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Experiment 4, Plug Flow Reactor was conducted to determine the effect of residence time
on the reaction of sodium hydroxide, NaOH with ethyl acetate Et(Ac), in a plug flow reactor.
In this experiment, back titration method was used to determine the conversion and rate law
in order to obtain the concentration of reacted and unreacted NaOH. Two samples were
taken from the reactor, for each flowrate, and was quenched with HCl and back titrated with
NaOH to determine the conversion of NaOH for each respective flowrate pairs. To put it
simply, the two solutions Sodium Hydroxide, NaOH and Ethyl Acetate, Et(Ac) were reacted
in the PFR and the product is then analysed by the method of titration to determine how well
did the reaction go. After the result was obtained, calculations were made and graph of
conversion versus residence time was plotted. Based on the experiment, the residence time
gives effect on the reaction in terms on conversion X, rate constant k, and rate =rA. Further
details can be obtained in the results and discussion sections. The objectives initially set for
this experiment was all obtained successfully
INTRODUCTION
Type of chemical reactors remains a highly discussed subject in chemical process
industries worldwide.The reactor is of course, the place where chemical reactions take
place. Hence it is arguably the single most important part of any chemical process design.
The design of a reactor must be finely tuned so that its mechanisms suit the necesseties of
the process that is to be carried. Depends on the nature of the materials in both the feed and
of course the products, the reactors may take a wide range of forms. This is why full
comprehension of a reactor of a particular design as well as its working mechanisms is very
much vital to actually conduct a particular chemical process
A plug flow reactor is a reactor in which the flow inside the reactor is continuous and
usually flows in a steady-state condition. Continuous flow means that the reactants are
continually consumed as they enter and go through the reactor, and the products formed
from the reaction are continuously flowing out of the reactor (Fogler, 2014). It is one of the
simplest of all reactor designs (Parr Instrument Company, n.d.). The PFR consists of
cylindrical pipes inside its reactor (Fogler, 2014). This type of reactor is widely used in the
industry. Unlike the Continuous Stirred Tank Reactor (CSTR), the PFR can be used for both
homogeneous and heterogeneous reactions. In other words, the PFR can be used for gasphase reactions as well as liquid-phase reactions. Another advantage of the PFR is that it
can give a high conversion rate per volume. Besides that, plug flow reactors are used for
chemical kinetic studies (Brown, n.d.).
AIMS
THEORY
The plug flow reactor is a continuous reactor, that is, the flow in and out of the reactor
is continuous throughout time. The feed enters the reactor, and at the same time, the
products leave the reactor. The plug flow reactor can be used for heterogeneous reactions
as well, for example, reactions in which the reactants are in gaseous phase.
aA+bB cC +dD
A and B represent reactants while C and D represent products. In this reaction, A and
B is being diminished and C and D is being produced. Rate of reaction, concerns it with how
fast the reactants diminish or how fast the product is formed. Rate of reaction of each
species corresponds respectively to their stoichiometric coefficient. As such:
r A r B r C r D
=
= =
a
b
c d
The negative sign indicates reactants.
A usual equation for rA is:
r A=k C A C B
Where:
k
rate constant
CA
concentration of A species
CB
concentration of B species
stoichiometric coefficient of A
stoichiometric coefficient of B
Conversion
Taking species A as the basis, the reaction expression can be divided through the
stoichiometric coefficient of species A, hence the reaction expression can be arranged as
follows:
b
c
d
A + B+ C + D
a
a
a
Conversion is an improved way of quantifying exactly how far has the reaction
moved, or how many moles of products are formed for every mole of A has consumed.
Conversion XA is the number of moles of A that have reacted per mole of A fed to the system.
As seen below:
X A=
moles of A reacted
moles of A fed
out + generation=0
When:
In=FA0, out=FA and
generation= r a dV
assumed to be perfectly and equally mixed, which is in the case for CSTR. Therefore, the
general equation becomes
F A 0F A + r a dV =0
V =F A 0
0
dX
(Equation1)
r A
Where:
-
r A=k (C A ) (C B ) ,
k is rate constant
and
V=
F A0
k C A0
C v
v
X
X
X
= A 0 02
= 0
( Equation3)
( 1X ) k C A 0 (1X ) k C A 0 (1 X)
APPARATUS
The following apparatus and equipment were used to conduct this experiment:
-
Control
Panel
Reactor
Tank
Flowrate
Adjusters for
P1 and P2
Reactant Tanks
PROCEDURE
A : Back Titration Procedures for Manual Conversion Determination
1. The 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 from the experiment was obtained and added immediately the
sample to the HCl in the flask to quench the saponification reaction.
4. A few drops of pH indicator was added into the mixture.
5. The mixture was titrated with NaOH solution from the burette until the mixture is
neutralized.The amount of NaOH titrated was recorded.
CALCULATION
Residence Time
1. For flow rates of 300 ml/min :
=
Residence Time,
Reactor volume ( L ) ,V
L
Total flow rate
,v
min 0
( )
Hence,
Residence Time,
4L
0.6 L/min
= 6.6667 min
Hence,
Residence Time,
4L
0.5 L/min
= 8.000 min
= 0.4 L/min
Hence,
Residence Time,
4L
0.4 L/min
= 10.000 min
Hence,
Residence Time,
4L
0.3 L/min
= 13.333 min
Hence,
Residence Time,
4L
0.2 L/min
= 20.000 min
4L
0.1 L/min
= 40.000 min
Conversion
1. For flow rates of 300 ml/min :
Moles of reacted NaOH, n1
n1
= Concentration NaOH x Volume of NaOH titrated
= 0.1 M x 0.000279 L
= 0.0000279 mole
Moles of unreacted HCl
= Moles of reacted NaOH
n2
n2
= n1
= 0.0000279 mole
n2
concentration HCl quenc h
0.0000279
0.25
= 0.000112 L
Volume of HCl reacted, V2
V2
n3
= Concentration HCl x V2
= 0.25 x 0.00989
= 0.00247 mole
=
=
n3
0.00247 mole
n4
volume sample
0.00247
0.05
= 0.0494 M
Xunreacted =
=
= 0.494
Xreacted
= 1 - Xunreacted
= 1 - 0.494
= 0.506
\
2. For flow rates of 250 ml/min :
Moles of reacted NaOH, n1
n1
n2
concentration HCl quenc h
0.0000287
0.25
= 0.0001148 L
Volume of HCl reacted, V2
V2
= Concentration HCl x V2
= 0.25 x 0.009885
= 0.002471 mole
= n3
= 0.002471 mole
Concentration of unreacted NaOH
CNaOH unreacted
n4
volume sample
0.002471
0.05
= 0.04942 M
Xunreacted =
=
= 0.4942
Xreacted
= 1 - Xunreacted
= 1 - 0.4942
= 0.5058
n2
concentration HCl quenc h
0.0000246
0.25
= 0.0000984 L
Volume of HCl reacted, V2
V2
= 0.01 0.0000984
= 0.009902 L
Moles of reacted HCl, n3
n3
= Concentration HCl x V2
= 0.25 x 0.009902
= 0.002476 mole
= n3
= 0.002476 mole
n4
volume sample
0.002476
0.05
= 0.04952 M
Xunreacted =
=
= 0.4952
Xreacted
= 1 - Xunreacted
= 1 - 0.4952
= 0.5048
= 0.0000265 mole
Moles of unreacted HCl, n2
Moles of unreacted HCl
n2
concentration HCl quenc h
0.0000265
0.25
= 0.000106 L
Volume of HCl reacted, V2
V2
= Concentration HCl x V2
= 0.25 x 0.009894
= 0.002474 mole
= n3
= 0.002474 mole
n4
volume sample
0.002474
0.05
= 0.04948 M
Xunreacted =
=
= 0.4948
Xreacted
Xreacted
= 1 - Xunreacted
= 1 - 0.4948
= 0.5052
placed in Table 2
Hence, at flow rate 150 mL/min of NaOH in the reactor, about 50.52% of NaOH is reacted with
Et(Ac).
5. For flow rates of 100 ml/min :
Moles of reacted NaOH, n1
n1
= Concentration NaOH x Volume of NaOH titrated
= 0.1 M x 0.000256 L
= 0.0000256 mole
Moles of unreacted HCl, n2
Moles of unreacted HCl
n2
concentration HCl quenc h
0.0000256
0.25
= 0.0001024 L
Volume of HCl reacted, V2
V2
= Concentration HCl x V2
= 0.25 x 0.009898
= 0.002475 mole
= n3
= 0.002475 mole
n4
volume sample
0.002475
0.05
= 0.0495 M
Xunreacted =
=
= 0.495
Xreacted
Xreacted
= 1 - Xunreacted
= 1 - 0.495
= 0.505
V1
n2
concentration HCl quenc h
0.0000281
0.25
= 0.0001124 L
Volume of HCl reacted, V2
V2
= Concentration HCl x V2
= 0.25 x 0.009888
= 0.002472 mole
= n3
= 0.002472 mole
n4
volume sample
0.002472
0.05
= 0.04944 M
Xunreacted =
=
= 0.4944
Xreacted
Xreacted
= 1 - Xunreacted
= 1 - 0.4944
= 0.5056
k=
v0
X
V TFR C AO 1X
VTFR
CAO
= 0.506
k=
0.6
0.506
(4)(0.1) 10.506
VTFR
CAO
= 0.5058
= 1.5365 L.mol/min
k=
0.5
0.5058
(4)(0.1) 10.5058
= 1.2793 L.mol/min
= 1.0194 L.mol/min
= 0.7658 L.mol/min
VTFR
CAO
= 0.5048
k=
0.4
0.5048
(4)(0.1) 10.5048
VTFR
CAO
= 0.5052
k=
0.3
0.5052
(4)(0.1) 10.5052
VTFR
CAO
= 0.5050
k=
0.2
0.5050
(4)(0.1) 10.5050
= 0.5101 L.mol/min
= 0.2557 L.mol/min
VTFR
CAO
= 0.5056
k=
0.1
0.5056
(4)(0.1) 10.5056
-rA
10
15
20
25
30
35
40
45
DISCUSSION
Based on the results and calculations that have been done, the conversion of NaOH pair
has been successfully obtained for each flowrate. The main objective of this experiment has
been achieved which is to observe the effect of residence time on the reaction between NaOH
and Et(Ac) in a plug flow reactor based on a graph of conversion against residence time was
plotted by referring the calculated result. Residence times, refers to the time that a certain
compound spends in a particular system, or in this case, in the reactor. It is also sometimes
known as space time, or holding time. The formula for residence time is given, as in the
calculations:
residence time, =
reactor volume , V ( L)
L
total flowrate , v 0 (
)
min
Only one type of reactor is used since the reactor volume is constant. The method was
applied to manipulate the residence time is by changing the total flowrate that enters the PFR.
In this experiment, the flowrates was changed from 300 to 50 ml/min for both reactants, at 50
ml/min decrements.
As for conversion, XA, the value can be obtained from a series of calculations based on
the back-titration result, which is the volume of NaOH titrated. Based on the graph of X vs
residence time was plotted, it can be observed that the conversion does not change significantly
as the residence time increases. There is only a slight increment in the conversion as the
residence time rises. Thus, it can be said that the residence time does not give a large and
significant effect on the conversion of NaOH in the saponification reaction between NaOH and
Et(Ac).
If the formula for calculating X is observed, the basis of the calculation is the volume of
NaOH titrated to change the quench sample solution colour to pink. When referring to the
results of titration, the volume required for titration show some increases and some decreases
as the total flowrate, v0 decreases. It may occur some error during back-titration process. In
other words, as the residence time increases, due to lower total flowrate, the volume of NaOH
titrated also increases, however not significantly. Also, when the volume of titrated NaOH
increases, the no. of moles of NaOH reacted n1 increases, thus n2 also increases as n1=n2.
When n2, which is no. of moles HCl unreacted increases, the volume of unreacted HCl V1 also
increases, as
v=
no . of moles
concentraion . When V1 increases, V2 which is the volume of reacted HCl
X unreacted =
concentration of unreacted
, will decrease, and finally, Xreacted or XA increases, since
initial concentration
XA/reacted=1-Xunreacted. Concluding this, as volume of titrated NaOH increases, the conversion XA will
also increase.
As for rate constant k, it is dependent on flowrate v0, as the formula is:
k=
v0
X
.(
)
V C A 0 1 X
Therefore, as the flowrate decreases, the rate constant also decreases. Residence time
effect is not significant in this case.
Finally, for reaction rate rA, it is dependent on k, thus also meaning that it is dependent
on the flowrate. Therefore, as the total flowrate continues to decrease in this experiment, the
reaction rate shall also decrease. Again, the effect of residence time is insignificant in this case,
as the residence time gives a small effect on X.
CONCLUSION
In conclusion, the experiment was conducted with several objectives in mind. The first
one is to carry out a saponification process between Sodium Hydroxide, NaOH and Ethyl
Acetate, Et(Ac). By using a Plug Flow Reactor, PFR, these two substances were flowed into the
reactor, mixed and let to react for a certain period of time. By doing that, saponification process
was completed. The experiment also targets to determine the reaction rate of this particular
reaction. From the calculated results, there is a small effect of residence time on the conversion
of sodium hydroxide, NaOH, in the reaction between NaOH and ethyl acetate Et(Ac), that is, as
the residence time increases, the conversion of NaOH will slightly increase. There is small
changes in the conversion as the residence time increases. Also, the rate constants and the
reaction rate, or in other words, the rate law, for the reaction has also been determined from the
calculations. Also, the rate constant k is found to be decreasing as the total flowrate decreases
in this experiment. The same conditions apply for the reaction rate, as rate depends on k, k
depends on flowrate. Residence time gives very small impact on these two variables, as it gives
a small change to conversion X, which is used for calculation of rate constant k, and therefore
reaction rate rA.
RECOMMENDATIONS
There are a few recommendations that can be done to get better results:
1. The flowrates should be constantly monitored to ensure that it remains constant
throughout the running time.
2. Ensure that the reactor is in good condition, that is, there is no leakage. Leakage in the
reactor can lead to errors as the output is no longer controllable. This can affect the
concentration of the samples taken for titration, thus affecting the results and
calculations.
3. When conducting back-titration, conduct it three times for each flowrate pair by using
three samples taken, and determine the average volume of NaOH titrated, to get better
and more accurate results.
4. When taking sample, ensure that the flask, or beaker used is properly cleaned,
especially from HCl and phenolphthalein to avoid the solution from turning pink even
before titration
5. Increase the running time, from 7.5 minutes to 10 minutes, to ensure that the system has
reached a stable steady-state condition. However, do not let the system run for too long
for each flowrate, as it can affect the reaction occurring inside.
REFERENCES
1. Fogler, H.S (2006). Elements of Chemical Reaction Engineering (3rd Edition). Prentice
Hall.
2. Brown, R. L., n.d. Tubular Flow Reactors With First-Order Kinetics
3. Levenspiel, O. (1999). Chemical Reaction Engineering (3rd Edition). John Wiley.
4. Laboratory Manual Tubular Flow Reactor.
5. Fogler, H. S., 2014. Continuous-Flow Reactors. In: Elements Of Chemical Reaction
Engineering, Fourth Edition. s.l.:Pearson New International Edition, pp. 14-15.
6. The Plug Flow (Retrieved from http://www.konferenslund.se/p/L16.pdf on 18th October
2013)
7. Reaction Kinetics (Retrieved from http://smk3ae.files.wordpress.com/2007/10/reaksikinetik.pdf on the 18th October 2013)
8. Christie J. Geankoplis(2003) Transport Processes and Separation Process Principles(4th
Edition)
9. Parr Instrument Company, n.d. 5400 Continuous Flow Tubular Reactors. [Online]
Available at: http://www.parrinst.com/products/specialty-custom-systems/5400continuous-flow-tubular-reactors/
10. https://www.scribd.com/doc/179120412/Plug-Flow-Reactor