ABSTRACT

Continuous stirred tank reactor (CSTR) is a common reactor in chemical engineering that had an
impeller or other mixing device to provide efficient mixing. The behavior of a CSTR is ideal and
all the calculations performed with CSTR can be assumed perfect mixing. Perfect mixing means
the output composition is identical to the materials at the inside the reactor. The objective of this
experiment is to study the effect of the temperature on the reaction rate constant and to determine
the activation energy for saponification reaction. The experiment started by mixing the sodium
hydroxide, NaOH and ethyl acetate, Et(Ac) with the equal volume into the reactor at the desired
temperature which is 30 ̊ c. After a certain time, for the mixture react, 50mL of the sample was
collected for the titration process. The volume of the sodium hydroxide used for titration was
recorded. The sample was collected again at the different reaction time. The same procedure was
repeated at the different temperatures which are 40 ̊ c and 50 ̊ c. From the data, plot the graph to
get the value of the reaction rate constant at the different temperatures.
INTRODUCTION

Continuous stirred tank reactor (CSTR) is a common reactor in chemical engineering that had an
impeller or other mixing device to provide efficient mixing. The reactants are continuously fed
into the reactor and the products are continuously removed from the reactor. The behavior of a
CSTR is ideal and all the calculations performed with CSTR can be assumed perfect mixing.
Perfect mixing means the output composition is identical to the materials at the inside the
reactor. CSTR is commonly used in the industries because it is easy maintained due to good
temperature controller beside it is cheap to construct as well as has large heat capacity. But, the
conversion of reactant to product per volume of the reactor is small compared to the other flow
reactors. Generally, CSTR that commonly used was jacketed or had coil in order to maintain the
reaction temperature in the reactor. The reaction that occurred in the reactor can be either
exothermic or endothermic. If the reaction is exothermic, the reaction will released the heat in
order to reduce the temperature in the reactor. For this, the coolant stream is required to pass
through the jacket or the coil to remove the extra heat. On the other hand, if the reaction is
endothermic, the reaction will absorb the heat in order rise the temperature in the reactor. For
this, the heating element will be applied in order to gain the extra heat.

In chemical industries, chemical kinetics and reactor design are the most important. The
successes or failed of a chemical plant is affected by the selection of a reaction system that
operates in the safest and most efficient way. If the reaction that occurred in the reactor operated
at the constant temperature, it is called as isothermal reaction.

In adiabatic reactor, there is no interchange of heat occurs between the system and the
surroundings which means, there is no cooling or heating element that will be needed to maintain
the temperature of the system.
OBJECTIVE

To determine the effect of the temperature on reaction rate constant, k and determine the
activation energy of saponification.

THEORY

Continuous stirred tank reactor (CSTR) is a common reactor in chemical engineering that had
been used in industries. It consists of an impeller or other mixing device to provide efficient
mixing. In other words, the contents are well stirred and uniform throughout. The behavior of a
CSTR is ideal which is modeled as having no spatial variation in concentration, temperature, or
reaction rate throughout the vessel. All the calculations performed with CSTR can be assumed
perfect mixing. Perfect mixing means the output composition is identical to the materials at the
elsewhere inside the reactor.

The general mass balance equation:

Inlet – Outlet + Generation = Accumulation

The general mass balance equation for continuous stirred tank reactor:

𝑉 𝑑𝑁𝐴
FA0 – FA + ∫0 𝑟𝐴 𝑑𝑉 = ~ equation 1
𝑑𝑡
There had some assumptions that have been usually used in the calculation that involves the
continuous stirred reactor.

1. The system is in steady state, which means there will be no accumulation.

𝑑𝑁𝐴
=0
𝑑𝑡

2. The system in the reactor is well mixed, which means reaction rate, rA is constant.
𝑉 𝑉
∫0 𝑟𝐴 𝑑𝑉 = rA ∫0 𝑑𝑉 = rAV

Substitute the assumptions into the equation 1, and rearrange the equation:
𝐹𝐴0−𝐹𝐴
V= ~ equation 2
−𝑟𝐴

Where FA = FA0 (1 – X), equation 2 becomes,

𝐹𝐴0 .𝑋
V=
−𝑟𝐴

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑢𝑝 𝑡𝑜 𝑝𝑜𝑖𝑛𝑡 𝑖

Where Xi =
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑓𝑒𝑑 𝑡𝑜 𝑓𝑖𝑟𝑠𝑡 𝑟𝑒𝑎𝑐𝑡𝑜𝑟

There are many different types of methods for data analysis which were used to identify the
reaction order and reaction rate constant, k. Differential, integral, initial rates, and half lives are
the methods involved in the data analysis. In this experiment, integral method was the chosen
method in data analysis.

For 0th order reaction:

-ra = kCa0

-dCa / dt = k

-dCa = k.dt

-( Ca – Ca0 ) = k.t

Ca = -k.t + Ca0
For 1st order reaction:

-ra = kCa1

-dCa / dt = kCa

-dCa / Ca = k.dt

- [ln (Ca) – ln (Ca0)] = k.t

Ln (Ca0 / Ca) = k.t

For 2nd order reaction:

-ra = kCa2

-dCa / dt = kCa2

-dCa / Ca2 = k.dt

- [ -Ca-1 + Ca0-1 ] = k.t

1 / Ca = k.t + 1 / Ca0

Activation energy, Ea is the minimum amount of energy that is required to activate atoms or
molecules to a condition in which they can undergo chemical transformation or physical
transport. Activation energy can be shown in the Arrhenius Law equation:

k = A * e-Ea/RT

Where;

k = rate reaction constant

Ea = activation energy

R = gas constant

T = temperature in unit of Kelvin

A = frequency factor constant or also known as pre-exponential factor or Arrhenius factor.

APPARATUS

1. Conical flasks
2. 50mL burrete
3. 100mL measuring cylinder
4. 0.25M hydrochloric acid
5. 0.1M sodium hydroxide
6. 0.1M ethyl acetate
7. Phenolphthalein
8. Continuous stirred tank reactor (model: BP100)
PROCEDURE

General start up procedure;

1. Prepared the following solutions:
a. 20L of sodium hydroxide, NaOH (0.1M)
b. 20L of ethyl acetate, Et (Ac) (0.1M)
c. 1L of hydrochloric acid, HCl for quenching (0.25M)
2. Closed all valves initially.
3. Charged the feed tank:
a. Opened the port charge for tank1 and tank2.
b. Carefully poured the NaOH solution into vessel T2 and Et(Ac) solution into T1.
c. Closed the charge port for both tanks.
4. Turned on the power for the control panel.
5. Did not switch on the heater until it was fully submerged in the liquid. To avoid the
damage on heater, liquid level was maintained above the heater.
6. To avoid the damage to the mechanical seal, the stirrer the assembly was secured
properly.
7. All tubes were inspected periodically for leakage and worm up leakage might cause
damage to equipment by corrosive reactants.
Experiment procedure;
1. Switched on the pump P1 to pump 1.25L of 0.05M ethyl acetate, Et(Ac), from the feed
tank into the reactor.
2. Then, switched on the pump P2 to pump 1.25L of 0.05M sodium hydroxide, NaOH, from
the feed tank into the reactor.
3. Switched off the pump2 when the total volume of the reactor reached 2.5L.
4. Switched on the heater to get the desired temperature which is 30 ̊ c.
5. Make sure the temperature maintained at 30 ̊ c by control the cool water flowrate.
6. Once the temperature of the reactor was reach the desired value, switched on the stirrer
and start the timer simultaneously.
7. After 1minute of reaction, collect 50mL of sample and then titrated with sodium
hydroxide following titration procedure.
 8. Repeated step 7 for the reaction time of 5minutes, 10minutes, 15minutes, 20minutes, and
25minutes.
9. Repeated the experiment for the temperature 40 ̊ c and 50 ̊ c.
Titration procedure;
1. Prepared the 10mL of 0.25M hydrochloric acid, HCl in the conical flask.
2. Added 50mL of the sample collected into the conical flask to quench the saponification
reaction.
3. Added 3 drops of phenolphthalein into the conical flask as indicator.
4. Then the mixture was titrated with 0.1M of sodium hydroxide, NaOH, until it neutralized
(turned into light pink).
5. The volume of the sodium hydroxide, NaOH used for the titrated was recorded.
General shut down;
1. Kept open the cool water valve from main pipe to allow the cool water to continue
flowing for the temperature reduced.
2. Switched off both pumps P1 and P2.
3. Switched off the stirrer and heater to let the equipment to cool down to room temperature.
4. Closed the cool water valve from the main pipe.
5. Turned off the power for control panel.
RESULTS

For the temperature 30 ̊ c

Time (min) Volume of NaOH Ca (mol/L) 1/Ca (L/mol)

used for titration
(mL)
1 9.7 0.0306 32.6797
5 10.3 0.0294 34.0136
10 10.8 0.0284 35.2113
15 11.0 0.0280 35.7143
20 11.6 0.0268 37.3134
25 11.9 0.0262 38.1679

For the temperature 40 ̊ c

Time (min) Volume of NaOH Ca (mol/L) 1/Ca (L/mol)

used for titration
(mL)
1 8.5 0.0330 30.3030
5 10.9 0.0282 35.4610
10 11.2 0.0276 36.2319
15 11.4 0.0272 36.7647
20 11.5 0.0270 37.0370
25 11.6 0.0268 37.3134

For the temperature 50 ̊ c

Time (min) Volume of NaOH Ca (mol/L) 1/Ca (L/mol)

used for titration
(mL)
1 7.9 0.0342 29.2398
5 15.9 0.0182 54.9451
10 16.8 0.0164 60.9756
15 17.4 0.0152 65.7895
20 17.5 0.0150 66.6667
25 18.7 0.0126 79.3651
 90
80 temperature 30
y = 1.6845x + 38.16
70
temperature 40
60
1 / Ca (L/mol)

50
temperature 50
y = 0.2312x + 32.59
40
30 y = 0.222x + 32.704 Linear (temperature
20 30)

10 Linear (temperature
40)
0
0 10 20 30 Linear (temperature
50)
time, t (minute)

Graph1: 1/Ca versus time for reaction at 30 ̊ c, 40 ̊ c, and 50 ̊ c

1.8
reaction rate constant, k (L/mol.min)

1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
20 25 30 35 40 45 50 55 60
temperature, c

Graph2: reaction rate constant versus temperature

CALCULATIONS

Sample of calculation

For temperature 30 ̊ c at 1minute;

Volume of unreacted quenching HCL, V1:

V1 = (CNaOH / CHCl) x volume of titrated NaOH = (0.1 mol.L-1 / 0.25mol.L-1) x 9.7mL

V1 = 3.88mL

Volume of HCl reacted, V2:

V2= VHCl – V1 = 10mL – 3.88mL

V2= 6.12mL

Moles of reacted HCl, n1:

n1 = CHCl x V2 = 0.25mol/L x 6.12mL (1L / 1000mL)

n1= 0.00153mol

Moles of unreacted NaOH in sample, n2:

n2 = n1 = 0.00153mol

Concentration of unreacted NaOH, CNaOH:

CNaOH = n2 / volume of sample = 0.00153mol / 0.05L

CNaOH = 0.0306mol/L

1/ Ca = 1/ 0.0306mol.L-1 = 32.6797 L/mol

For temperature 30 ̊ c

Time Volume of Volume of Volume of Moles of Ca (mol/L) 1/Ca

(min) NaOH unreacted HCl reacted HCl (L/mol)
used for quenching reacted, V2 =
titration HCL, V1 (mL) Moles of
(mL) (mL) unreacted
NaOH in
sample
n1=n2
(mol)
1 9.7 3.88 6.12 0.00153 0.0306 32.6797
5 10.3 4.12 5.88 0.00147 0.0294 34.0136
10 10.8 4.32 5.68 0.00142 0.0284 35.2113
15 11.0 4.40 5.60 0.00140 0.0280 35.7143
20 11.6 4.64 5.36 0.00134 0.0268 37.3134
25 11.9 4.76 5.24 0.00131 0.0262 38.1679

45
40
y = 0.222x + 32.704
35
30
1 / Ca (L/mol)

25
20
15
10
5
0
0 5 10 15 20 25 30
time, t (min)

Graph3: 1/Ca versus time at temperature 30 ̊ c

Compare equation from the graph with the equation from the theory part

Y = 0.222 X + 32.7 ~ from graph

1 / Ca = k.t + 1 / Ca0 ~ from theory

So, reaction rate constant is equal to 0.222 L/mol.min

For temperature 40 ̊ c

Time Volume of Volume of Volume of Moles of Ca (mol/L) 1/Ca

(min) NaOH unreacted HCl reacted HCl (L/mol)
used for quenching reacted, V2 =
titration HCL, V1 (mL) Moles of
(mL) (mL) unreacted
NaOH in
sample
n1=n2
(mol)
1 8.5 3.40 6.60 0.00165 0.0330 30.3030
5 10.9 4.36 5.64 0.00141 0.0282 35.4610
10 11.2 4.48 5.52 0.00138 0.0276 36.2319
15 11.4 4.56 5.44 0.00136 0.0272 36.7647
20 11.5 4.60 5.40 0.00135 0.0270 37.0370
25 11.6 4.64 5.36 0.00134 0.0268 37.3134

45
40
y = 0.2312x + 32.59
35
30
1 / Ca (L/mol)

25
20
15
10
5
0
0 5 10 15 20 25 30
time, t (min)

Graph4: 1/Ca versus time at temperature 40 ̊ c

Compare equation from the graph with the equation from the theory part

Y = 0.231 X + 32.59 ~ from graph

1 / Ca = k.t + 1 / Ca0 ~ from theory

So, reaction rate constant is equal to 0.231 L/mol.min

For temperature 50 ̊ c

Time Volume of Volume of Volume of Moles of Ca (mol/L) 1/Ca

(min) NaOH unreacted HCl reacted HCl (L/mol)
used for quenching reacted, V2 =
titration HCL, V1 (mL) Moles of
(mL) (mL) unreacted
NaOH in
sample
n1=n2
(mol)
1 7.9 3.16 6.84 0.00171 0.0342 29.2398
5 15.9 6.36 3.64 0.00091 0.0182 54.9451
10 16.8 6.72 3.28 0.00082 0.0164 60.9756
15 17.4 6.96 3.04 0.00076 0.0152 65.7895
20 17.5 7.00 3.00 0.00075 0.0150 66.6667
25 18.7 7.48 2.52 0.00063 0.0126 79.3651

90
80 y = 1.6845x + 38.16
70
60
1/Ca (L/mol)

50
40
30
20
10
0
0 5 10 15 20 25 30
time, t (min)

Graph5: 1/Ca versus time at temperature 50 ̊ c

Compare equation from the graph with the equation from the theory part

Y = 1.684 X + 38.16 ~ from graph

1 / Ca = k.t + 1 / Ca0 ~ from theory

So, reaction rate constant is equal to 1.684 L/mol.min

From Arrhenius Law equation:

k = A * e-Ea/RT

ln k = ln A – Ea / RT

ln k = -(Ea / R) (1/T) + ln A ~equation1

Determine the activation energy by using graph:

Temperature (K) Rate reaction Ln (k) 1/T

constant, k
(L/mol.min)
303 0.222 -1.5051 0.0033
313 0.231 -1.4653 0.0032
323 1.684 0.5212 0.0031

0.5

0
0.00305 0.0031 0.00315 0.0032 0.00325 0.0033 0.00335
ln (k)

-0.5

-1

-1.5

y = -10131x + 31.604
-2
1 / T (K-1)

Graph6: graph ln(k) versus 1/T

Compare equation from the graph with the equation Arrhenius Law

Y = -10132 X + 31.6 ~ from graph

ln k = -(Ea / R) (1/T) + ln A ~ from Arrhenius Law

So, -Ea / R = -10132 K where R = 8.314 J/mol.K

Ea = (10132 K).R

Ea = (10132 K) (8.314 J/mol.K)

Ea = 84237.448 J/mol

Determine the activation energy by using equation:

At temperature 303K, rate reaction constant is equal to 0.222 L/mol.min

At temperature 323K, rate reaction constant is equal to 1.684 L/mol.min

From equation1: ln k = -(Ea / R) (1/T) + ln A

ln k1 = -(Ea / R) (1/T1) + ln A ~equation 1.a

ln k2 = -(Ea / R) (1/T2) + ln A ~equation 1.b

Equation 1.a minus equation 1.b:

𝑘1 𝐸𝑎 1 1
Ln (𝑘2) = [𝑇2 − ]
𝑅 𝑇1

1.684 𝐸𝑎 1 1
Ln (0.222) = 8.314 [303 − ]
323

Ea = 82436.2378 J/mol
DISCUSSION

There are many different types of methods for data analysis which were used to identify the
reaction order and reaction rate constant, k. Differential, integral, initial rates, and half lives are
the methods involved in the data analysis. In this experiment, integral method was the chosen
method in data analysis. In integral method, the first thing that should be done is to guess the
order of the reaction either it is zeroth, first, or second order reaction. The rate law equation can
be modified by some derivation and integration to get the straight line equation y= mx+c. Then,
by ploting the graph, the one that give the straight line graph is the right order of the reaction.

From the data collected, the one that fitted and can give the straight line graph is the second
order reaction. From the graph1, the slope or gradient of the graph can be represented as the
reaction rate constant. This is because of the rate law equation that was modified as stated in the
theory’s part. From the graph2, it can be shown that as the temperature increases from 30 ̊ c to
50 ̊ c, the value of the reaction rate constant, k also increases from 0.0222L/mol.min to
0.1684L/mol.min. In other words, the value of the reaction rate constant is directly proportional
to the temperature.

Arrhenius equation used in order to determine the activation energy of the saponification
reaction. In order to determine the activation energy, there are two different ways which are by
using the graphical method and by using the Arrhenius equation. In graphical method, Arrhenius
equation can be modified by some derivation to get the straight line equation and by using the
data of rate reaction constant and temperature, the graph6 was plotted. From the graph, the slope
of the graph can be represented as the ratio of activation energy to universal gas constant. With
the universal gas constant is equal to 8.314J/mol.K, the activation energy can be determined. The
other way to determine the activation energy is by using Arrhenius equation. By some derivation
of Arrhenius equation with the data collected from results and calculations, the value of
activation energy can be determined. The value of the activation energy form the graphical
method is 84237.448 J/mol, while the value of the activation energy form the calculation method
is 82436.2378 J/mol. The values of the activation energy has slightly different, this is may be
because of the some error that was occurred during the conducting the experiment.
Actually the value of the reaction rate constant is directly proportional to the temperature.
But, from the graph2, it can be shown that the value of the reaction rate constant at the
temperature 30 ̊ c and 40 ̊ c was approximately similar into each other. This is because of the
error that had been occurred during the experiment conducted. One of the errors that cause the
data was affected is the error that occurred during the titration process. The volume of the
sodium hydroxide used for titration should be recorded as soon as the solution of turned into
light pink color. The results is probability was affected because of the volume of sodium
hydroxide used for titration was recorded slightly late than it should be. Which means, the
volume of sodium hydroxide used for titration was recorded when the sample was turned into the
dark pink color or purple color. Besides, the parallax error is the common error that always
occurred during recorded the data such as taking the reading of the volume of sodium hydroxide
titrated. Parallax error is the error that affected by the perceived shift in an object’s position as it
is viewed from the different angles.
CONCLUSION

From the results and calculation of this experiment, it can be concluded that the reaction was
second order. This is because of the data collected was fitted and it can give the straight line
graph as shown in the graph1. Besides, by referring to the graph2, it can be concluded that the
value of the reaction rate constant is directly proportional to the temperature. It is because, as the
temperature increases, the value of the reaction rate also increases. The values of the activation
energy that was determined from the graphical and calculation method show that the
saponification reaction is endothermic reaction. In overall, the experiment was successfully done
as the objectives of the experiment which are to determine the effect of the temperature on
reaction rate constant, k and determine the activation energy of saponification was cleared.
RECOMMENDATION
To improve this experiment in order to ensure that the better results can be obtained, there are
some recommendations that should be focused:
1. Before conduct the experiment, make sure consultation and discussion with lecturer and
lab assistant has been made to ensure the right procedure and technique will be used.
2. This experiment should be done in 4 or 5 different temperatures in order to get more
accurate results but due to the limited of time, this experiment just conducted only at 3
different temperatures.
3. The apparatus should be clean thoroughly by using deionized water to avoid
contamination in titration process.
4. The person who collected the sample every 1, 5, 10, 15, 20, and 25 minutes must be sharp
in order not to early or late to get the sample at the desired time. This is important to get
the accurate data because the value of concentration of the sample changing with time.
5. The color of the mixture of sample and hydrochloric acid that turned into the light pink
color that obtained after the titration must be same for entire experiment to avoid any
variation in results.
6. The conical flasks should be shakes gently in order to ensure that the mixture of sample
was well mixed when conducting titration process.

REFERENCES
1. Fogler, H. (2010). Continuous-Flow Reactors. In Essentials of Chemical Reaction,
Engineering: Mole Balances (p. 4). Prentice Hall.
2. CHE502 Chemical Reaction Engineering I, chapter 3method of analysis.
3. Prof. William H. Green, (2017), Chemical and Biological Reaction Engineering,
continuous stirred tank reactors
https://www.google.com/url?sa=t&source=web&rct=j&url=https://ocw.mit.edu/courses/c
hemical-engineering/10-37-chemical-and-biological-reaction-engineering-spring-
2007/lecture-
notes/lec05_02212007_g.pdf&ved=2ahUKEwi9kZzwl8zeAhVD6Y8KHTBnAnAQFjAP
egQIBBAB&usg=AOvVaw2ulH4l7dGbsC-ZQp6eUWdz
4. Continuous Stirred Tank Reactors (CSTRs)
http://umich.edu/~elements/asyLearn/bits/cstr/index.htm
5. https://www.chem.purdue.edu/gchelp/howtosolveit/Kinetics/IntegratedRateLaws.html
APPENDIX

Control
panel

CSTR Rotameter Rotameter

1 1

The mixture of sample that was titrated with sodium hydroxide

Sodium hydroxide and ethyl acetate feed tanks