1.

0 ABSTRACT

The purpose of this experiment is to study the effect of reaction rate at constant
temperature, the effect of different temperature on reaction rate constant, k and the activation
energy of saponification. This experiment was conducted by mixing the Ethyl Acetate, Et(Ac) and
sodium hydroxide, NaOH which both volume are equal in the continuous stirred-tank reactor
(CSTR) at temperature of 30oC. At 0 minute 5 mL volume of sample solution was collected and
the sample will be titrate with 0.1M NaOH. The run time for the experiment is 25 minutes. The
sample will be collected again every 5 minutes, which is 5, 10, 15, 20 and 25 minutes. Every
sample will be titrate same as at 0 minutes. The volume of NaOH use in the titration has been
recorded. Graph of rate of reaction (-rA) was plotted at constant temperature 30oC. The same
experiment was repeated using different temperature which are at 40 oC and 50oC. The result has
been recorded and calculate. Based on calculation graph of 1/CA (L/mol) vs time (min) was plotted
for each temperature. Based on the slope from graph represent the value of reaction rate constant,
k. From the value k, few calculation has been made and graph ln k (L/mol. Min) vs 1/T (K-1) was
plotted. The value of activation energy can be calculated in two ways using Arrhenius equation:
ln (k2/k1) = E/R (1/T1 – 1/T2) and using the value of slope of the graph ln k vs 1/T, the value of
activation energy of the slope based on equation ln k = (Ea/R)(1/t).

1
2.0 INTRODUCTION

Reactor is an equipment that used to turn raw material into desired product. In chemical
engineering, chemical reactors are heart of chemical process. It is a device which containing and
controlling a chemical reaction. All chemical process are centered in a chemical reactor. The
design of a chemical reactor are the most important factor in determining the overall process
economics. Basics factor that should be consider to design chemical reactor are: reaction type;
removal/ addition of heat; presence of catalyst; mode of temperature and pressure control;
production capacity or flow, residence time and mixing between reactors (Nasir, 2015).

A chemical reactor needs to be able to carry out at least three functions: provide the necessary
residence time for the reactants to complete the chemical reaction; allow the heat exchange
necessary; place the phases into intimate contact to facilitate the reaction (Maurizio, M). The
reaction occurred in the endothermic and exothermic reaction. Endothermic reaction/’within –
heating’ describes a process or reaction that absorbs energy in the form of heat meanwhile,
exothermic reaction describes the process or reaction release energy in the form of heat, light or
sound (Nasir, 2015). Jacket or coil generally assembled with a reactor in order to maintain the
reaction temperature. If heat is evolved due to exothermic reaction, a coolant stream required pass
through the jacket o remove the heat. Meanwhile during endothermic reaction occurs the flow of
heating medium is passing through jacket or coil for maintain the reaction temperature. When
endothermic and exothermic occurs the temperature of the reaction mixture varies with time and
this called non-isothermal reactor. If the reactor operate with constant temperature it is called
isothermal reactor.

A chemical reactor can be classified by mode of operation such as: batch reactor; continuous
reactor and semi-batch reactor. Continuous reactor mode of operation was chosen in this
experiment. In continuous reactor, reactant are added and products removed continuously at a
constant mass flow rate. Large daily production rates are mostly conducted in continuous
equipment (Nasir, 2015). There are several types of continuous reactor which are: CSTR
(continuous stirred-tank reactor); plug flow reactor and tubular flow reactor. In this experiment,
Continuous stirred-tank reactor (CSTR) has been used to conduct a chemical process.

2
3.0 OBJECTIVES

The purpose of CSTR experiment:

a) To determine the effect of reaction rate at constant temperature.

b) To determine the effect of different temperature on reaction rate constant, k for batch reaction.
c) To determine the activation energy of saponification.

4.0 THEORY
A continuous stirred tank reactor (CSTR) represent a model of continuous reactor, where there is
continuous feed of reactants and simultaneous extraction of the products (Maurizio, M). CSTR is
a vessel to which reactants are added and products removed while the contents within the vessel
are vigorously stirred using internal agitation or by internally (or externally) recycling the contents
(E.Heinzle, 2009). CSTRs may be employed in series or in parallel (William, 2007).

Figure 1 Continuous stirred-tank reactor (CSTR).

Usually, stirred reactors are operated by keeping the reaction volume constant, conditions easily
realized through a level control, thus transferring any possible reaction mixture density change
effects on the volumetric flow rate leaving the reactor (Maurizio, M). Stirred tanks run under
continuous flow conditions (CSTRs) are used extensively in the process industries as they can
easily be integrated in a continuous process whilst providing long residence times at a relatively
low capital cost. In addition, the back-mixed nature of the CSTR's flow history is favorable for
certain reactions and provides “smoothing” of time-varying fluctuation of product or reactant
properties to aid process control (E.Heinzle, 2009).

3
 General mole equation:

𝑉 𝑑𝑁𝐴
FA0 – FA + ∫0 𝑟𝐴 dV =
𝑑𝑡

Assumption in CSTR: (William, 2007)

i. Operated at steady state (i.e., conditions do not change with time), therefore:
𝑑𝑁𝐴
=0
𝑑𝑡
ii. Perfect mixing (there are no spatial variations in the rate of reaction), therefore rA is the same
throughout reactor:
𝑉 𝑉
∫0 𝑟𝐴 dV = rA ∫0 𝑑𝑉= rA V

iii. Rearrange:

𝐹𝐴0− 𝐹𝐴
V=
𝐹𝐴0

iv. In terms of conversion:

𝐹𝐴0− 𝐹𝐴
X=
𝐹𝐴0

𝐹𝐴0 𝑋
V= −𝑟𝐴

4
Reactor sizing:

Given –rA as a function of conversion, -rA = f(X) , one can size any type of reactor. Either FA0 /
-rA or 1 / -rA are plot as a function of X. The volume of a CSTR can be represented as the shaded
areas in the Levelspiel Plots shown below:

Figure 2 Volume of CSTR in the Levenspiel Plots

Effect of temperature on rate of reaction in CSTR:

As temperature increase, the rate of reaction also increase. When temperature is high the
particles of the substances move faster and collision occur more frequently. The velocity increase
as the temperature increase lead to the collision of particle more violent. Reaction are roughly
doubled when temperature increases by 10 degrees Klevin.

Every reaction has energy barrier. The energy barrier or minimum energy a molecule must
possess to overcome this barrier is called activation energy (Ea) which can be shown on Arrhenius
Law Equation:

k = A*𝑒 −𝐸𝑎 / 𝑅𝑇

Given:

 k = The rate constant.

 Ea = The activation energy
 R = The gas constant
 T = Temperature in Kelvin
 A = Frequency factor constant or also known as pre-exponential factor or Arrhenius factor.

5
5.0 APPARATUS & MATERIALS

Figure 3 Continuous Stirred-Tank Reactor (Model: BP100)

Apparatus:

a) Continuous stirred-tank reactor (Model: BP100)

b) Conical flask
c) 50 mL burette
d) 100 mL measuring cylinder
e) Stopwatch

Materials:

a) 0.25M Hydrochloric Acid

b) 0.1M Sodium Hydroxide
c) 0.1M Ethyl Acetate
d) Phenolphthalein

6
6.0 PROCEDURE

General Start-up procedure:

1. The following solution were prepared: 20 L of sodium hydroxide, NaOH (0.1 M); 20 L of ethyl
acetate, Et(Ac) (0.1 M) and 1 L of hydrochloric acid. HCL for quenching (0.25 M)
2. All valve were initially closed.
3. Feed tanks were charged: charge port caps were opened for tanks T1 and T2; NaOH solution
was carefully poured into vessel T2 and Et(Ac) solution into vessel T1 and the charge port
caps were closed for both tanks.
4. The power was turned on for the control panel.
5. The heater was not switched on until it was fully submerged in the liquid. Liquid level was
maintained above the heater to avoid the damage to the heater.
6. The stirrer assembly was secured properly to avoid damage to the mechanical seal.
7. All tubings were inspected periodically for leakage and worn out cause leakage lead to
equipment damage by corrosive reactant.

Experimental procedure:

1. Pump P1 was switched on to pump 1.25 L of 0.05M Ethyl Acetate, Et(Ac), from the feed tank
into reactor. Pump P1 was switched on.
2. Pump P2 was switched on to pump 1.25 L of 0.05M Sodium hydroxide, NaOH, into the reactor.
Pump P2 was stopped when 2.5 L of total volume was reached.
3. The stirrer and the heater were switched on and temperature was set to 30oC and the timer was
started.
4. After 1 minute of reaction, 50 mL of sample was collected from the reactor. The sample was
titrated with sodium hydroxide, NaOH.
5. Step 4 was repeated of reaction time of 5, 10, 15, 20 and 25 minutes.
6. The experiment was repeated for temperature 40oC and 50oC.

7
Titration procedure:

1. 10 mL of 0.25M hydrochloric acid, HCL was prepared in a conical flask.

2. 5 mL sample collected was added to the conical flask to quench the saponification reaction.
3. 3 drops of phenolphthalein were added in conical flask as indicator.
4. The mixture was the titrated with 0.1M NaOH until it turned light pink (neutralized).
5. The volume of NaOH was recorded.

General Shut-down procedure:

1. The cooling water valve from main pipe was kept open to allow the cooling water to continue
flowing.
2. Both pumps P1 and P2 were switched off. The stirrer and heater were switched off to let the
equipment to cool down to room temperature.
3. Cooling water valve from main pipe was closed.
4. The power for control panel was turned off.
5. After each experiment, the reactor tubings were cleaned properly as NaOH and Et(Ac) are
corrosive and could damage tubings.

8
7.0 RESULT

Table 1: Rate of reaction (-rA) at 30oC

Time (min) CA (mol/L) Rate of reaction (-rA)
(mol/ min. L)
0 0.100 0.0010
5 0.100 0.0010
10 0.120 0.0015
15 0.072 0.0005
20 0.092 0.0009
25 0.084 0.0007

0.0016

0.0014
Rate of reaction (-rA) (mol/ min.L)

0.0012

0.001

0.0008

0.0006

0.0004

0.0002

0
0 5 10 15 20 25
Time (min)

Graph 1: Rate of reaction (-rA) vs time (min) at 30oC

9
For temperature: 30oC

Table 2: The volume of NaOH solution titrated at 30oC

Time (min) Volume of Volume of CA (mol/L) 1
(L/mol)
sample (mL) NaOH used for 𝐶𝐴

titration (Ml)
0 5 20.0 0.100 10.00
5 5 20.0 0.100 10.00
10 5 19.0 0.120 8.33
15 5 21.4 0.072 13.89
20 5 20.4 0.092 10.87
25 5 20.8 0.084 11.90

16

14
y = 0.101x + 9.5695
12 R² = 0.2459

10
1/CA (L/mol)

0
0 5 10 15 20 25

Time (min)

Graph 2: 1/CA vs time at temperature of 30oC

Value of k based on slope = 0.101 L/mol. min

Order of reaction = 2nd order.

10
For temperature: 40oC

Table 3: The volume of NaOH solution titrated at 40oC

Time (min) Volume of Volume of CA (mol/L) 1
(L/mol)
sample (mL) NaOH used for 𝐶𝐴

titration (Ml)
0 5 20.0 0.100 10.00
5 5 20.0 0.100 10.00
10 5 20.2 0.096 10.42
15 5 20.8 0.084 11.90
20 5 20.7 0.086 11.63
25 5 20.6 0.088 11.36

16

14
y = 0.0753x + 9.9443
R² = 0.6895
12

10
1/CA (L/mol)

0
0 5 10 15 20 25
Time (min)

Graph 3: 1/CA vs time at temperature of 40oC

Value of k based on slope = 0.0753 L/mol. min

Order of reaction = 2nd order.

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For temperature: 50oC

Table 4: The volume of NaOH solution titrated at 50oC

Time (min) Volume of Volume of CA (mol/L) 1
(L/mol)
sample (mL) NaOH used for 𝐶𝐴

titration (Ml)
0 5 20.5 0.090 11.11
5 5 21.3 0.074 13.51
10 5 21.3 0.074 13.51
15 5 20.3 0.094 10.64
20 5 20.5 0.090 11.11
25 5 20.6 0.088 11.36

16

14
y = 0.0504x + 12.503
R² = 0.1338
12
1/CA (L/mol)

10

0
0 5 10 15 20 25
Time (min)

Graph 4: 1/CA vs time at temperature of 50oC

Value of k based on slope = -0.0504 L/mol. min

Order of reaction = 2nd order.

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Table 5: Calculated values of k, -rA, ln k and 1/T
Temperature, T Specific reaction Rate of reaction. ln k 1
(K-1)
(K) rate constant, k -rA (L/mol. min) 𝑇

(L/mol.min) (mol/min. L)

303 0.101 0.0010 -2.2926 0.0033

313 0.0753 0.0008 -2.5863 0.0032

323 0.0504 s0.0004 -2.9878 0.0031

-2
0.00314 0.00316 0.00318 0.0032 0.00322 0.00324 0.00326 0.00328 0.0033 0.00332

-2.1

-2.2
y = 2937x - 11.985
R² = 1
ln k (L/mol. min)

-2.3

-2.4

-2.5

-2.6

-2.7
1/T (K-1)

Graph 5: ln k vs 1/T between temperature 303K and 313K

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 -2
0.00308 0.0031 0.00312 0.00314 0.00316 0.00318 0.0032 0.00322
-2.1

-2.2

-2.3
ln k (L/mol. min)

-2.4

-2.5 y = 4015x - 15.434

R² = 1
-2.6

-2.7

-2.8

-2.9

-3
1/T (K-1)

Graph 6: ln k vs 1/T between temperature 313K and 323K

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8.0 SAMPLE CALCULATIONS

Calculate CA at 30oC at 0 min

Volume of unreacted quenching HCL, V1:

V1 = (CNaOH/ CHCL) × Volume of titrated NaOH

= (0.1 mol L-1 / 0.25 mol L-1) × 20 mL

= 8 mL

Volume of HCL reacted, V2:

V2 = VHCL – V1

= 10 mL – 8 mL

= 2 mL

Moles of reacted HCL, n1:

n1 = CHCL × V2

= 0.25 mol L-1 × 2 mL ×1 L/1000 mL

= 0.0005 mol

Moles of unreacted NaOH in sample, n2:

N2 = n1

= 0.0005 mol

Concentration of unreacted NaOH, CNaOH:

CNaOH unreacted = n2 / volume sample

= 0.0005 mol / 0.005 L

CA = 0.1 mol/ L

1/CA = 10 L/mol

15
Specific reaction rate constant, k

Slope from the graph

Calculate the reaction rate, -rA

-rA = kCA2

= (0.101 L/mol. Min) × (0.1 mol/ L)2

= 0.0010

Calculate activation energy from the reaction Ea

From the graph ln k vs 1/T:

Temperature 303 K and 313 K

y = 2937× – 11.985

ln k = 2937 (1/T) – 11.985

and the slope of the line given is

-Ea/R = 2937K

Ea1 = -2937K (8.314 J/mol. K)

= -24 418.22 J/mol

Temperature 313 K and 323 K

y = 4015× – 15.434

ln k = 4015 (1/T) – 15.434

and the slope of the line given is

-Ea/R = 4015K

Ea2 = -4015K (8.314 J/mol. K)

= -33 380.71 J/mol

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Ea = Ea1+ Ea2

= - 57 862.93 J/mol

Activation energy from Arrhenius equation:

Temperature 303 K and 313 K

ln (k2/k1) = E/R (1/T1 – 1/T2)

ln (0.0753/ 0.101) ÷ (1/303 – 1/ 313) = E/(8.314)

E1 = - 23 153.29 J/mol

Temperature 313 K and 323 K

ln (k2/k1) = E/R (1/T1 – 1/T2)

ln (0.0504/0.0753) ÷ (1/313 – 1/ 323) = E/(8.314)

E2 = -33 746.64 J/mol

E = E1 + E2

= - 56 899.93 J/mol

17
9.0 DISCUSSION

The experiment was carried out by using special NaOH and Et(Ac). The purpose of this experiment
is to study the effect of reaction rate at constant temperature, effect of different temperature on rate
constant and to find the value of activation energy. Based on the Arrhenius equation k=koe-E/RT
show that temperature has an effect to the reaction constant. In this experiment, 3 different
temperature were used which are 30oC, 40oC and 50oC.

Based on result obtained at temperature 30oC, as the time increases the volume of NaOH
used for titration also increase. CA and 1/CA has been calculated and Graph 1: reaction rate (-rA)
vs time was plotted. From the graph shows as the time increase the reaction rate was decreasing.
Graph 2: 1/CA vs time for temperature 30oC was plotted. From the graph we can see the value of
1/CA is drop at 10 minute but increase significantly at 15 minutes. This may due to error when
handling titration, the solution that has been titrate may not be light pink but a little darker. During
titration, the volume of NaOH needed to neutralize should be taken as soon as the sample turns
into light pink color. The result could be affected if volume taken slightly late than it should be.

The experiment was repeated at different temperature. At 40 oC, as the time increases the
volume of NaOH used for titration increase. Graph 3: 1/CA vs time for temperature 40oC was
plotted. From the graph we can see the value of 1/CA is increase linearly. There are no significant
error occurs during handling titration process. For experiment that conduct at temperature of 50oC
the error occur at 5 to 10 minutes. Graph 4: 1/CA vs time for temperature 50oC shows the value
of 1/CA is increase significantly at 5 to 10 minutes and then the value drop back to normal.

From the result and calculation, the data was found to be 2nd order reaction. The slopes
from the graph represents the specific reaction rate constant, k. For temperature 30oC, the value of
k is 0.101 L/mol.min, for 40oC the value of k is 0.0753 L/mol.min whereas 0.0504 L/mol.min are
specific reaction rate constant for 50oC. Based on the equation, the value of rate constant should
be increase as the temperature increasing.

The value of ln k (L/mol. Min) and 1/T (K-1) has been calculated to find the value of
activation energy. Graph 5 which represent ln k vs 1/T between temperature 303K and 313K and
Graph 6 which represent ln k vs 1/T between temperature 313K and 323K was plotted. The
activation energy for this experiment can be calculated in two ways: using Arrhenius equation: ln

18
(k2/k1) = E/R (1/T1 – 1/T2) and using the value of slope of the graph ln k vs 1/T, the value of
activation energy of the slope based on equation ln k = (Ea/R)(1/t).

Using value of slope on the graph the activation energy value obtained was - 56 899.93 J/mol and
based on the Arrhenius equation was - 57 862.93 J/mol. This two value not very far apart. It is
proven that the graph are valid.

10.0 CONCLUSION

After the end of the experiment, it can be conclude that temperature can affect the value of k. When
the temperature increase the reaction rate also increase. The order of the reaction is 2nd order this
can be conclude by the graph 1/CA versus time has been plotted in Graph 2, 3 and 4 and we got
the slope which represent k, reaction rate constant for each graph. Arrhenius law says for a reaction
that have same concentration but two different temperature the value of activation energy is
constant. This has been prove by equation of Arrhenius which is ln (k2/k1) = E/R (1/T1 – 1/T2).
The graph of ln k versus 1/T that has been plotted also valid to use. This can prove by the value
activation energy obtain based on the slope of the graph which is use this equation ln k =
(Ea/R)(1/t) are not far apart from the value obtain by using Arrhenius equation.

11.0 RECOMMENDATIONS

There are several factor that can be fix and has to take into consideration in order for the experiment
run smoothly and get accurate result. First recommendation is reading the volume in burette need
to be precise and should be on the correct eye level. Misread the volume by looking at the
measurement on an angle can affect the result. From above, it can seem the volume is lower while
from below, the volume might seem higher. Secondly, the color of light pink obtain during titration
should be consistent to avoid any variation result. Next, all equipment need to be used correctly
and make sure it is clean. For example, errors in filling burette can cause air bubbles that affect the
flow of the liquid in the burette. If the equipment use are not clean it can lead to contamination
and defect in titration process. Lastly, the experiment should repeat 2 times at least 3 times is the
best in order to get more accurate result.

19
12.0 REFERENCES

1. Nasir, H. (2015). Types of Chemical reactors. Production and Operation Engineer, pp 81.

Retrieved from:

http://appliedchem.unideb.hu/Unit%20Operation%203/Reactors/reactortypes.pdf

2. Maurizio, M. Chemical Reactor. Encylopedia of Hydrocarbons, pp 351-368. Retrieved from:

http://www.treccani.it/export/sites/default/Portale/sito/altre_aree/Tecnologia_e_Scienze_appl

icate/enciclopedia/inglese/inglese_vol_5/351_368_ing.pdf

3. E.Heinzle. (2009). Introduction to Ideal Reactors. Technische Chemie, pp 17. Retrieved from:

https://sistemas.eel.usp.br/docentes/arquivos/5817712/326/IntroductionReactor.pdf

4. William, H, G. (2007). Continuous Stirred Tank Reactor (CSTRs). Chemical and Biological

Reaction Engineering, pp 4. Retrieved from: https://ocw.mit.edu/courses/chemical-

engineering/10-37-chemical-and-biological-reaction-engineering-spring-2007/lecture-

notes/lec05_02212007_g.pdf

5. H. Scott Fogler. (2010). Essentials of Chemical Reaction Engineering: Mole Balances.

Engineerin, pp 5. Retrieved from: http://www.informit.com/articles/article.aspx?p=1652026

20
13.0 APPENDIX

21
 CSTR reactor 3 drops of phenolphthalein
Titration process using
(MODEL: BP100) 0.1M NaOH. mix with sample.

Titration result for temperature: 30oC for Titration result for temperature: 40oC for
every 5 minutes. From 0-25 minutes every 5 minutes. From 0-25 minutes

Titration result for

temperature: 50oC for every 5
minutes. From 0-25 minutes

22