CHEMICAL ENGINEERING LABORATORY V1 (EP328)

NO. OF EXPERIMENT: 1

TITLE OF EXPERIMENT: BATCH SAPONIFICATION OF Et(Ac) AND NaOH

NAME: CHAN YEE MUN

ID: 1001643260

LAB SESSION: TUESDAY

DATE OF EXPERIMENT: 22 JAN 2019

TUTOR: NURUL HUDA BINTI M.ALI

SCHOOL OF ENGINEERING
FACULTY OF ENGINEERING, TECHNOLOGY & BUILT
ENVIRONMENT

JAN – APRIL 2019

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 TABLE OF CONTENTS

PAGE
1. Objectives 3

2. Introduction 3-4

3. Material and Procedure 5

4. Results and calculation 6-9

5. Discussion 10-

6. Limitation of Report 11

7. Conclusion 11

8. References 11

9. A p p e n d i x
1 2

10. R u b r i c
1 3

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 EXPERIMENT 1: BATCH SAPONIFICATION OF Et(Ac) AND NaOH

OBJECTIVES

1. To carry out a saponification reaction between NaOH and Et(Ac) in a batch reactor.
2. To determine the order of reaction and rate constant.
3. To study the liquid phase reaction kinetics in batch reactor.

INTRODUCTION

Reactor is one of equipment used mostly in the industrials sector. It changes the raw
material into the desired product. A good reactor will give a high production and economical.
One of criteria to choose or to design a good reactor is to know the effectiveness of the
reactor itself. There are many types of reactor depending on the nature of the feed materials
and products. There are three types of reactors which are batch reactor, continuous-stirred
tank reactor (CSTR) and plug flow reactor (PFR). Batch reactors are commonly used for a
small production. It is usually for either testing new product created by research and
development team or for manufacturing high cost products. In batch reactor, reactants are fed
into a reactor, perfectly mixed, left to react and the mixture is discharged. The benefits of
batch reactor include obtaining large conversion by leaving the reactant in the reactor for a
long time while its disadvantage is that batch reactor is a little bit complicated for the
production of large-scale products. Some of the important key points for batch reactor is that
it is suitable for unsteady-state operation due to neither inflow nor outflow of reactants and
products while the reaction is being carried out. The temperature and concentration of
reactants are well mixed in this kind of reactor. As for the reaction, batch reactor is well
compatible with slow reactions. Batch reactors are usually used when the production
involving different reactants and reactor conditions. Hence, same equipment can be used for
these reactions. Examples of processes that use batch reactors include the manufacture
of colorants and margarine.

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 Figure 1: Batch Reactor

The advantages of using batch reactor including it gives high conversion rate per unit
volume for one pass, easy to clean and produce one product at one time and a different
product for the next due to the flexibility of the operation. However, the operating cost of a
batch reactor is high. The product quality may vary more than of continuous operation and it
is less preferable when it comes to large size-scale product.

In addition, batch reactors are often used to determine rate law parameters for
homogenous reaction. This can be done by measuring concentration as a function of time.
The data is then used to determine reaction order and rate constant. This experiment studies
the saponification reaction between ethyl acetate Et(Ac), and sodium hydroxide NaOH in a
constant volume batch reactor. The saponification reaction of Et(Ac) and NaOH can be
represented by the following stoichiometric equation:

CH3CO2C2H5 + NaOH → C2H5CO2Na + CH3OH

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MATERIAL AND APPARATUS
SOLTEQ BP109 Batch Reactor, 0.1 M of sodium hydroxide, NaOH and 0.1M of ethyl
acetate, Et (Ac), stopwatch

PROCEDURE

1. The general start-up procedures were performed as in appendix A.

2. To begin a batch reaction experiment, valve V3 and V7 were closed, pump P2 was
switched on and valve V8 was opened to obtain highest possible flow rate into the
reactor. Reactor R1 was filled with 0.1 M of Et (Ac) to 1L volume. The pump P2 was
stopped.
3. Pump P1 was switched on and V4 was opened to obtain highest possible flow rate
into the reactor. Reactor R1 was filled with the 0.1 M of NaOH until the solution
reached a total 2L volume. Pump P1 was stopped.
4. The stirrer M1 was switched on and the timer was started immediately.
5. The conductivity values were recorded at 1-minute interval.
6. The experiment was stopped when the conductivity values were remained constant.
(ie. Steady state condition)
7. Valve V10 was opened and all the solution was drained from the reactor into the
waste tank B4.

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 RESULTS AND CALCULATION
Solution mixture volume =2L
Initial concentration of NaOH in the reactor vessel = 0.1 M
Initial concentration of Et(Ac) in the reactor vessel = 0.1 M
Concentration
Time, t Conductivity Conversion, -dCA/dt
NaOH, CA In CA ln (-dCA/dt)
(min) QI01 (mS/cm) X (M/min)
(M)
0 0 0.05000 0.0000 -2.303 -0.04947 -3.006
1 8 0.03306 0.3388 -3.409 -0.00915 -4.694
2 7.7 0.03170 0.3659 -3.451 -0.00136 -6.601
3 7.4 0.03034 0.3931 -3.495 -0.00113 -6.784
4 7.2 0.02944 0.4112 -3.525 -0.00068 -7.294
5 7.1 0.02899 0.4203 -3.5410 -0.00045 -7.700
6 7 0.02853 0.4293 -3.557 -0.00045 -7.700
7 6.9 0.02808 0.4384 -3.573 -0.00045 -7.700
8 6.8 0.02763 0.4475 -3.589 -0.00045 -7.700
9 6.7 0.02717 0.4565 -3.605 -0.00045 -7.700
10 6.6 0.02672 0.4656 -3.622 -0.00023 -8.393
11 6.6 0.02672 0.4656 -3.622 -0.00023 -8.393
12 6.5 0.02627 0.4746 -3.639 -0.00023 -8.393
13 6.5 0.02627 0.4746 -3.639 0 ∞
14 6.5 0.02627 0.4746 -3.639 -0.00023 -8.393
15 6.4 0.02582 0.4837 -3.657 -0.00023 -8.393
16 6.4 0.02582 0.4837 -3.657 0 ∞
17 6.4 0.02582 0.4837 -3.657 0 ∞
18 6.4 0.02582 0.4837 -3.657 0 ∞
19 6.4 0.02582 0.4837 -3.657 0 ∞
20 6.4 0.02582 0.4837 -3.657 0 ∞

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Sample Calculation
At t = 8 min, conductivity = 6.8 mS/cm:
1. Determine conversion X,

The calibration curve for conductivity and conversion was represented by the equation of y =
-11.04x + 11.74. The equation was rearranged to determine the conversion using the
conductivity obtained throughout the experiment.

(11.74−𝑦 )
Conversion, X = 11.04
(11.74−6.8 )
Conversion, X =
11.04

X = 0.44746

2. Determine concentration of NaOH in the reactor at time t, CA:

Initial concentration of NaOH, CAO = 0.05 M

CA = CAO (1- X)

CA = 0.05 (1 - 0.44746)

= 0.05525 M

3. Calculate ln CA, -dCA/dt, ln (-dCA/dt)

For an equimolar reaction with the same initial reactants’ concentration (CAO = CBO), the rate
law is shown to be:

-rA = -dCA/dt = kCAa

ln (-dCA/dt) = ln k + a ln CA

The value of ln𝐶A was determined by taking the natural logarithm of the concentration of
NaOH, for example when 𝐶A = 0.02899

ln CA = ln 0.05535

= -2.89582

The value of dCA/dt was determined by using Three-point numerical differentiation formulas:

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At t = 8 min, the value of dCA/dt was determined by using interior point formula as the point
is in between the first and the last.

𝑑𝐶𝑎 1
− ( 𝑑𝑡 )t5 =− [ CA(8+1) – CA(8-1) ]
2∆𝑡

1
=− [ CA(9) – CA(7) ]
2(1)

1
= − 2 [0.05616-0.05435]

= 0.00091M/min

The value of ln (-dCA/dt) was determined by taking the natural logarithm of the -dCA/dt, for
example when -dCA/dt = 0.00091

ln (-dCa/dt) = ln (0.00091)

ln (-dCa/dt) = -7.00670

4. Find order of reaction and rate constant:

Based on Figure 3, y =4.0271x + 6.766:

Order of reaction, a = slope = 4.0271 ≅ 4

ln k = y-intercept = 6.766

Rate constant, k = 867.83 M3/min-1

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 Conversion against Time
0.6000

0.5000

0.4000
Conversion, X

0.3000

0.2000

0.1000

0.0000
0 5 10 15 20 25
Time, t

Figure 2: Graph of Conversion of NaOH against time

ln (-dCA/dt) against In CA
0.000
-4 -3.5 -3 -2.5 -2 -1.5 -1 -0.5 0
-1.000

y = 4.0271x + 6.766 -2.000

R² = 0.774 -3.000
ln (-dCA/dt)

-4.000
ln (-dCA/dt)
-5.000
Linear (ln (-dCA/dt))
-6.000
-7.000
-8.000
-9.000
In CA

Figure 3: Graph of ln (-dCA/dt) against In CA

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DISCUSSION
In this experiment, the saponification reaction between 1L of 0.1M ethyl acetate
Et(Ac), and 1L of 0.1M sodium hydroxide NaOH was studied in a constant volume batch
reactor. The saponification reaction of Et(Ac) and NaOH can be represented by the following
stoichiometric equation:

CH3CO2C2H5 + NaOH → C2H5CO2Na + CH3OH

Batch reactors are often used to determine rate law parameters for homogenous reaction. This
can be done by measuring concentration as a function of time. The data is then used to
determine reaction order and rate constant.
The conductivity of the solution starts to become constant at t = 15 min with G = 6.4
mS/cm. The constant value of conductivity continuously indicated the reaction has reached
its steady state condition. Based on the calculation, the conversion of NaOH is increasing
initially then constant gradually. Therefore, the results shown that the conversion increased
from 33.88% with time until it reached a maximum of 48.37%. A graph of conversion of
NaOH over time was plotted as shown in Figure 2. By comparing with the graph of
conductivity against conversion for a batch reactor that pre-calibrated, it was shown that the
conductivity decreased with increased in conversion. The conversion cannot achieve 100%
because the reaction involved was an equilibrium reaction, which means the products of the
reaction (sodium acetate and ethanol) can be converted back into the reactants. As the
conductivity and conversion were determined, the concentration of NaOH was calculated as a
function of time.

To determine the reaction order, a and rate constant, k, a graph of ln (-dCa/dt) against
ln Ca was plotted in which a is the slope and ln k is the y-intercept of the graph. In order to
plot the graph, the derivative -dCa/dt was obtained first. There were four different methods of
analyzing data which are differential method, integral method, half-lives method and initial
rates method. In this experiment, given that the experimental data was collected in equal time
interval, three-point numerical differentiation formulas was applied to calculate -dCa/dt more
accurately. As shown on Figure 3, the reaction order and rate constant were determined to be
5th order and 5.274 x 109 M/min respectively.
Based on the stoichiometric equation CH3CO2C2H5 + NaOH → C2H5CO2Na +
CH3OH, the saponification of Et(Ac) with NaOH is an irreversible second-order reaction.

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For irreversible reactions, maximum conversion is 100%. The conversion of maximum 64.67%
in this experiment was acceptable. Besides, the differential method is used for irreversible
reaction. Hence, the application of numerical differential method to analyze the experimental
data was acceptable. However, the reaction order was found to be 5th order where
theoretically it is a 2nd order reaction.

LIMITATION
Several limitations of the experiment were discussed as follow. Laboratory coats
and safety goggles should be worn throughout the experiment. One of the limitations for this
experiment is that tap water was used in the experiment instead of deionized water as a
diluent and solvent for the reactants. Tap water contains minerals and have a relatively high
conductivity compared to deionized water. The experimental results may be affected if tap
water is used. Deionized water should be used to increase the accuracy of results. It is also
important to ensure the reactor is clean before conducting any experiment. Hence, the reactor
should be cleaned by rinsing with distilled water to remove impurities.
Based on the graph, the R-squared value is not approaching 1 which means that the
best-fit line deviate from the data points quite significantly. The equation used to calculate
the rate constant and the order of reaction is only valid for equimolar concentration of
reactants. However, it is hard to control the pump to ensure the initial concentration of
reactants are exactly equal. A premeasured amount of solution can be used as the reactants to
compensate this error.
Besides that, the experiment was only conducted once which was insufficient to
obtain a precise result. The experiment should be repeated at least 3 times and take average
results to increase the accuracy or results.

CONCLUSION

REFERENCE
1. Folger, H. S. (2016). Elements of Chemical Reaction Engineering. (5th Edition).
Upper Saddle River: Pearson Education Inc.
2. Li, S., Xin, F., & Li, L. (2017). Reaction Engineering (1st Edition). Butterworth-
Heinemann 2017.

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3. Smith, J. M. (2009). Chemical Engineering Kinetics. (3rd Edition). New York:
McGraw-Hill Companies, Inc.

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