Lab Report: Batch reactor

Instituto Tecnológico y de Estudios Superiores de Monterrey

Author:
Jesús Antonio Villanueva Barrón
A00830666

Professor:
Dra. Yatziri Rodriguez
M.Sc. Orlando Castilleja Escobedo

Due Date:
September 05, 2022
Keywords: Batch, conductivity, concentration, energy of activation, K.

1 Objective
● To study the kinetics of the homogeneous reaction in the liquid phase for the
saponification of ethyl acetate with sodium hydroxide to determine the
parameters of the reaction constant: activation energy and frequency factor.

2 Introduction
The rate of a reaction can be measured directly or indirectly through some property of
the reactive mixture that changes as the reaction progresses, that is easily measurable, such as
the concentration of some reactant or product, refractive index, absorbance, pressure,
conductivity, etc.
Chemical kinetics studies the rate and mechanism by which a reaction occurs. For

example, for the reaction A + B → C + D in liquid phase carried out in a reactor of

constant volume, perfectly mixed and with an intermittent regime (batch), the molar

balance of reagent A is:→

1 d NA dCA
−r A = = (1)
V dt dt
And the reaction rate can be expressed as:
α β
r A =k C A C B (2)
The constant of the reaction rate k is a function of temperature and can be
expressed by the Arrhenius equation:
−Ea
k= Ae RT (3)

An analysis of ethyl acetate saponification in a batch reactor was made. The reaction
that occurs is shown on formula number one.

NaOH +C H 3 COO C2 H 5 → C H 3 COONa +C H 5 OH (4)

A+B→C+D (5)

All stoichiometric coefficients are the same, on equation 1. So we can rewrite like equation 2,
where we can see that NaOH is the substance A and C H 5 OH is the substance D. The
formula that describes the behavior and establishes the measurements of a batch reactor can
be deduced from the general mass balance formula for a substance or element J and is shown
in formula 3.
V
d Nj
F j 0−F j ±∫ r j dV = (6)
0 dt
If the integral is considered as V and rj constant and considering accumulation we
know that:
dCj
r j= (7)
dt
The relationship between the concentrations of A and B is found through the
stoichiometry of the reaction. If the initial concentrations of the reactants are CA0 and CB0
then:
C B=C B 0−(C A 0 −C A ) (8a)
C B=C A −(C B 0−C A 0) (8b)
Combining equations (8a) and (8b) we obtain an equation for the reaction rate as a function
of CA:
r A =k C A−(C B 0−C A 0 ) (9)

Combined equations (7) and (9) yields:

dCA
=k C A −(C B 0 −C A 0) (10)
dt

Rearranging terms:
CA t
dCA0
∫ C A −( C B 0−C A 0 )
=−k ∫ dt (11)
C A0 0

In this case CA0=CB0 so:

1 1
=kt+ (12)
CA C A0

3 Methodology
a. Materials and substance
● 1 Stopwatch ● 1 Pipette
● 1 L aforation flask ● 1 Suctioner
 ● 1 Spatula ● 1 graduated tube of 250 mL
● 1 250 mL beaker ● 1 watch glass
● 1 L Beaker ● 1 wash bottle
● 2 L beaker ● Sodium hydroxide (NaOH)
● 1 graduated tube of 50 mL ● Ethyl acetate
● 1 graduated tube of 100 mL (CH3COOC2H5)

Figure 1. Experiment design of Batch run.

b. Experiment Procedure
There will be 3 runs at different temperatures, the duration of each run is of about 25
minutes.
1. Determine the operating temperatures, being the maximum operating temperature of
50°C and with a temperature difference between each run of 7°C.
2. Prepare 1 liter of 0.4 N solution of NaOH as follows:
3. Verify that the reactor is empty. If it is not empty, open the valve at the bottom of the
reactor. When emptying is finished, the valve must be closed.
4. Turn on the computer by pressing the red button at the bottom right (I/O).
5. With the help of the funnel, pour 1750 ml of distilled water into the reactor.
6. Turn on the agitator and set the rotational speed at about 500 rpm.
7. Add 250 ml of the 0.4 N Solution of NaOH to the reactor using the funnel.
8. Set the desired temperature following the process described below:
a. Turn on the heating resistor by pressing the red button (ON/OFF)
 b. 2 temperatures will appear on the panel. PV is the current temperature of the
system (in red) and PS is the temperature to be set (in green). Set the PS
temperature to the temperature decided by your team by pressing the third
blue button on the screen (left to right) and varying the value with the
arrows: ▲▼.
c. Press the third blue button on the display (left to right) to set the temperature.
d. Wait for the system to stabilize (around 10 min).

NOTE: In case the experiment is carried out at room temperature, do

not turn on the resistance, just record the temperature reading displayed on
the screen. It is advisable to make the first run at room temperature and then
gradually increase the temperature.
9. Verify that the conductivity meter is on. If not, turn it on by pressing the button
(ON/OFF). Assign the measurement to 2 decimal places by pressing the 19.99 mS/cm
button.
10. When the system is stabilized, record the conductivity of the 0.05 N solution of
NaOH.
NOTE: When emptying 250 ml of the 0.4 N solution of NaOH to 1750 ml of water,
the initial concentration will be different.
11. Weigh 8.811 g of Ethyl Acetate (CH3COOC2H5).
12. Empty the reagent into the reactor and start the chronometer at the same instant.
13. Take and record on the lab log the conductivity measurements as follows:
a. From start to the 3rd minute, every 10 seconds.
b. From minute 3 to minute 9 every 30 seconds.
c. From minute 9 until the conductivity remains constant every minute. (At
least 3 equal measurements)
NOTE: It is very important to record the initial conductivity of the
system, before adding Ethyl Acetate.
14. When finished, turn off the resistor first and then empty the contents by
opening the lower valve of the reactor. Turn off the propeller. Empty some distilled
water to clean the bottom of the reactor.
15. Clean your work area.
4 Calculations and Results
For this experiment a 0.25 L of 0.4 N solution of NaOH with 1,750 L of distilled
water was introduced on the reactor, giving a total volume of 2 L. The motor was turned on
and an initial conductivity of NaOH was measured. Then 8,811 g of ethyl acetate were added
and the measurements of the conductivity over time started. This was done at three different
temperatures and we can see the results on table 2.
Table 2.- Valores experimentales de las tres diferentes pruebas en 2400 segundos.

Run 1 2 3

Temperature (°C) 27 36 43
Initial conductivities 9.02 10.57 11.42
of NaOH

Time (s) Mixture Conductivity (mS/cm)

0 9.02 10.57 11.42

10 8.99 10.61 11.26

20 8.77 10.15 10.52

30 8.42 9.50 9.72

40 8.12 9.02 9.01

50 7.87 8.61 8.47

60 7.65 8.31 8.04

70 7.44 8.02 7.71

80 7.25 7.76 7.47

90 7.10 7.53 7.24

100 6.93 7.32 7.06

110 6.80 7.14 6.89

120 6.67 6.98 6.73

130 6.54 6.83 6.63

140 6.43 6.70 6.53

150 6.32 6.57 6.42

160 6.22 6.47 6.32

170 6.12 6.38 6.22

180 6.04 6.29 6.14

210 5.80 6.05 5.93

240 5.59 5.85 5.83

270 5.42 5.69 5.70

300 5.26 5.55 5.58

330 5.13 5.44 5.49

360 5.01 5.33 5.40

390 4.90 5.25 5.33

420 4.81 5.17 5.27

450 4.73 5.10 5.21

480 4.65 5.04 5.16

510 4.58 4.98 5.12

540 4.51 4.93 5.08

600 4.40 4.84 5.01

660 4.30 4.77 4.96

720 4.22 4.70 4.91

780 4.15 4.65 4.86

840 4.08 4.60 4.82

900 4.03 4.55 4.78

960 3.98 4.52 4.75

1020 3.94 4.48 4.72

1080 3.91 4.45 4.69

1140 3.87 4.42 4.66

1200 3.84 4.40 4.64

1260 3.81 4.37 4.62

1320 3.78 4.35 4.60

1380 3.75 4.33 4.58

1440 3.73 4.31 4.56

1500 3.71 4.29 4.55

1560 3.69 4.28 4.53

1620 3.67 4.26 4.52

1680 3.65 4.25 4.50

1740 3.64 4.23 4.49

 1800 3.62 4.22 4.48

1860 3.61 4.21 4.47

1920 3.59 4.19 4.46

1980 3.58 4.18 4.44

2040 3.57 4.17 4.43

2100 3.56 4.16 4.42

2160 3.54 4.16 4.41

2220 3.54 4.15 4.40

2280 3.52 4.14 4.39

2340 3.52 4.13 4.38

2400 3.51 4.13 4.38

With these results, we can obtain the concentration of substance A, for this it is
necessary to obtain the number m, this number is a coefficient that relates the concentration
with the conductivity. The initial conductivity of NaOH changed with temperature, taking the
data from time 0. With this information, the initial concentration of NaoH that is 0.05M and
equation number 4, it can be obtained the number m of NaOH.
S NaOH
m NaOH = (13)
C NaOH
S NaAc
m AcNa = (14)
C NaAc

On the other hand, to obtain the m number of the NaAC substance, the conductivity of
0.05 M was obtained with the help of figure 2 and then using equation 5.
 Figure 2. Conductivity temperature correlation of 0.05 M Sodium Acetate.

On table 3 we can appreciate the m values through the substance at the different temperatures
used in the experiment.

Table 3. Values of m of NaOH and NaAc at different temperatures.

Temperatures (°C) mNaOH mNaAc

27 180.4 74.256

34 211.4 81.834

43 228.4 87.728

Once these data are obtained, the concentration of CA can be determined with equation 6.

Smixture −m NaAc C NaOH 0

C A= (15)
m NaOH −m NaAc

The conductivity of the mixture is what was reached when the values stabilized and
this will cause the concentration values to change. The results are shown in table 4.

Table 4.- Concentrations of each run at a certain time.

Run 1 3 5

Time (s) 1020 1860 1800

CA (mol/L) 0.002140 0.000913 0.000665

After this, the calculation of the proportionality constant of the rate reaction (k) is
needed. We can obtain this through the mass balance and knowing that this saponification
reaction is second order, equation 11 can be deduced, which will be used for these
calculations. The results are shown in table 5.

Table 5.- Temperatures and its K values.

Run 1 3 5

Temperature (°C) 27 36 43
 K (L/mol*s) 0.3529 0.4711 0.6327

With these values, the activation energy and the Arrhenius constant can be obtained.
Taking into account equation 16, it can be linearized by applying a natural logarithm.
−Ea
k = Ae❑ RT (16)

−Ea
ln (k )=ln ( A )+ (17)
RT
By making a table of ln(k) (dependent variable) against 1/T (dependent variable) and
doing a linear regression with these three values, your ln(K) and ln(A) can be obtained from
this linear equation , comparing it with the one obtained in equation 17.

Figura 3. Table of ln(K) vs 1/T to obtain the linearized equation of k.

y=−3434.7 x +10.389 (18)

−Ea
Putting together equations 17 and 18 we obtain that =−3434.7, thus
R
Ea=(3434.7)(8.31447)=28558 J /mol . Putting the above equations together, we also get that
ln (A )=10.389 therefore A=e 10.389=32,500 .

5. Analysis of results
As we can see in table 2, as time passes, the conductivity is reduced, this can be seen in the
three tests carried out. On the other hand, when the temperature increases, the conductivity
rises. As can be seen, in the range of 2400 seconds or 40 minutes it was not possible to
clearly see that stability will be reached, in addition to this, each test from a certain result
gave a strange behavior. It is for this reason that test one ends at time 1020 s, test two at 1860
s and test three at 1800 s, this in order to give us values that can be analyzed more easily with
the knowledge acquired in the grade.
Table 4 shows how the concentration decreases with respect to the increase in
temperature, this can be justified, since at a higher temperature the molecules move faster,
therefore the rate of the reaction will be faster, and therefore lowest final reactant
concentration in this reaction.
On the other hand, it can be seen in table 5 that as the temperature increases, the
constant K also does. This helps us to appreciate the values obtained for the Arrhenius
number 32,500 and the activation energy 28,558 kJ/mol.

6. Conclusions
It can be concluded that the present work was successful, since the objectives of the report
were completed with satisfaction, because an experimental test was carried out, in this the
conductivities of the mixture of the substance was obtained and thanks to that it was possible
to obtain the concentration, the constant K, the energy of activation and the Arrhenius
number.
In the work of Borovinskaya, E.; Khaydarov, V.; Strehle, N. and Musaev, A. It can be
seen that an ethyl acetate saponification experiment was carried out at 17, 22 and 36 °C. In
this experiment it can be confirmed that the units of the reaction rate constant coincide with
the reaction being second order. In addition to this, it can be seen that to a certain extent the
temperature increases, the constant K also does, which agrees with the behavior seen in the
present work. It can be seen that in the work of Borovisnkaya E. and company, its activation
energy is 45.38 kJ/mol and that its A is 1*10^6.
Although it can be seen that the behavior of the present work is similar to that of the
literature and that the activation energy is presented in the same order as that of the literature,
the values are still different.
Although satisfactory behavior results were obtained, it should be clarified that there
could have been several factors that could have modified the results of the experiment, such
as human error, erroneous calibration, reagent contamination, imprecise tools, among other
factors, where human error is the most likely of all.
A variety of changes can be applied when setting the experiment, like the use of more
accurate tools than the human eye and therefore minimize the error of using the senses as
tools or a better calibration on the reactor computer. In addition to this, to reduce the error of
the experiment, multiple runs could be carried out to obtain more data and thus have a result
closer to the literature.

7. Bibliography
● Fogler, H. Scott, 2001, Elements of Chemical Reaction Engineering, Third Edition.
Prentice Hall.
● Kuheli Das, P. Sahoo, M. Sai Baba, N. murali, P. Swaminathan. (November 2011).
Kinetic Studies on Saponification of Ethyl Acetate Using an Innovative Conductivity-
Monitoring Instrument with a Pulsating Sensor. International Journal of Chemical
Kinetics, 43, 648-656. January 2015, De Wiley Online Library Database.
● Terry, Ethel M. and Stieglitz, Julius, 1927, "The coefficient of saponitication of ethyl
acetate by sodium hydroxide", J. Am. Chem. Soc., vol. 49, pp 2216.
● Borovinskaya, E.; Khaydarov, V.; Strehle, N. and Musaev, A. (2019). Experimental
Studies of Ethyl Acetate Saponification Using Different Reactor Systems: The Effect
of Volume Flow Rate on Reactor Performance and Pressure Drop. Septmeber 4, 2022,
de Applied Sciences Sitio web:
https://www.researchgate.net/publication/330904214_Experimental_Studies_of_Ethyl
_Acetate_Saponification_Using_Different_Reactor_Systems_The_Effect_of_Volume
_Flow_Rate_on_Reactor_Performance_and_Pressure_Drop

8. Annexes
a. Course information used.
i. Anexo_reactor_batch.pdf
ii. Batch Lab.pdf
b. Nomenclature
i. T (°C) → Temperature in degrees celsius

ii. XA → Also X, that means the conversion

iii. K → Kinetic constant of the rate

iv. F j 0 → Molar flow of j species

❑
v. C A❑→ Concentration of species A
❑
vi. C B❑→ Concentration of species B

vii. C A0❑→ Concentration of a species at the inlet of the reactor.

viii. α → reaction order with respect to reagent A

ix. β → reaction order with respect to reagent B

x. k → reaction rate constant.

xi. Smixture → Selectivity of the mixture

xii. r A → Rate law of substance A.