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ABSTRACT

INTRODUCTION
Reactor is one of the most important parts in industrial sector. Reactor is equipment that changes
the raw materials to the product that we want. A good reactor will give a high production and
economical. Two types of commonly use industrial reactors are Continuous Stirred Tank Reactor
(CSTR) and Plug Flow Reactor (PFR).

CSTR also known as vat- or back mix reactor is a common ideal reactor types in chemical
engineering. CSTR operates at steady state by feeding the reactants into the reactor and
continuously withdrawing the products. The CSTR is the idealized opposite of the well-stirred
batch and tubular plug-flow reactors. Ideally, a CSTR is perfectly well-mixed and has no spatial
variation in concentration or temperature. Since concentration and temperature are identical at all
points in the reactor, they are also the same at the point of discharge from the tank. Other
advantages are a wide temperature and pressure range and the ability to control temperature. A
disadvantage of the CSTR is that the conversion of reactants per volume of the reactor is the
smallest among the flow reactors for most reactions.

The key or main feature of this reactor is that mixing is complete so that properties such as
temperature and concentration of the reaction mixture are uniform in all parts of the vessel.
Material balance of a general chemical reaction described below. The conservation principle
requires that the mass of species A in an element of reactor volume dV obeys the following
statement:
(Rate of A into volume element) - (rate of A out of volume element) + (rate of A produced within
volume element) = (rate of A accumulated within vol. element)

OBJECTIVES
EXPERIMENT A: BATCH STIRRED TANK REACTOR EXPERIMENT
1. To determine the order saponification reaction.
2. To determine the reaction rate constant.

EXPERIMENT B: EFFECT TEMPERATURE ON REACTION RATE CONSTANT


1. To determine the effect temperature on reaction rate constant, k for batch reaction.
2. To determine the activation energy of saponification.

THEORY

IDEAL STIRRED-TANK REACTOR

A stirred- tank reactor (STR) may be operated either as a batch reactor or as a steady-state flow
reactor (better known as Continuous Stirred-Tank Reactor (CSTR)). The key or main feature of
this reactor is that mixing is complete so that properties such as temperature and concentration of
the reaction mixture are uniform in all parts of the vessel. Material balance of a general chemical
reaction is described below.
The conservation principle requires that the mass of species A in an element of reactor volume
V obey the following statement:

Rate of

Rate of

into

out of

Rate of A
+

produced

Rate of A
=

Accumulated

within

within

volume

volume

volume

volume

element

element

element

Element

BATCH STIRRED-TANK REACTOR (BSTR)


The reaction studied in this is the saponification of ethyl acetate. This reaction is elementary
and second-order. The reaction equation is
NaOAc + EtOH

NaOH + EtOAc
A

-->

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

within volume

within volume

element

element

(2)

For a constant volume isothermal batch reactor, the design equation is:

dC A
rA
dt
For a bimolecular second order reaction, the rate equation is:
-rA = k CACB
The rate of reaction of component A is defined as:

moles A appear by

rA

1 dN A
=

V dt by reaction

reaction
volume time

(3)

By this definition, if A is a reaction product, the rate is positive; whereas if it is a reactant, which
is consumed, the rate is negative.

Rearranging equation (3);

rA V

N AO

dX A
dt

(4)

Integrating equation (4);

t N AO

dX A
rA V

(5)

where t is the time required to achieve a conversion XA for either isothermal or non-isothermal
operation.

Figure 1: Graphical representation of the performance equations


for batch reactor, isothermal or non-isothermal at constant density.

STEADY STATE MIXED FLOW REACTOR


The general material balance for this reactor is as equation (1) except no accumulation of the
material A in rector. As shown in figure 2 below, if FAO = vOCAO 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)

Output of A (moles/time)

FAO (1 XAO) = FAO


=

Disappearance of A by reaction (moles/time)

FA = FAO (1 XAO)
=

(-rA) V

moles A reacting
volume of reactor
(time )( volume)

Replacing equation (1) with mathematical formula above,

FAOXA

(-rA) V

Which on arranging, will form the performance equation for mixed flow reactors,

X A

FAO C AO
rA

or,

1 V VC AO C AO X A

s vO
FAO
rA

(7)

Figure 2: Components of Mixed Flow Reactor

In mixed flow reactors, XA = XAF and CA= CAF. In a constant density system,
XA =

1 (CA/CAO)

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

V
X
C CA
V C X
A AO
, or , AO A
FAO rA C AO (rA )
v
(rA )

(8)

These expressions relate the four terms XA, -rA, V, FAO; thus, knowing any three allows the fourth
to be found directly. In design, the size of reactor needed for a given duty or the extent of
conversion in a reactor of given size is found directly. Each steady-state point in a mixed flow
reactor gives the reaction rate for the conditions within the reactor. The mixed flow reactor
provides easier interpretation of reaction rate data and makes it very attractive in kinetic studies.

Graphical Representation of the Design Equations for Steady State Mixed Flow Reactor.

Figure 3: Plot of 1 / (-rA) versus XA

Or in constant systems,

Figure 4: Plot of 1 / (-rA) versus CA

Irreversible Second-order Reaction (Bimolecular Type)


Consider the reaction:
A+ B

Products

The rate equation can be written as:

rA

dCA
dC
A kCACB
dt
dt

(11)

Plot of ln (CB/CA) versus t (time) will produce a straight line with slope equals (CBO CAO)k.

Figure 5: Plot of ln (CB/CA) versus t, CAO CBO (for equation 11)

While for steady state mixed flow reactor, the plot of rA versus CACB will give a straight line (pass
through the origin) with the slope equal to k.

Figure 6: Plot of rA versus CACB, CAO CBO (for equation 11)

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

rA

dCA
2
kCA2 kCAO
(1 X A )2
dt

(12)

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

Figure 7: Plot of rA versus CACB, CAO CBO (for equation 11)

In the case of

steady

state mixed flow reactor, the plot rA versus

CA2

will give the value of k and a straight-line pass

through the origin.

Figure 8: Plot of rA versus CACB, CAO CBO (for equation 11)

EXPERIMENT B: Effect of Temperature on Reaction Rate Constant, k

In any single homogenous reaction, temperature, composition, and reaction rate are uniquely
related. They can be represented graphically in one of three ways as shown below:
r3
r2
r1

C3

C2
C1

Figure 9: Plot of C versus T, r versus T, and r versus C

The effect of temperature on reaction rate constant can be demonstrated by performing a batch
reaction run at different temperatures.

RESULTS
EXPERIMENT A
Table 1:

Time (min)
(A)

Volume of
Titrating
NaOH (ml)
(B)

1
5
10
15
20
25

16.2
17.7
18.7
20.4
21.5
22.5

Volume of
Quenching
HCL
Unreacted
with NaOH
in Sample
(ml)
(C)
6.48
7.08
7.48
8.16
8.6
9.0

Steady State
Fraction
Conversion
of NaOH
XA
(H)

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

Mole of
NaOH
Reacted with
Ethyl Acetate
in Sample
(J)

0.604
0.708
0.748
0.792
0.844
0.888

0.0302
0.0354
0.0374
0.0396
0.0402
0.0444

0.00151
0.00177
0.00187
0.00198
0.00201
0.00222

Volume of
HCL Reacted
with NaOH
in Sample
(ml)
(D)

Mole of HCL
Reacted with
NaOH in
Sample
(E)

Mole of
NaOH
Unreacted in
Sample
(F)

3.52
2.92
2.52
1.84
1.4
1.0

0.00099
0.00073
0.00063
0.00052
0.00039
0.00028

0.00099
0.00073
0.00063
0.00052
0.00039
0.00028

Concentration
of Ethyl
Acetate
Unreacted
(moles/litre)
(L)

ln(CB/CA)

0.0698
0.0646
0.0626
0.0604
0.0598
0.0556

1.253
1.466
1.578
1.759
2.037
2.295

Table 2 :
Concentration
of Ethyl
Acetate
Reacted with
NaOH
(moles/litre)
(K)
0.0302
0.0354
0.0374
0.0396
0.0402
0.0444

The time required for 95% conversion is


m = (CBo /CAo) = 0.1/0.05 = 2
ln

m XA
m(1-XA)

ln
t=

= (CBO CAO) kt

m XA
m(1-XA)

(CBO CAO) k

ln
=

2 - 0.95
2(1-0.95)

(0.1 0.05)0.0173

= 2764.71 min

EXPERIMENT B

Temperature = 35C
Table 3 :

Time (min)
(A)

Volume of
Titrating
NaOH (ml)
(B)

Volume of
Quenching
HCl Unreacted
with NaOH in
Sample
(ml)
(C)

1
5
10
15
20

21.7
22.1
22.4
23.1
23.6

8.69
8.84
8.96
9.24
9.44

Volume of HCl
Reacted with
NaOH in
Sample
(ml)
(D)

Mole of HCL
Reacted with
NaOH in
Sample
(E)

Mole of NaOH
Unreacted in
Sample
(F)

Concentration
of NaOH
Unreacted with
Ethyl Acetate
(moles/litre)
CA
(G)

1.32
1.16
1.04
0.76
0.56

0.00033
0.00029
0.00026
0.00019
0.00014

0.00033
0.00029
0.00026
0.00019
0.00014

0.0066
0.0058
0.0052
0.0038
0.0028

25

24

9.6

0.4

0.0001

0.0001

0.0020

Steady State
Fraction
Conversion
of NaOH
XA
(H)

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

Mole of NaOH
Reacted with
Ethyl Acetate
in Sample
(J)

Concentration
of Ethyl
Acetate
Reacted with
NaOH
(moles/litre)
(K) (D)

Concentration
of Ethyl
Acetate
Unreacted
(moles/litre)
(L)

ln(CB/CA)

ln K

0.868
0.884
0.896
0.924
0.944
0.960

0.0434
0.0442
0.0448
0.0462
0.0472
0.048

0.00217
0.00221
0.00224
0.00231
0.00236
0.00240

0.0434
0.0442
0.0448
0.0462
0.0472
0.0480

0.0566
0.0558
0.0552
0.0538
0.0528
0.0520

2.149
2.264
2.362
2.650
2.937
3.258

-3.137
-3.119
-3.106
-3.075
-3.053
-3.037

Table 4 :

ln Ca/Cb VS Time
3.5
3

ln Ca/Cb

2.5
2
1.5

Series1

1
0.5
0
0

10

15

20

25

30

Time
Figure 1 Graph ln Ca/Cb versus Time for Temperature 35 Degree

TEMPERATURE = 40C

Table 5 :

Time (min)
(A)

Volume of
Titrating
NaOH (ml)
(B)

Volume of
Quenching
HCl Unreacted
with NaOH in
Sample
(ml)
(C)

Volume of HCl
Reacted with
NaOH in
Sample
(ml)
(D)

Mole of HCL
Reacted with
NaOH in
Sample
(E)

Mole of NaOH
Unreacted in
Sample
(F)

Concentration
of NaOH
Unreacted with
Ethyl Acetate
(moles/litre)
CA
(G)

1
5
10
15
20
25

16.3
17.4
17.6
18.3
19.2
20.4

6.52
6.96
7.04
7.32
7.68
8.16

3.48
3.04
2.96
2.68
2.32
1.84

0.000874
0.000760
0.000740
0.000670
0.000580
0.000460

0.000874
0.000760
0.000740
0.000670
0.000580
0.000460

0.0175
0.0152
0.0148
0.0134
0.0116
0.0092

Steady State
Fraction
Conversion
of NaOH
XA
(H)

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

Mole of NaOH
Reacted with
Ethyl Acetate
in Sample
(J)

Concentration
of Ethyl
Acetate
Reacted with
NaOH
(moles/litre)
(K) (D)

Concentration
of Ethyl
Acetate
Unreacted
(moles/litre)
(L)

ln(CB/CA)

ln K

0.650
0.696
0.704
0.732
0.768
0.816

0.0325
0.0348
0.0352
0.0366
0.0384
0.0408

0.00163
0.00174
0.00176
0.00183
0.00192
0.00204

0.0325
0.0348
0.0352
0.0366
0.0384
0.0408

0.0675
0.0652
0.0648
0.0634
0.0616
0.0592

1.3508
4.2895
4.3784
4.7313
5.3103
6.4348

-3.4259
-3.3581
-3.3467
-3.3077
-3.2597
-3.1991

Table 6 :

ln ( Cb/Ca) versus time


30
25

ln (Ca/Cb)

20
15
10
5
0
0

time
Figure 2 Graph of ln Ca/Cb versus Time for Temperature 40 Degree

TEMPERATURE = 45C
Table 7 :

Volume of
Titrating
NaOH (ml)
(B)

Volume of
Quenching
HCl Unreacted
with NaOH in
Sample
(ml)
(C)

Volume of HCl
Reacted with
NaOH in
Sample
(ml)
(D)

Mole of HCL
Reacted with
NaOH in
Sample
(E)

Mole of NaOH
Unreacted in
Sample
(F)

Concentration
of NaOH
Unreacted with
Ethyl Acetate
(moles/litre)
CA
(G)

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

Mole of NaOH
Reacted with
Ethyl Acetate
in Sample
(J)

Concentration
of Ethyl
Acetate
Reacted with
NaOH
(moles/litre)
(K) (D)

Concentration
of Ethyl
Acetate
Unreacted
(moles/litre)
(L)

ln(CB/CA)

ln K

Time (min)
(A)

1
5
10
15
20
25

Table 8 :
Steady State
Fraction
Conversion
of NaOH
XA
(H)

-1.253
-1.466
-1.578
-1.759
-2.037
-2.295

ln Cb/Ca versus time


2.5

ln Ca/Cb

2
1.5
1
0.5
0
0

10

15

20

25

time(min)
Figure 3 Graph ln Ca/Cb versus Time for Temperature 45 Degree

Figure 4 Graph ln K versus 1/T

30

ln K versus 1/T
0
-0.5

0.2

0.4

0.6

-1

0.8

1.2

y = 0.7193x - 1.906

ln K

-1.5
-2

-2.5
-3

y = -0.0746x - 3.0697
y = -0.1604x - 3.2773

-3.5
-4

1/T

T=35

T=40

T=45

Linear (T=35)

Linear (T=40)

Linear (T=45)

Figure 5 Graph ln K versus 1/T

From graph ln k vs 1/T, we can find the activation energy from the slope.

Knowing that, slope = E /R


Where,

E is the activation energy


R is the gas law constant

Therefore,

= (slope X R)

= (0.16143X 8.314)

= 1.3422 J / mole

DISCUSSION
In this Continuous Stirred-Tank Reactor (CSTR) experiment, the objective is to
determine and examine the reaction of chemical process. There are three area of
investigation of reaction, the stoichiometry, the kinetics and the mechanism. First by
using the stoichiometry of the equation, the kinetics is then investigated. With empirical
rate expression available, the mechanism is then looked into.

Let B be the component with highest concentration (Ethyl Acetate), while the
most convenient way to follow reaction is by titration of A (NaOH). The reaction
is elementary and since it is bimolecular, it is natural to first try second order
kinetics. In this experiment, the volume of Ethyl Acetate must equal to volume of
NaOH and completely fed into the reactor at beginning since batch reaction is
considered. Stirrer is used because agitation is also necessary to equalize the
temperature in the reactor and to keep it at the desired level.

In the integral method of analysis, the first step is to guess a particular form of
rate equation and after appropriate integration and mathematical manipulation,
predict that the plot of certain concentration function versus time should yield a
straight line.

Rate constant, k for the n-order reaction of homogenous reaction is (time)-1


concentration)1-n where n is the order of the reaction. In this experiment, there are
experiment A and experiment B which is respective to time and temperature
respectively. In experiment A, the which is batch reactor experiment we use 0.1
M, 1.25 liter Ethyl acetate and 0.05 M, 1.25 liter sodium hydroxide as the
reactants. After that, the stirrer is switched to mix the reactant well. The sample
of the products produced in every 1, 5, 10, 15, 20 and 25 min is taken out. In each
sample titration has been carried out with 0.1 M NaOH to evaluate the amount of
unreacted HCL. From Table 1 it shows that at 1 minute of sample it needs 16.2 ml

of 0.1 M NaOH to react. At 5 minute of sample it needs 17.7 ml of 0.1 M NaOH to


react, whereas in sample of 10, 15, 20 and 25 minute it needs 18.7, 20.4, 21.5 and
22.5 ml of 0.1 M of NaOH to react respectively. It shows that the volume of
NaOH is increasing. When plotting the graph of ln CB/CA vs. time, it shows that
it gives almost straight line. From this result it showed that it follows second
order of reaction. The rate constant from experiment A is 1.4595 with the time
taken of 2764.17 min

For the experiment B, the procedures using same as the previous but at different
temperatures are varying. The range of the temperature is 35C, 40oC and 45oC.
The result shows the effect of temperature on reaction rate constant. The
temperatures are not constant for the whole experiment as well as the pattern of
the graph. The heater is using to raise the temperature and in order to get a
constant temperature, the cooling system is using. The start up experiment is
same as experiment A, it is just in experiment B, heat is supplied to the system.
The temperature was set up at first but this system also cannot give a very
constant temperature. Therefore, it affects the value of concentration for NaOH
and ethyl acetate. The graph should be a straight line but it is not because since
there are some errors due to human, environment and the equipment itself. The
activation energy of saponification is 1.3422J/mole and from the plotted graph of
each temperature shows that temperature did affect the reaction rate constant, k
for batch reaction. The pH also is not constant at one specific pH because it is
fluctuate. The range of the pH changes is 0.01.

For the temperature 30 oC, the time taken is 1, 5, 10, 15, 20 and 25 minutes show
reading of volume NaOH needed is 16.3, 17.4, 17.6, 18.3, 19.2 and 20.4 ml
respectively. The volume needed is increasing as the time increasing. For the
temperature 35 oC, the time taken is 1, 5, 10, 15, 20 and 25 minutes show reading
of volume NaOH needed is 21.7, 22.1, 22.4, 23.1, 23.6 and 24 ml respectively.
After that table 7 shown the reading of volume NaOH needed for temperature 45
0C.

One of the common errors that occur during this experiment is the human

errors which are during the titration process. This is because sometimes over
titrate the solution make the concentration that being obtained is not accurate. In
addition, during taking reading of amount HCL from the burette also contribute
to the error which is parallax errors. The environment also contributes errors
since this experiment base on the effect of temperature. During taking a sample
may cause heat loss as well as the cool condition in the laboratory because air

conditioner is on. The machine itself also causes some deviations to the result
because of inconstant of temperature level and speed of stirrer.