CHE331: PROJECT LAB REPORT

Name of the Experiment Esterification of ethanol

Date of Experiment 13th Nov 2024

Date of Report Submission 3rd Oct 2024

Batch

Name Roll Number

Akshat Shrivastav 220103

Students’ Details Vardaan Vig 221170

Rohan Nimesh 220907

Kaushalendra Singh 220511

To be filled by the T.A/Instructor:

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 Hypothesis:

This study aims to investigate the accuracy of the second-order kinetic model for a
reversible reaction of the form

A+B⇌C+D

where the rate equation is given by

𝑟 =𝑘C𝐴C𝐵

Specifically, we aim to validate whether this model's qualitative characteristics align

with observed experimental data for the esterification of ethanol and acetic acid in a
fed-batch reactor.

Explanation of the Hypothesis:

Using a fed-batch reactor to examine the esterification reaction provides insight into
whether the second-order kinetics model accurately reflects the behavior of this
reaction type, particularly in a catalyzed system. The hypothesis will be validated by
comparing our collected data to theoretical second-order kinetic graphs and
investigating the reaction rate's dependence on reactant concentrations. Additionally,
the effects of temperature on reaction kinetics will be studied, as temperature plays a
key role in altering the reaction rate constant and equilibrium position.
 Objective:

The goal of this project is twofold:

To verify the second-order rate law for the catalytic esterification reaction of ethanol
and acetic acid in a fed-batch reactor.
To explore how temperature variations affect reaction kinetics and equilibrium for
this second-order reaction..

Introduction:
A Batch Reactor is a closed system with no input and output streams. A batch
reactor can operate under the following conditions:
• Isothermal (temperature of reaction mass remains constant)
• Perfectly mixed (composition of the reaction mixture is uniform throughout)
• Constant volume (volume of the reaction mixture within the reactor remains
constant; there is no appreciable change in the density of reaction mass) In
homogeneous reactions, all reacting species remain in a single phase. The rate of
reaction for such a reaction can be defined as the moles of a component appearing
by reaction per unit volume of the reaction mixture per unit time. Time rate is
influenced by variables like temperature, pressure and concentration.

Materials Required:

• Apparatus Constant temperature bath with stirrer, Batch Reactor System

• Measuring cylinders, dropper, Conductivity meter
• Utilities required Electricity, Water

Chemicals Required:

● 0.2(N) Ethanol aqueous Solution - 1 Litre

● 0.2(N) Acetic acid - 1 Litre
● Conc. HCl
Theory:

For isothermal operation of the constant volume batch reactor, rate of reaction is dependent
only on the composition so that a solution for conversion XA with respect to time is
obtained from the mass balance.

At constant volume the fractional conversion XA and reactant concentration CA are

related by:

XA = (CAo − CA) / CAo

where CAo is the initial reactant concentration and is equal to NAo/V

( NAo is the moles of reactant A corresponding to zero conversion at time t= 0 and V is the
reaction mixture volume).

For a reversible second order reaction:

A+B↔C+D

the specific reaction rate (rate of formation of C or disappearance of A) is given by,

From stoichiometry, if CA =CAo (1− XA)

expressing in terms of fractional conversion, we obtain,

where t is the time required for conversion XA, K is the reaction equilibrium constant,

The experiment involves the study of the esterification of ethyl alcohol and acetic acid.
A B C D

CH3COOH + C2H5OH → CH3COOC2H5 + H2O ………………..(3)

In an isothermal batch reactor with stirrer using HCl as a catalyst.

Line Diagram:

Equations Used:
 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 ethanol
solution. Another temperature controller is supplied to keep the stirring heated tank (for
acetic acid 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 acetic acid
solution with the ethanol solution.

Procedure:
• Add a known quantity (1000 ml) of aqueous solutions of ethyl alcohol of known concentration
to the given reactor.
• Start the stirrer and control the hot water at the desired reaction temperature (approx. 40ᴼC).
• Heat a known quantity (1000 ml) of aqueous solution of acetic acid of known concentration to
the desired reaction temperature separately.
• Add the aqueous solution of acetic acid quickly in the reactor after the reactor temperature
reaches 45deg C. Start the conductivity meter.
• Add measured quantity (2 ml) of Conc. HCl (as catalyst) in to the reactor mixture.
• Keep taking the values in the device till it reaches a steady value.

Calculation
Done through matlab

Observations and Calculations:

Conductivity is in mS/cm.
(Concentration of Reactants and Product vs. Time):
Reactant Depletion:
• The concentrations of ethanol and acetic acid (represented by the blue and
yellow lines, respectively) decrease quickly at the start of the reaction.
• Both reactants are nearly consumed by around 20-30 seconds, suggesting a
fast reaction rate, especially in the initial stages.
Product Formation:
• The concentration of ethyl acetate (represented by the orange line) increases
sharply in the first few seconds, mirroring the depletion of the reactants.
• After about 20-30 seconds, ethyl acetate reaches a plateau, indicating that the
reaction has approached equilibrium.
Reaction Equilibrium:
• The leveling off of all lines (reactants and product) indicates that the reaction
reaches equilibrium within a short period, after which there is little to no
change in concentrations.

(Reaction Volume vs. Time):

Volume Decrease:
• The reaction volume decreases rapidly in the first few seconds, which could
be due to the consumption of reactants or possibly changes in density as
products are formed.
• The rapid initial decrease is followed by a leveling off, indicating a stable
reaction environment after equilibrium is reached.
Volume Stabilization:
• Similar to the concentration graph, the reaction volume stabilizes around the
same time as equilibrium is achieved, reinforcing that most reaction activity
happens in the initial phase.

Overall Insights:
• Fast Reaction Rate: The esterification reaction proceeds very quickly, with
most of the change occurring within the first 20-30 seconds.
• Equilibrium Achievement: Both graphs show that equilibrium is reached
relatively quickly, with stable concentrations and volume after this point.
• Reaction Dynamics: The rapid depletion of reactants and formation of the
product suggests that the reaction is favorable and efficient, particularly under
the conditions provided (possibly a high temperature or use of a catalyst).
Conversion Rate Differences:
• The reaction at 60°C (blue line) achieves a higher conversion rate than the
reaction at 40°C (orange line).
• This higher conversion at 60°C suggests that temperature positively
influences the reaction rate, as expected in many chemical reactions,
including esterification.
Reaction Completion Time:
• Both reactions reach their maximum conversion relatively quickly, within the
first 20-30 time units (assuming these units are minutes, hours, etc.,
depending on the experimental setup).
• After this initial period, both curves stabilize, indicating that the reaction has
reached equilibrium.
Equilibrium Conversion:
The reaction at 60°C stabilizes at a slightly higher conversion rate than the
one at 40°C. This difference reflects the effect of temperature on the
equilibrium position, where higher temperatures favor a greater extent of the
esterification reaction.
Reaction Kinetics:
• The faster rise in conversion at 60°C indicates a quicker approach to
equilibrium, consistent with increased molecular activity at higher
temperatures.
• The reaction at 40°C reaches equilibrium more slowly, indicating a slower
reaction rate.

Results and Conclusion:

● The rate constant is given by 𝑘 =0.01123lt/mol sec for 40C

● The rate constant is given by 𝑘 =0.0155lt/mol sec for 60C

● The rate expression comes out to be r = kC2

Experiment Failures:
Valve Leakage and Delayed Opening:
• In the first experiment, a leak was detected in the valve, which impacted the
consistency of the reactant feed rate. Additionally, the valve was not opened
instantaneously, causing uneven flow and fluctuations in the reactant
concentration profiles. This inconsistency led to unreliable data on reaction
kinetics, necessitating immediate adjustments to prevent further deviations in
subsequent trials.
Catalyst Overdose:
• During one of the initial setups, an excessive amount of sulfuric acid catalyst
was added by mistake, resulting in an unusually high conductivity reading.
This overload in ion concentration overwhelmed the conductivity meter,
causing it to display an upward trend rather than the expected gradual
decrease. This error compromised our initial data collection and highlighted
the need to carefully calibrate catalyst concentration for accurate reaction
monitoring.
Temperature Control Malfunction:
During one trial, the temperature control system malfunctioned, leading to
significant temperature fluctuations in the reactor. This variability directly
affected the reaction rate constant and caused unpredictable shifts in the
reaction equilibrium, introducing significant error in our data.
Equilibrium Shift Due to Accumulation of Water:
As the reaction proceeded, the esterification process generated water as a
byproduct, which began to accumulate in the reactor. Since the experiment
used an aqueous solution of acetic acid and ethanol as the reactants, this initial
presence of water, combined with additional water formed during the
reaction, created a situation where the equilibrium started to shift back toward
the reactants. This reversible shift led to a reduction in the yield of ethyl
acetate, as the reaction favored the formation of reactants over products in the
presence of excess water. Recognizing this equilibrium shift, we explored
potential ways to manage water content in future trials to
maximize product yield.

Troubleshooting Steps:
Valve Replacement and Adjustment:
• In the first experiment, a leak was detected in the valve, which impacted the
After detecting leakage and inconsistent feed rates due to the faulty valve, we
took several actions to correct this issue. First, we thoroughly inspected the
valve system. We made sure to perform the mixing instantaneously.
Catalyst Calibration and Standardization:
• The initial trials revealed that excessive sulfuric acid catalyst caused an
unexpected increase in conductivity, which overwhelmed the conductivity
meter. To address this, we recalibrated the catalyst concentration by
conducting a series of smaller-scale test reactions to determine the optimal
amount needed to maintain reaction efficiency without exceeding the meter’s
measurement capacity. We found that reducing the catalyst concentration to
0.5% of the reaction mixture provided sufficient catalytic activity while
maintaining stable conductivity readings. To ensure consistency across trials,
we used a precision pipette to add the sulfuric acid catalyst and standardized
this concentration for all subsequent experiments. This approach allowed for
more accurate conductivity monitoring, which directly improved the quality
of our kinetic data.
 Temperature Control Malfunction:
During one trial, the temperature control system malfunctioned, leading to
significant temperature fluctuations in the reactor. This variability directly
affected the reaction rate constant and caused unpredictable shifts in the
reaction equilibrium, introducing significant error in our data.
Explored but Unimplemented Troubleshooting Strategies for Equilibrium
Control:
Reduction of Initial Water Content:
We considered reducing the initial water content in the reaction mixture by
using anhydrous ethanol and pre-drying the acetic acid with molecular sieves.
By minimizing the starting amount of water, we aimed to limit its impact on
the reaction equilibrium. However, implementing this strategy was not
feasible as batch reactor required 1L of reactants.
Temperature Adjustment for Enhanced Water Removal:
Another strategy we explored was to adjust the reactor’s temperature profile
to allow for controlled water evaporation at specific stages of the reaction. By
running the reactor at a slightly elevated temperature, we could encourage the
evaporation of water, thus shifting the equilibrium more favorably toward
ester formation. However, this approach was ultimately deemed impractical
because maintaining a higher temperature risked deactivating the sulfuric acid
catalyst, which would compromise the reaction kinetics and potentially lead
to incomplete conversion.
Continuous Stirring and Reactor Venting for Water Removal:
To further address water accumulation, we discussed the possibility
incorporating a calibrated vent to allow the slow release of water vapor. This
approach would help reduce water buildup without losing a significant
amount of reactant. However, due to limitations in our equipment, we could
not implement an adequate venting system that would release water
effectively while ensuring minimal reactant loss. This strategy would have
required more precise control mechanisms than were available in our setup.

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

Appendix:
Matlab code
% Isothermal fed-batch reactor operating at 40°C
clc,clear

mw=[0.04607 0.06005 0.08811 0.01802]; % molecular weights (kg/mol)

ro=[ 780 1049 902 998]; % densities (kg/m3)
ni=[ -1 -1 1 1]; % stoich. coefficients

n0=[0.2 0.2 0 0]; % initial moles (mol)

tspan=0:0.1:100; % time span (s)
k=1.23e-4; % kinetic constant (m3/(mol s))
F=[0 0 0 0]; % feed (mol/s)
% for the experiment we took feed to be 0
Vmax=0.002; % maximum volume (m3)

options=odeset('MaxStep',0.1);
fn=@(tx,nx)ode_ex2_09(tx,nx,mw,ro,ni,k,F,Vmax);
[tx,nx]=ode45(fn,tspan,n0,options);
for j=1:length(nx)
Vr(j)=0;
for k=1:4
Vr(j)=Vr(j)+nx(j,k)*mw(k)/ro(k);
end
end

%% plot

subplot(1,2,1)
plot(tx,nx(:,1),tx,nx(:,2),tx,nx(:,3))
grid
xlabel('Time (s)')
ylabel('Moles (mol)')
legend('ethanol','acetic acid','ethyl acetate')

subplot(1,2,2)
plot(tx,Vr)
grid
xlabel('Time (s)')
ylabel('Reaction volume (m^{3})')

function [dn] = ode_ex2_09(t,n,mw,ro,ni,k,F,Vmax)

Vr=sum(n'.*mw./ro); % reaction volume (m3)

c=n/Vr; % concentrations (mol/m3)
r=k*c(1)*c(2); % reaction rate (mol/(m3 s))

if Vr<Vmax % check if Vmax is reached

Fx=F;
else
Fx=[0 0 0 0];
end

dn(1)=ni(1)*Vr*r + Fx(1);
dn(2)=ni(2)*Vr*r + Fx(2);
dn(3)=ni(3)*Vr*r + Fx(3);
dn(4)=ni(3)*Vr*r + Fx(4);
dn=dn';
end