not affect the conversion of the reaction. It
only speeds up the rate for the reaction to reach equilibrium. Apart from that, the rate of the
reaction at lower temperatures is extremely slow, so a higher temperature must be used to speed
up the reaction which results in a lower yield of ammonia. Theoretically, after increasing the
dosing pump, the product conductivity has to be higher due to more NaOH molecules remained
in the solution. However, the conductivity does not change much. This is because the
conductivity meter is measuring the fluid with the previous set of condition (lower dosing pump
percentage) since the solution in the CSTR is mixture of product from current dosing pump and
previous dosing pump. So, the conductivity shown does not represent the actual case.

CONCLUSIONS
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In this experiment, the objectives for first experiment are to determine the order of
saponification reaction and determine the reaction rate constant. We also have to determine the
effect of residence time onto the reaction extent of conversion. From the results, the value of CA
and CB are the same. So, the order of this reaction is a second order. From the graph of 1/CA
versus time, this graph should be a straight line.

From the first experiment, the value of k or the slope of graph at room temperature is
5.4989. This plotted graph shows the reaction is second order. For conversion 90%, time
required for temperature 35
o
C, 45
o
C and 55
o
C is 10.36 minutes, 3.70 minutes and 9.48 minutes.
The activation energy can be determined through the graph of ln k versus 1/T. Using the value of
k from the slope of that graph, the activation energy is 6377 kJ / mole. From the plotted graph of
C versus time and r versus time, concentration of A, C
A
and reaction rate are decrease when the
time is decreased. While for graph of r versus C, reaction rate is increasing when concentration is
increased.












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RECOMMENDATIONS

1) Use another method other than titration. This is because a lot of error comes from
titration.
2) Use another indicator to observe the change of color. The phenolphthalein gives light
pink which are difficult to obtain.
3) Use white tile to see light pink while do titration.
4) After each experiment, drain off any liquids from the reactor and make sure that the
reactor and tunings are cleaned properly. Flush the system with de-ionized water until no
traces of salt are detected.
5) Dispose all liquids immediately after each experiment. Do not leave any solution or waste
in the tanks over a long period of time.
6) Wipe off any spillage from the unit immediately. Always observe all safety precautions
in laboratory.
7) Always wear protective clothing, shoes, helmet and goggles throughout the laboratory
session.
8) Always run the experiment after fully understand the equipment and procedures.
9) Always plug in all cables into appropriate sockets before switching on the main power on
the control panel. Inspect all cables for any damage to avoid electrical shock.
10) Replace if necessary.
11) Make sure that the stirrer assembly is secured properly. Avoid excessive load to the
electrical motor to prevent damage.
12) Inspect the unit, including tubing and fittings, periodically for leakage and worn out.
13) Leakage might cause damage to equipments by corrosive chemical in the long run.





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REFERENCES

1. Chemical Reaction Engineering, Third Edition, Octave Levenspiel, 1999 John Wiley &
Sons
2. Elements of Chemical Reaction Engineering; Third Edition; H. Scott Fogler; Prentice
Hall.
3. http://en.wikipedia.org/wiki/Continuous_stirred-tank_reactor
4. http://www.engin.umich.edu/~cre/asyLearn/bits/cstr/






















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APPENDIX














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