CHE331: Unit Operations and Process Control

Laboratory
Experiment No. 03

Name of the Experiment Batch Reactor

Date of Experiment 14th Sept 2024

Date of Report Submission 3rd Oct 2024

Group No. 02

Batch

Name Roll Number

Adarsh Pal 220054

Students’ Details Ajay Singh 220090

Abhishek Maurya 220047

Kaushalendra Singh 220511

Akansha Ratnakar 220093

To be filled by the T.A/Instructor:

Instructor

Name of the T.A

Evaluation

Aim/Objective Comments (if any):

Materials

Equations

Description

Observation

Analysis

Plots

Scaling Laws
 Error Analysis

Summary

Total (out of 20)

Objective:
To determine experimentally the rate equation for the saponification of ethyl acetate using a
batch reactor.

Aim:
To measure the conductivity of the NaOH solution to get the conversion value. To plot
the concentration v/s time graph by using conversion values to get a rate equation.

Introduction:
The experiment investigates the saponification of ethyl acetate in a batch reactor. Finding the
rate equation for this reaction and comprehending how reaction rates relate to concentration
and temperature are the main objectives. A temperature controller is used to manage both the
temperature of the hot water bath and the 2-liter stirring reaction vessel in the setup. NaOH
solution in a preset volume is added to the reaction vessel. A heated stirred tank with another
temperature controller is also utilised to keep the ethyl acetate solution at a constant
temperature. The reaction vessel is attached to this tank's output, and once the NaOH and
ethyl acetate solutions have reached the proper temperature, the outlet valve is adjusted to
mix the two solutions together inside the reaction vessel.

Materials Required:
● Distilled Water (To Prepare Solution).
● Conical Flasks.
● Measuring cylinder.
● Stopwatch.
● Burette.
● Weighing machine
● Conductivity metre

Chemicals Required:
● 0.1(N) NaOH Solution - 1 Litre
● 0.1(N) Ethyl Acetate - 1 Litre
● N/10 HCl
Theory:
Ethyl acetate and weak sodium hydroxide react. This reaction is a second-order reaction,
which indicates that it is concentration-dependent.

One container holds a one-liter solution of sodium hydroxide, and the other holds an ethyl
acetate solution. In the reaction container, we combine them, and we have control over when
that mixing takes place. We don't add extra chemicals during the reaction, and nothing leaks
from the container. We'll conduct a mass balance to better understand the reaction. In a batch
reactor, there is neither an inflow nor an outflow of reactants or products during the reaction.

Line Diagram:

Fig: Line Diagram of Batch Reactor

Equations Used:

Where,
 C = Specific Conductivity at time t
CO = Specific conductivity at time t=0
C∞= Specific conductivity at time t = ∞
CB =NaOH concentration at time t
CBO =NaOH concentration at time t = 0
CB∞= NaOH concentration at time t = ∞

Where,
Ko = Frequency factor
Ea = Activation energy
R = Gas constant
T = Temperature

N = Moles of ethyl acetate present in the reactor at time t k1,

k2 = Rate constant for the forward and backward reactions.

Where,
CA, CB, CC, CD = concentrations of A, B, C and D respectively
V = Volume of the reaction mixture t = time

Description:

The system comprises a stirring reaction vessel (2 litres) housed in a hot water bath with a
temperature controller to regulate the bath temperature in addition to the reactor's
temperature. The stirring reaction vessel must be filled with a measured amount of NaOH
solution. Another temperature controller is supplied to keep the stirring heated tank (for ethyl
acetate solution) at a constant temperature. When the reaction vessel reaches the correct
temperature, the outflow valve of this tank must be opened in order to mix the ethyl acetate
solution with the NaOH solution.

Procedure:
● The temperature bath was switched ON to maintain a temperature of 29oC.
● A solution of 1 L of 0.1N NaOH was prepared and poured inside the reactor
 ● A solution of 1 L of 0.1N ethyl acetate was prepared and poured into the CSTR heat
tank
● The CSTR valve was opened when the temperature of the bath reached 38oC, The
conductivity meter was switched on to record the values. The values were recorded
until the value of conductivity reaches some steady state value. After reaching the
steady state value, the reactor was drained out.
● The same procedure was carried out at 39oC and 49oC.
Observations and Calculations:

Concentration of NaOH solution used = 0.05 M.

We used the following equation to create the following observation table:

𝐶𝑜 −𝐶
=𝑋 Fractional conversion of NaOH at time t
𝐶𝑜 −𝐶∞

Cinf = 4800 μS/cm

C0 = Conductivity of solution at t = 0.

C = Conductivity at time t

C = Co*(1-X)

T=29℃

Table1.1
 Fig1.1

Fig1.2

Fig1.3

Equation of Line:
𝟏
= 𝟎. 𝟐𝟎𝟒 + 𝟐𝟎. 𝟗𝟓𝟕
𝑪𝒂
T=39o C

Table 2.1

Fig2.1
 Fig2.2

Fig2.3

Equation of Line:
𝟏
= 𝟎. 𝟒𝟑𝟐𝟓 + 𝟏𝟖. 𝟓𝟏𝟖
𝑪𝒂
T=49o C

Table 3.1
 Fig3.1

Fig3.2

Fig3.3

Equation of Line:
𝟏
= 𝟎. 𝟔𝟑𝟕𝟐 + 𝟏𝟒. 𝟕𝟗𝟑
𝑪𝒂
 Temperature (in ◦ C) k (in l/mol*s)
29 0.204

39 0.4325

49 0.6372
ln(k) vs 1/T plot:

𝑬𝒒𝒖𝒂𝒕𝒊𝒐𝒏: 𝒍𝒏(𝒌) = 𝒍𝒏(𝒌𝒐 ) − 𝑬𝒂 /𝑹𝑻

ln(ko) = 16.86

ka=exp (16.86) l/mol*s

Ea = 5555 J/mol

Observations:

1. Electrical conductivity decreases as the reaction proceeds to completion. This is

because the strong base (exhibits much ionic dissociation into Na+ and OH- ions)
gets used up in the reaction to form a soap and an alcohol (not much ionic
dissociation)
2. Conversion increases as the reaction occurs, but the rate of increase is negative.
This is because as the reaction proceeds, lesser reactant is present to react. Hence,
 according to le Chatelier’s principle, the rate of reaction becomes slower as the
reaction proceeds.
3. This is a second order reaction (rate depends on the concentration of both the
reactants: ethyl acetate and NaOH), and the concentration of both reactants is equal.
Thus, we get a linear relation between 1/C and time of reaction. The slope of this
graph gives the rate constant k (where rate of reaction (-r) = k*C^2) at the
temperature at which we carry out the reaction.
4. For the 1/C vs time graph, we only consider the initial points that give us a linear
relation. We ignore the later points while calculating the rate constant, since we don’t
want to account for the decreasing reaction rate due to le Chatelier’s principle.
5. We perform the reaction at three temperatures: 29℃, 39℃ and 49℃, and compare
the rate constants across the three temperatures by plotting ln(k) vs 1/T (T now in
Kelvin). The slope of this graph gives us the activation energy and along with the
intercept we get a general formula for the rate constant.

Results and Conclusion:

● The slope of the ln(k) vs 1/T graph gives the value of activation energy as Ea = 5555
J/mol.

● The rate constant is given by 𝑘 = kaexp(-5555/RT)

● The rate expression comes out to be r = kC2

Scaling Laws:
If we were to perform the saponification reaction at the industry level, we would need to
select the reactor equipment carefully, ensuring that it can handle the exothermic reaction
well. We would also need to look at appropriate pumps and control systems.

Questions:

1. Set up the equations and show how you will calculate the constants if the

concentrations CA and CB are not equal.

2. Can you use this type of reactor for determining rate of reaction of a

(i) Heterogeneous reaction

(ii) Rapid reaction

(iii) Reaction yielding a number of products

(iv) Gas phase reaction

3. In case you can use this reactor mention additional equipment’s needed.

Otherwise, point out the difficulties which make it impractical to be used in a

case.

4. Write down the drawbacks of this method of finding kinetics.

5. Suggest improvements in the experimental set up if you come across any

drawbacks and shortcomings.

Answers:

1. If the initial concentration of the reactants:

𝒎𝒐𝒍
𝑪𝑨𝑶 = 𝒊𝒏𝒊𝒕𝒊𝒂𝒍 𝒄𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒐𝒇 𝒆𝒕𝒉𝒚𝒍 𝒂𝒄𝒆𝒕𝒂𝒕𝒆 ( )
𝑳
𝒎𝒐𝒍
𝑪𝑩𝑶 = 𝒊𝒏𝒊𝒕𝒊𝒂𝒍 𝒄𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒐𝒇 𝑵𝒂𝑶𝑯 ( )
𝑳

Using rate law, we can write

𝑑[𝐶𝐴 ]
− = 𝑘𝐶𝐴 𝐶𝐵
𝑑𝑡
𝑁𝑜𝑤, 𝐶𝐴 = 𝐶𝐴𝑂 − 𝑋𝐴 𝑎𝑛𝑑 𝐶𝐵 = 𝐶𝐵 = 𝐶𝐵𝑂 − 𝑋𝐴 , ℎ𝑒𝑟𝑒 𝑋𝐴 𝑖𝑠 𝑒𝑥𝑡𝑒𝑛𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
𝒅[𝑪𝑨 ]
− = 𝒌(𝑪𝑨 −𝑿𝑨 )(𝑪𝑩− 𝑿𝑨 )
𝒅𝒕

Hence, for the non-equal concentrations, the above differential equation can be solved
using numerical methods.
2. a. Heterogenous Reaction: Batch reactors can handle heterogeneous reactions but need
effective mixing
b. Rapid Reaction: Not ideal for rapid reactions due to difficulty in measuring fast
concentration changes
c. Multiple Products: Batch reactors can be used, but determining rate constants
become complex
 d. Gas Phase Reactions: Suitable for gas phase reactions with design modifications such
as pressure vessels.

3. Heterogeneous Reaction: Requires a high-shear mixer or agitator and solid separators if

the catalyst is to be recovered.

Rapid Reaction: Requires accurate and high-speed concentration measurement techniques

like a stopped-flow reactor setup.

Reaction with Multiple Products: Requires advanced analytical equipment such as GC or

HPLC.

Gas Phase Reaction: Requires a pressure-resistant vessel and temperature control system,
along with safety precautions for handling gases.

4. Drawbacks of this Method for Finding Kinetics

1. Inaccuracy for Rapid Reactions: Rapid reactions may complete before reliable
concentration measurements can be made.

2. Complexity for Multiple Reactions: Determining the kinetic parameters for each
reaction pathway can become cumbersome.

3. Non-Uniform Mixing: In large-scale batch reactors, mixing may not be uniform,

leading to concentration gradients.

4. Gas-Phase Reactions: Handling and maintaining gas-phase reactions can be difficult

without specialized equipment.

5 . Suggested Improvements

1. Use of Automated Sensors: Employ automated sensors for continuous measurement

of concentrations, pH, or conductivity.
2. Enhanced Mixing: Use advanced mixing technologies to eliminate concentration
gradients, especially for heterogeneous reactions.
3. Microreactors for Rapid Reactions: For very fast reactions, use microreactors to
ensure better control and quick mixing.
4. Addition of Inert Solvents: For reactions yielding multiple products, use inert
solvents to slow down undesired side reactions.
 5. Real-Time Analytical Tools: Integrate real-time analytical tools like FTIR (Fourier-
transform infrared spectroscopy) for tracking reaction progress without sampling.

Precautions:
1. Clean the reactor after disposing of the hot-reacted solution.
2. Ensure the required temperature is in both the reactor and tank , mix accordingly
3. Ignore the initial reading because mixing will not start suddenly after some it will star