CSTR
CSTR
CSTR
Based on the experiment that has been done, the experiment is conducted to measure
the conversion of ethyl acetate in saponification as a function of design parameters in a
continuous stirred tank reactor (CSTR), to determine the effect of residence time onto
the reaction and also to determine the reaction rate constant. First of all, the general set
up experiment is conducted before started the experiment. After collecting the data, the
value of reaction rate constant is calculated.
Theory has stated that the saponification process is known to be the second order
reactions.There are two experiments, in which the first experiment we use constant
temperature and the second one is different temperature. After run the experiment, the
sample is taken and was titrated using 0.1M NaOH and ethyl acetate to evaluate the
amount of unreacted HCL. This has provide us with the information to determine the
amount of NaOH in feed solution which has reacted.
INTRODUCTION
Continuous-flow stirred-tank reactor is an equipment where the reactants and the
products are continuously added and withdrawn. It is also known as vat- or backmix
reactor.
Figure 1.1 : continuous stirred tank reactor a) with agitator and internal heat transfer
surface, b) with pump around mixing and external heat transfer surface
Basically, mechanical or hydraulic agitation is needed in order to achieve temperature
and uniform composition. Analysis of selected combinations of these reactor types can
be useful in quantitatively evaluating more complex gas, liquid and solid-flow behaviors.
Figure 1.1 is a continuous stirred tank reactors, (a) With agitator and internal heat
transfer surface, (b) With
Because the compositions of mixtures leaving a CSTR are those within the reactor, the
reaction driving forces, usually the reactant concentrations, are necessarily low.
Therefore, except for reaction orders zero- and negative, a CSTR need the largest
volume of the reactor types to obtain desired conversions.
However, the low driving force makes possible better control of rapid exothermic and
endothermic reactions. When high conversions of reactants are needed, several CSTRs
in series can be used. Equally good results can be obtained by dividing a single vessel
into compartments while minimizing back-mixing and short-circuiting. The larger the
number of CSTR stages, the closer the performance approaches that of a tubular plugflow reactor.
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:
OBJECTIVES
The objectives of the experiment are to measure the conversion of ethyl acetate in
saponification as a function of design parameters in a continuous stirred tank reactor
(CSTR), to determine the effect of residence time onto the reaction and also to
determine the reaction rate constant.
THEORIES
One of the common ideal reactor type in the prospect of chemical engineering is
the continuous flow stirred-tank reactor (CSTR) or also known as back mix reactor.
Generally, a CSTR refers to an instrument used to estimate the key unit operation
variables particularly when using a continuous agitated tank reactor to reach a specified
output. The mathematical model works for all fluids: liquids, gases, and slurries.
The reactor run at a steady state with continuous flow of reactants and products; the feed
assumes a uniform composition throughout the reactor, exit stream has the same
composition as in the tank. Since the temperature and concentration are constant for
every inch of the reactor, it is assume it also constant at the exit points as elsewhere in the
tank.
Assuming:
perfect or ideal mixing, as stated above
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.
r dV r dV r V
A
isothermal conditions, or
constant temperature (k is
constant)
F FA
rA
FA0 FA
FA0
FA0 X
rA
0
A0
Reactor sizing
Given -rA as a function of conversion, -rA = f(X), one can size any type of reactor. The
volume of a CSTR can be represented as the shaded areas in the Levenspiel Plot shown
below:
Usually
conducting a reaction at a higher temperature delivers more energy into the system and
increases the reaction rate by causing more collisions between particles, as explained by
collision theory. However, the main reason that temperature increases the rate of reaction
is that more of the colliding particles will have the necessary activation energy resulting
in more successful collisions (when bonds are formed between reactants). The influence
of temperature is described by the Arrhenius equation.
k Ae
Taking the
E
RT
k = rate of constant
E = the activation energy
R = The gas constant
T = temperature
A = frequency factor constant
The reaction involve is a saponification reaction (the reverse reaction would be
esterification). The reaction is 2nd order elementary within the range of 0-0.1 M
concentration and 20-40 C. This reaction may be either reversible or irreversible. For the
irreversible case, the rate equation for a batch reactor may be written:
rA = -d[A]/dt = k[A][B]
where k is the rate constant and [A] and [B] are the concentrations of the reactants in the
appropriate units. If strictly equimolar concentrations of reactants are used, the rate
equation can be simplified to a general nth-order reaction. r A = kn [A]n where n 2. With
good experimental data, this model allows the determination of the reaction order for an
irreversible reaction.
The effect of temperature on the rate constant can be compared with that predicted by
the Arrhenius expression: k = Ae
(-E/RT)
energy of the reaction, R is the gas constant, and T is the absolute temperature. Rate
data at various temperatures can be used to determine the frequency factor and
activation energy of the reaction.
REACTOR:
Material : borosilicate glass; stainless steel top and bottom plate Total Volume : 4 L
Working Volume : 2 to 3.5 litre (adjustable)
Cooling System : cooling water through stainless steel cooling coil
Heating System : 1.5 kW; immersion heater; Temperature Sensor; Temperature
Controller
Gas Sparger : perforated stainless steel tube
Sample analysis : sampling valves (analytical instruments are not included)
STIRRER SYSTEM:
Motor Rating : 75 W (input); 55 W (output)
Variable Speed : 50 to 2,000 rpm; with speed controller and LCD indicator
Impellers : 2 dia.; stainless steel
Electrical : 240VAC/1-phase/50-60Hz.
FEED TANKS:
Capacity : 30 litre (cylindrical)
Material : Stainless steel
PRODUCT TANKS:
Capacity : 60 litre (rectangular)
Material : Stainless steel
FEED PUMPS:
Capacity : 1 LPM
Electrical : 240VAC/1-phase/50-60Hz.
FLOW CONTROL:
Liquid Flowmeter : up to 500 ml/min; electronic
Gas Flowmeter : up to 30 LPM; electronic
Control valves : needle valves
INSTRUMENTATIONS:
The unit is fitted with all necessary instruments for the measurements of reaction
temperature, reactants flow rates, and conductivity
1.
2.
50ml burette
3.
4.
Phenolphtalein
5.
6.
PROCEDURE
Experiment A:
1. The overflow tube in the reactor is being adjusted to give desired working volume 2.5
liters. The pump 1 was switched on to start on pumping 1.25 liters of 0.1M ethyl acetate
from the feed tank into reactor.The pump P1 stopped.
2. Then, the pump P2 was switched on and started to pump another 1.25 liters of the
0.1M NaOH into the reactor. When the 2.5 liters volume is reached, then the pump P2
were being stopped. The stirrer then being switched on and the speed was set in the mid
180rpm.The time is being observed. The start time are recorded.
3. 10ml of 0.25M HCL were quickly measured in a flask.
4. After 1 minute of reaction, sampling valve v7 is opened to collect 50ml sample. 10ml
of HCL is quickly added into sample. The HCL quenched the reaction between ethyl
acetate and sodium hydroxide.
5. The mixture is titrated with the 0.1M NaOH to evaluate the amount of unreacted HCL.
Information is obtained to determine the amount NaOH in feed solution which has
reacted.
Experiment B:
1. The overflow tube in the reactor is being adjusted to give desired working volume 2.5
liters. The pump 1 was switched on to start on pumping 1.25 liters of 0.1M ethyl acetate
4. After 1 minute of reaction, sampling valve v7 is opened to collect 50ml sample. 10ml
of HCL is quickly added into sample. The HCL quenched the reaction between ethyl
acetate and sodium hydroxide.
5. After 1 minute of reaction, sampling valve v7 is opened to collect 50ml sample. 10ml
of HCL is quickly added into sample. The HCL quenched the reaction between ethyl
acetate and sodium hydroxide.
6. Steps 4 and 5 were repeated for reaction times of 5, 10, 15, 20, and 25 minutes.
7. The experiment is repeated for temperature of 40oC and 50oC.
8. The graph ln(CB/CA) vs. t and ln k vs 1/t were plotted.
9. The activation energy was found from the ln k vs 1/T graph.
RESULT
Experiment A
Time
Volume of titrating NaOH (ml)
Volume of quenching HCl
Unreacted with NaOH in Sample
(ml) [C]
Volume of HCl reacted with
NaOH in Sample (ml)
Mole of HCl reacted with NaOH
in Sample
Mole of NaOH Unreacted in
Sample
Concentration of NaOH
Unreacted with Ethyl Acetate
(mol/L)
Steady state fraction of NaOH,
XA
Concentration of NaOH reacted
with Ethyl Acetate (mol/L)
Mole of NaOH reacted with Ethyl
Acetate in Sample
Concentration of Ethyl Acetate
Reacted with NaOH (moles/L)
Concentration of Ethyl Acetate
Unreacted (moles/L)
1
6.3
5
21.3
10
24.1
15
24.6
20
25.2
25
25.0
2.52
8.52
9.64
9.84
10.08
10
7.48
1.48
0.36
0.16
-0.08
0.0018
7
0.0018
7
0.0003
7
0.0003
7
9E-05
4E-05
9E-05
4E-05
0.0037
4
0.0007
4
0.0001
8
8E-05
0.00004
0.9626
0.9926
0.9982
0.9992
1.0004
0.0462
6
0.0231
3
0.0462
6
0.0537
4
0.0992
6
0.0496
3
0.0992
6
0.0007
4
0.0998
2
0.0499
1
0.0998
2
0.0001
8
0.0999
2
0.0499
6
0.0999
2
0.10004
0.1
0.05002
0.05
0.10004
0.1
-4E-05
8E-05
0.00002
0.00002
0
0
Experiment B
T= 29.3 C
Time
10
15
20
6.3
21.3
24.1
24.6
25.2
25
25.
0
2.52
8.52
9.64
9.84
10.08
10
7.48
0.0018
7
0.0018
7
0.0037
4
0.9626
0.0462
6
0.0231
3
0.0462
6
0.0537
4
1.48
0.0003
7
0.0003
7
0.0007
4
0.9926
0.0992
6
0.0496
3
0.0992
6
0.0007
4
0.36
0.16
9E-05
4E-05
9E-05
0.0001
8
0.9982
0.0998
2
0.0499
1
0.0998
2
0.0001
8
4E-05
-0.08
0.00002
0.00002
0.00004
1.0004
0.10004
0.05002
0.1
0.0
5
0.10004
0.1
-4E-05
8E-05
0.9992
0.0999
2
0.0499
6
0.0999
2
8E-05
0
0
0
1
T = 40C
Time
Volume of titrating NaOH (ml)
Volume of quenching HCl
Unreacted with NaOH in
Sample (ml) [C]
Volume of HCl reacted with
NaOH in Sample (ml)
Mole of HCl reacted with NaOH
in Sample
Mole of NaOH Unreacted in
Sample
Concentration of NaOH
Unreacted with Ethyl Acetate
(mol/L)
Steady state fraction of NaOH,
XA
Concentration of NaOH reacted
with Ethyl Acetate (mol/L)
Mole of NaOH reacted with
Ethyl Acetate in Sample
Concentration of Ethyl Acetate
Reacted with NaOH (moles/L)
Concentration of Ethyl Acetate
Unreacted (moles/L)
1
26.7
5
25.2
10
25.6
15
25.6
20
25.8
25
25.0
10.68
10.08
10.24
10.24
10.32
10
-0.68
0.0001
7
0.0001
7
0.0003
4
-0.08
0.0000
2
0.0000
2
0.0000
4
-0.24
-0.24
-0.32
-6E-05
-6E-05
-8E-05
-6E-05
0.0001
2
-6E-05
0.0001
2
-8E-05
0.0001
6
1.0034
0.0503
4
0.0251
7
0.0503
4
0.0496
6
1.0004
0.0500
4
0.0250
2
0.0500
4
0.0499
6
1.0012
0.0501
2
0.0250
6
0.0501
2
0.0498
8
1.0012
0.0501
2
0.0250
6
0.0501
2
0.0498
8
1.0016
0.0501
6
0.0250
8
0.0501
6
0.0498
4
0.05
0.02
5
0.05
0.05
T = 50C
Time
10
15
20
25
26.8
24.5
24.0
25.0
24.8
24.7
10.72
9.8
9.6
10
9.92
9.88
-0.72
0.2
0.4
0.08
0.12
5E-05
1E-04
2E-05
3E-05
5E-05
1E-04
2E-05
3E-05
0.00036
1E-04
0.000
2
4E-05
6E-05
1.0072
0.999
0.998
0.9996
0.9994
0.05036
0.0499
0.02518
0.02495
0.05036
0.0499
0.04964
0.0501
0.0499
6
0.0249
8
0.0499
6
0.0500
4
0.0499
4
0.0249
7
0.0499
4
0.0500
6
0.00018
0.00018
0.049
8
0.024
9
0.049
8
0.050
2
0.05
0.02
5
0.05
0.05
29.3
-434.42
40
-0.0031
50
-0.0038
SAMPLE OF CALCULATION
Experiment A
Volume of Quenching HCl Unreacted with NaOH in Sample (ml) = (0.1 6.3) / 0.25
=2.52
Volume of HCl reacted with NaOH in Sample (ml) = 10 2.52 = 7.48 ml
Mole of NaOH Unreacted in Sample =
Concentration of NaOH reacted with Ethyl Acetate (mol/L)=
Steady state fraction of NaOH, XA =
Concentration of NaOH reacted with Ethyl Acetate (mol/L)
Mole of NaOH reacted with Ethyl Acetate in Sample =
Concentration of Ethyl Acetate Reacted with NaOH (moles/L) =
Concentration of Ethyl Acetate Unreacted (moles/L) =
From the graph, k=the gradient of the graph. k=-434.42 L mol-1 min-1
Since the reaction is second order, -rA=kCA2 = -434.42 L mol-1 min-1 (0.05374 mol L-1) =
-23.3457
Experiment B
The slope form graph of Ln k vs 1/T = 882.27
slope = -Ea / R = 882.27(8.314)
= 7335.19 J/mol
DISCUSSION
The experiment was carried out by using special sodium hydroxide and ethyl acetate.
Inside the reactor, the saponification of sodium hydroxide and ethyl acetate producing
sodium acetate and ethanol. Order of the reaction is based on the powers of the
concentration which are raised in the kinetic law. Based on result and the sample of
calculation, the value of data was fitted to second order reaction. Therefore the rate law
for this experiments is:
-dCa/dt = kCa2
The time taken for each sample taken is from the first minute the time started and
followed by the next 5th minute, 10th minute and so on. The volume of titrating sodium
hydroxide to calculate the amount of quenching hydrochloric acid, phenolphtalein is used
to be the indicator of the mixture to be in neutral condition. Volume of quenching
hydrochloric acid unreacted with sodium hydroxide in sample is calculated using the
amount of sodium hydroxide titrated with the mixture.
The slopes of the graph are representing the specific reaction rate constant, K. K
constant can be obtained by considering all the data obtained throughout the
experiment. Based on the calculation present on the sample of calculation, K can be
calculated.
For the first temperature which is at 29.3C, since the reaction is second order,
-rA = kCA2 = -434.42 L mol-1 min-1 (0.05374 mol L-1) = -23.3457. Then, for this
experiment, the volume of quenching HCl unreacted with NaOH in Sample (ml) is 2.52
ml. Next, the volume of HCl reacted with NaOH in Sample (ml) is 7.48 ml.
The volume of titrating NaOH for experiment A was increase from 6.3 ml, 21.3 ml, 24.1
ml, 24.6 ml, 25.2ml and 25.0 ml. That means the the higher the concentration HCL, the
more volume of NaOH is needed to neutralize the mixture.
However, for the experiment B, the volume of NaOH required was decreasing because
the temperature of the HCL was increasing.
So that, from the Arrhenius equation has been use to give the temperature behavior of
the most reaction rate constant within experimental accuracy over temperature range.
The slope was indicated value of -E/R. The value of ln k2 is higher that ln k1 which has
the positive value of the slope. Based on the equation obtained from the graph ln k vs
1/T,
y = 6730x-21.442, the value of activation energy, E could also be calculated. Activation
energy is important for the molecules to use energy to complete the reaction. After
calculating all the data obtained, values of constant K can be known.
From the graph, the value of k at temperature 29.3C is -434.42 L mol-1 min-1. At
temperature of 40C, the value of k is -0.0031 and the value of k at temperature 50C is
-0.0038.
After that, referring to the graph, the value of the slope can be determined of ln k vs 1/T
= 882.27. Meanwhile the value of slope -Ea / R is 7335.19 J/mol. The amount of
activation energy are not too large for a reaction. The larger the activation energy, the
more temperature sensitive in the rate of reaction. Thus, this shows that the temperature
is not too sensitive in the rate of reaction.
This experiment also need to have the some precaution, for example when if needed to
read the value of the sodium hydroxide from the burette, make sure to look the value at
eye level to get the accurate value from the burette. The same person should be taking
the reading since everyone might have different opinion of the value.
CONCLUSION
After the experiment has been done and the parameters needed is found, a conclusion
for this experiment had been made. First and foremost, this reaction is a 2 nd order.
Therefore the reaction rate by the rate law is in the form of r A=kCACB. The second
conclusion is that by the graph obtain for experiment B, the value of reaction constant, k,
is very dependant of temperature. From the graph value of k is clearly seen as not the
same since the temperature is varies. This conclusion is related with the Arrhenius
equation where it state that k=k0eE/ (RT).
Recommendations
There is several factors in this experiment that might have to change or displace to
obtain more accurate data for this objective. First of all, do not use very high temperature
since the temperature will affect the k value. Then this value will affect the reaction rate.
When high temperature is in use, rather fast reaction is obtain therefore the data is not
suitable for study of rate of reaction.
Repetition of this experiment also needed to make this experiment data obtain much
more accurate and better. Other than that, make sure to stop titrate immediately when
first pink color is observed. Different shade of pink will indicate the different of pH value
as well as the volume of NaOH being used in the titration is no longer accurate. This
situation surely will give out error.
RECOMMENDATION
There is several factors in this experiment that might have to change or displace to
obtain more accurate data for this objective. First of all, do not use very high temperature
since the temperature will affect the k value. Then this value will affect the reaction rate.
When high temperature is in use, rather fast reaction is obtain therefore the data is not
suitable for study of rate of reaction.
Repetition of this experiment also needed to make this experiment data obtain much
more accurate and better. Other than that, make sure to stop titrate immediately when
first pink color is observed. Different shade of pink will indicate the different of pH value
as well as the volume of NaOH being used in the titration is no longer accurate. This
situation surely will give out error.
REFERENCES
1. Fogler, H. S., Elements of Chemical Reaction Engineering,4th Edition, Prentice-Hall,
Inc., Englewood Cliffs, NJ, 2006.
2. Levenspiel, O., Chemical Reaction Engineering, 3rd edition, Cambridge University,
1999.
3. An introduction to chemical engineering kinetics and reactor design by Charles G. Hill,
Jr. and Thatcher W. Root the University of Wisconsin. publish by John Wiley & sons.
Brisbane Toronto Singapore 2014 273-280
4. Chemical Reactant Design by Peter Harriott Page 296-300 publish by CRC Press on
18 April 2014
5. Chemical Reaction Engineering: Essentials, Exercises and Examples by Martin
Schmal
6. Chemical Process Engineering: Design and Economics by Harry Silla published by
CRC Press on 8 August 2003 m/s 383-385.
7. Effect of Operating Conditions on CSTR performance: an Experimental Study, Mohd
Danish , Mohammed K. Al Mesfer, Md Mamoon Rashid, February 2015, retrieved from
http://www.ijera.com/papers/Vol5_issue2/Part%20-%202/K502027478.pdf on 15/3/2016
8. Modeling and Simulation Study of the CSTR for Complex Reaction by Using
Polymath,Kanse Nitin G. , Dhanke P.B. and Thombare Abhijit, 2012, retrieved from
http://www.isca.in/rjcs/Archives/vol2/i4/15.ISCA-RJCS-2012-031%20Done.pdf
on
13/3/2016
9. Aspen Plus Simulation of Saponification of Ethyl Acetate in the Presence of Sodium
Hydroxide in a Plug Flow Reactor, U. P. L. Wijayarathne, K. C. Wasalathilake, 2014,
retrieved
from
http://waset.org/publications/9999474/aspen-plus-simulation-of-
saponification-of-ethyl-acetate-in-the-presence-of-sodium-hydroxide-in-a-plug-flowreactor on 12/3/2016.
10. An Integrated Chemical Reaction Engineering Lab Experiment, Adelio M. Mendes,
Luis
Madeira,
Fernao
D.
Magalhaes,
Jose
M.
Sousa,
retrieved
from
http://www.engr.uky.edu/~aseeched/SummerSchool/2007/session_handouts/new_approac
hes/kinetics/v38p228.pdf on 20/3/2016.
APPENDICES
Continuous stirred-tank reactors (CSTR) commonly used in industrial processing
especially in homogeneous (same phase) liquid-phase, in series or in a battery.
In pharmaceutical industry, CSTRs often used in biological processes, such as cell
culture in research or production. Next, Fermentors are CSTR used in biological process
such as brewing, antibiotics, and waste treatment.
A CSTR
reactor
also used
in
the