Saponification of Ethyl Acetate and Sodium Hydroxide in Constant Volume

Batch Reactor and Continuous Stirred Tank Reactor

Abstract
This experiment aims to find the rate law parameters for the saponification of ethyl acetate (EA)
and sodium hydroxide (NaOH) solution, to determine the effects of reaction temperature and
reactants flow rate on saponification process in continuous stirred tank reactor (CSTR) and to
compare the performance of constant volume batch reactor (CVBR) and CSTR in handling this
chemical reaction. Chemical Reactor Trainer CE 310 incorporated with a combined temperature
and conductivity sensor was used to study this reaction. Rate law was determined through
differential method of analysis and performance comparison was made on the basis of the
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conversion of NaOH solution. rNaOH = (0.859e7.224x10 /RT )CNaOH 0.03 was proposed to
describe this saponifaction process. In CSTR, a 5% of increment in conversion was reported when
saponification process took place at 35.6C as compared to the one at 28.7C. Moreover, as the
flow rate of both reactants increased from 5.4 mL/min to 7.4 mL/min, the conversion declined by
approximately 14%. Lastly, conversion achieved in CVRT was 11% higher than in CSTR for
saponification proceeded at 35C.

1.0 Introduction
Saponification of ethyl acetate (EA) and sodium hydroxide (NaOH) solution is a homogeneous
reaction as it only involves liquid phase. Products formed in this reaction are ethanol and sodium
acetate.
CH3 COOCH2 () + NaOH() CH3 CH2 OH() + CH3 COONa()

Sodium acetate possesses both lipophilic and hydrophilic behaviour and this makes it a wonderful
surfactant. One can easily find surfactant in a wide range of industrial applications especially in
hygiene and toiletries products.

The major concern of a chemical reaction is its reaction rate (r). It shows how fast a number of
moles of one chemical species are being consumed to form another chemical species. Sometimes,
it is known as rate law which is a product of a temperature-dependent term and a composition-
dependent term.
r = 1 (temperature) 2 (composition)

General form of the rate law used in this experiment is illustrated as follows and its derivation is
shown in Appendix 1.
ri = k Ci (1)
where

1
k = rate constant,
Ci = concentration of chemical species i in
reactor at time t,
= the order of reaction with respect to i.

In addition, reaction rate constant can be described by Arrhenius law (Levenspiel, 1999).
k = k o eE/RT (2)

where
k o = frequency or pre-exponential factor,
E = activation energy of reaction,
R = universal gas constant,
T = absolute temperature.

At same concentration, but at two different temperatures (T1 and T2 ), E may be calculated by the
following equation provided that it is a constant.
k
R ln ( 2 )
k1
E= (3)
1 1
(T T )
1 2

In this experiment, saponification of EA and NaOH solution was carried out in a constant volume
batch reactor (CVBR) and a continuous stirred tank reactor (CSTR) respectively.
For CVBR, reaction rate can be represented by
dCi
ri = (4)
dt

Derivation of Equation (4) is available in Appendix 2.

Combining Equations (1) and (4) gives
dCi
= kCi (5)
dt

dCi
( ) can be evaluated by fitting the concentration of chemical species i to a polynomial in time
dt
and then differentiate the resulting polynomial (Fogler, 2006). This method is known as differential
method of analysis.
Taking natural logarithm of both sides of Equation (5) gives
dCi
ln ( ) = ln Ci + ln k (6)
dt

2
 dCi
Then, reaction order can be found from the slope of the plot of ln ( ) as a function of ln Ci
dt
whilst rate constant can be evaluated from the y-intercept.

Another important parameter in a chemical reaction is called conversion (X). It helps to quantify
the moles of product formed for every mole of reactant consumed and is expressed as
Ci
X=1 (7)
Ci0

The objectives of the experiment are to..

2.0 Methodology
A calibration curve (Figure 1) was prepared by measuring the conductivity of different
concentration of NaOH solution (0.2M 1.0M) prior to the start of experiment. Chemical Reactor
Trainer CE 310 consisted of a 1.5 litre reactor incorporated with heating and agitating features,
two pumps and a combined conductivity and temperature sensor was used to carry out the reaction
between EA and NaOH solution.

500 mL of 0.1 M NaOH solution was reacted with 500 mL 0.1 M EA in CVBR at two different
temperatures, i.e. 30C and 50C. Conductivity of the solution in CVBR was recorded every 2
minutes for a total of 10 minutes.
For CSTR, 0.1M NaOH solution and 0.1M EA were pumped into the reactor at same flow rate,
i.e. 5.4 mL/min, and reacted at 30C. Conductivity was started to measure once overflow of
solution inside the reactor was observed. The conductivity was recorded every 2 minutes until 5
readings were obtained.

Next, the temperature of CSTR was increased to 35C while maintaining the same flow rate at 5.4
mL/min in order to examine the effect of reaction temperature on saponification process. After
that, flow rate for both reactants was ascended to 7.4 mL/min but the reaction temperature
remained unchanged. This helped to investigate the influence of flow rate on saponification
process in CSTR. Similarly, conductivity was measured and recorded on a 2 minutes interval as
described in the previous paragraph.

Job Safety Analysis

Please comment in detail the safety aspects of the experiment in this section.

3.0 Results and Discussion

3.1 Calibration curve

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According to Figure 1, conductivity was related to the concentration of NaOH solution by y =
220x. Throughout this experiment, it was used to determine the concentration of NaOH solution
in the reactor via the recorded conductivity.

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Conductivity (mS/cm)
20

15

10

y = 220x
5 R = 0.9996

0
0.00 0.02 0.04 0.06 0.08 0.10
Concentration of NaOH solution (M)

Figure 1: Conductivity as a function of concentration of NaOH solution.

3.2 Determination of rate law parameters

Rate law parameters were determined solely based on the experimental data obtained from CVBR
since it was independent of the type of reactor in which the reaction was carried out (Fogler, 2006).

Here, differential method was used to analyse the experimental data. As expected, when
dCNaOH
ln ( ) was plotted against CNaOH , straight line was obtained. Therefore, reaction order and
dt
rate constant can be determined from the slope and intercept and they were listed in table 1.

50.0 degree Celcius 33.2 degree Celcius

ln CNaOH
-5.0 -4.0 -3.0 -2.0 -1.0 0.0
-2.7
ln(-dCNaOH/dt)

y = -0.029x - 2.8427 -2.8

R = 0.9921

-2.9

y = -0.0304x - 2.9907
R = 0.9831 -3.0

Figure 2: Determination of rate law parameters for saponification of ethyl acetate and sodium
hydroxide solution in constant volume batch reactor by differential method of analysis.

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From Table 1, it could be clearly seen that reaction order was independent of the reaction
temperature as it remained constant at -0.030. Besides that, negative reaction order was attributed
to the fact that saponification of EA and NaOH solution is a reversible reaction (Nauman, 2008).

Table 1: Summary of the rate law parameters extracted from Figure 2

Reaction temperature Order of reaction Rate constant
(C) (x10-2 M1.03min-1)
33.2 -0.030 5.03
50.0 -0.029 5.83

Additionally, frequency factor and activation energy were calculated from rate constant values
listed in Table 1 with the aid of Equations (2) and (3). It was found that k o = 0.859 M1.03min-1 and
E = 7.224x103 kJ/kmol. Hence, the rate law for this saponification process can be written as
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rNaOH = (0.859e7.224x10 /RT )CNaOH 0.03
All calculation steps involved in determining rate law expression were shown in Appendix 3.

3.3 Influences of flow rate of reactants and reaction temperature on saponification process
in CSTR
For the same inlet flow rates of reactants (5.4 mL/min), an increment in reaction temperature from
28.7C to 35.6C caused the conversion of NaOH solution increased by about 5%. It was due to
the fact that molecules of reactants are more energetic at higher temperature. Subsequently,
collision between EA and NaOH molecules occurred more frequently which led to higher
conversion.

Table 2: Effects of reactants flow rate and temperature on the conversion of NaOH solution in
CSTR
Temperature (C) Flow rate of reactants Conversion of NaOH
(mL/min) solution (X)
28.7 5.4 66.67
35.6 5.4 69.86
34.1 7.4 59.82

On the other hand, at the same reaction temperature, when EA and NaOH solution entered CSTR
at higher flow rate, i.e. 7.4 mL/min, contact time between both reactants was then decreased. As a
result, conversion of NaOH solution dropped by 14%.

In short, to create a better reacting environment in CSTR, higher reaction temperature and lower
inlet flow rate are preferable.

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3.4 Performance of saponification process in CVBR and CSTR
Based on Table 3, at nearly same reaction temperature, conversion achieved in CVBR was 11%
higher than the one in CSTR. Even higher conversion was attained in CVBR, one must be taking
into account the desired production rate during the selection of reactor. It should be borne in mind
CVBR merely suitable for small scale production due to its operating mode whereas CSTR should
be chosen for large scale of production.

Table 3: Saponification of ethyl acetate and sodium hydroxide solution in CVBR and CSTR at
35C
Type of Reaction Flow rate of Conversion of NaOH
reactor temperature (C) reactants solution (X)
(mL/min)
CVBR 33.2 - 77.63
CSTR 35.6 5.4 69.86

4.0 Conclusions
In conclusion, rate of saponifcation of ethyl acetate and sodium hydroxide solution can be
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described by the following rate law: rNaOH = (0.859e7.224x10 /RT )CNaOH 0.03. It quantifies the
effects of reaction temperature and concentration of NaOH solution on saponification process.
Conversion increased by 5% when saponification process in continuous stirred tank reactor took
place at 35.6C as compared to at 28.7C. Furthermore, raising the flow rate from 5.4 mL/min to
7.4 mL/min caused a 14% drop in NaOH solution conversion. For this particular saponification
process, higher conversion was achieved in constant volume batch reactor (77.63%) as compared
to continuous stirred tank reactor (69.86%) worked under same isothermal operating condition,
i.e. 35C.

5.0 References
Fogler, H. S. (2006). Elements of chemical reaction engineering. 4th ed. Pearson Education, NJ.
Levenspiel, O. (1999). Chemical reaction engineering. 3rd ed. John Wiley & Sons, NJ.
Nauman, E. B. (2008). Chemical reactor design, optimization and scale up. 2nd ed. Hoboken, John
Wiley & Sons, NJ.