Reactor Design (IQ2011B) – Batch reactor

BATCH REACTOR
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.

Objectives

1. Verify that the kinetic expression for saponification of ethyl acetate with sodium hydroxide
is a second-order irreversible reaction.
2. Obtain the kinetic parameters: activation energy and frequency factor.
3. Interpret and explain the procedure for the calculation of concentration using the
conductivity of the mixture. Include your calculations in the report.
4. Check and verify the validity of the results; compare them with the values reported in the
literature.

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.

The kinetic study is performed in the laboratory on a small scale, trying to run the experiment at
conditions that facilitate the interpretation of the data such as:
1. The concentration of a reactant or product and the temperature are the same at any
position in the reactor (ideal mixing).
2. The concentration only changes due to the reaction and not by change in volume
(constant volume).

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 𝑑𝑁𝐴 𝑑𝐶𝐴 (1)

−𝑟𝐴 = =
𝑉 𝑑𝑡 𝑑𝑡

and the reaction rate can be expressed as:

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 Reactor Design (IQ2011B) – Batch reactor

𝛽
𝑟𝐴 = 𝑘𝐶𝐴𝛼 𝐶𝐵 (2)

Where:
𝑟𝐴 : reaction rate of A
𝐶𝐴 : Concentration of reagent A
𝐶𝐵 : Concentration of reagent B
α: reaction order with respect to reagent A
β: reaction order with respect to reagent B
k: reaction rate constant.

The constant of the reaction rate k is a function of temperature and can be expressed by the
Arrhenius equation:

𝐸𝑎
𝑘 = 𝐴 𝑒 −𝑅𝑇 (3)

In this laboratory practice, the reaction of saponification of ethyl acetate with sodium hydroxide
to produce sodium acetate and ethanol is studied:

CH3 COOC2 H5 + NaOH → CH3 COONa + C2 H5 OH

The reaction is known to be global second order, first order with respect to sodium hydroxide and
first order with respect to ethyl acetate. The expression for the reaction rate is:

𝑟𝐴 = 𝑘𝐶𝐴 𝐶𝐵 (4)

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:

𝐶𝐵 = 𝐶𝐵0 − (𝐶𝐴0 − 𝐶𝐴 ) (5a)

𝐶𝐵 = 𝐶𝐴 + 𝐶𝐵0 − 𝐶𝐴0 (5b)

Combining equations (4) and (5b) we obtain an equation for the reaction rate as a function of CA:

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 Reactor Design (IQ2011B) – Batch reactor

𝑟𝐴 = 𝑘𝐶𝐴 (𝐶𝐴 + 𝐶𝐵0 − 𝐶𝐴0 ) (6)

Combined equations (2) and (6) yields:

𝑑𝐶𝐴
= −𝑘𝐶𝐴 (𝐶𝐴 + 𝐶𝐵0 − 𝐶𝐴0 ) (7)
𝑑𝑡

Rearranging terms:

𝐶𝐴 𝑡
𝑑𝐶𝐴
∫ = −𝑘 ∫ 𝑑𝑡 (8)
𝐶𝐴0 𝐶𝐴 (𝐶𝐴 + 𝐶𝐵0 − 𝐶𝐴0 ) 0

Case 1

𝐶𝐴0 = 𝐶𝐵0
1 1
= 𝑘𝑡 + (9)
𝐶𝐴 𝐶𝐴0

Case 2

𝐶𝐴0 ≠ 𝐶𝐵0
1 𝐶𝐴 𝐶𝐵 − 𝐶𝐴 + 𝐶𝐴
𝑘𝑡 = ln [( 0 ) ( 0 )] (10)
𝐶𝐵0 − 𝐶𝐴 𝐶𝐵0 𝐶𝐴

MATERIALS AND SUBSTANCES

• 1 Stopwatch • 1 graduated tube of 50 mL

• 1 L aforation flask • 1 graduated tube of 100 mL
• 1 Pipette • 1 graduated tube of 250 mL
• 1 Suctioner • 1 watch glass
• 1 Spatula • 1 wash bottle
• 1 250 mL beaker • Sodium hydroxide (NaOH)
• 1 L Beaker • Ethyl acetate (CH3COOC2H5)
• 2 L beaker

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 Reactor Design (IQ2011B) – Batch reactor

APPARATUS

Below is a figure describing the experimental equipment used in practice.

Figure 1: Batch reactor available at the Chemical Engineering laboratory, Campus Monterrey.

METHODOLOGY

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). (DO NOT turn on
the resistor, which is the round button (ON/OFF) found on the panel.)

Figure 2: Button to turn on the computer, located at the bottom of the panel.

5. With the help of the funnel, pour 1750 ml of distilled water into the reactor.

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 Reactor Design (IQ2011B) – Batch reactor

6. Turn on the agitator and set the rotational speed at about 500 rpm.

Figure 3: Propeller; the power button is located at the bottom right, to adjust the speed, use
the knob just below the screen.

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).

Figure 4: Temperature control panel.

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.

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 Reactor Design (IQ2011B) – Batch reactor

Figure 5: Conductivity meter, power button; first right-hand side button, 19.99 mS/cm
button; last left-hand side button.

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.

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.