Manipal University Jaipur

Department of Chemical Engineering

CE 1732- Chemical Reaction Engineering Lab

IV Year, 7th Semester, 2019

EXPERIMENT #3
Reaction Kinetics Study for Plug Flow Reactor

INSTRUCTORS:
Dr. Gaurav Kataria
Dr. Nandana Chakinala

Submitted By:
Harshit Joshi (179101014)

Experiment carried on: December 24, 2020

Report submitted on: December 28, 2020

PRELAB (010)
EXECUTIVE SUMMARY (010)
INTRODUCTION/OBJECTIVES/PROCEDURE (030)
RESULTS & DISCUSSION (030)
CONCLUSIONS (005)
REFERENCES (005)
APPENDIX
a) Original data, sample calculations, other information (005)
GENERAL COMPLETENESS
a) Conciseness and neatness (005)
TOTAL (100)
TABLE OF CONTENT
List of Tables...................................................................................................................................3
List of Figures..................................................................................................................................3
Nomenclature...................................................................................................................................4
Executive Summary….....................................................................................................................5
Introduction…..................................................................................................................................6
Objective..........................................................................................................................................7
Scope................................................................................................................................................7
Experimental Setup…......................................................................................................................7
Procedure.........................................................................................................................................8
Results and Discussion…................................................................................................................9
Conclusion and Recommendations................................................................................................11
References…..................................................................................................................................11
Appendix…...................................................................................................................................12
A1. Raw Data…................................................................................................................12
A2. Observations and Calculations...................................................................................12
A3. Sample Calculation…................................................................................................13
List of Figures
Figure 1. Slope for second order
reaction Figure 2. Experimental Setup
for PFR

Figure 3. Plot between f(x) and 𝛕 for CAS/CBS = 0.03/0.025

Figure 4, Plot between f(x) 𝛕 for CAS/CBS = 0.04/0.035

Figure 5. Plot between Flowrates and Conversion

List of Tables
Table 1. Observations and Calculations for CAS/CBS =

0.035/0.04 Table 2. Observations and Calculations for CAS/CBS

= 0.04/0.03 Table 3. Values of k for different set of readings

NOMENCLATURE
Symbol Meaning

CiO Initial Concentration

CiS Stock Concentration
Ci Final Concentration
Xi Conversion
M Initial Molar Concentration
k Rate Constant
ri Rate of Reaction
vi Volumetric flow rates of Reactants
vT Total volumetric flow rate
VR Volume of Reactor
𝛕 Space time
dcoil Coil Diameter
dtube Tube Diameter
n No. of turns

Chemicals Used

Formula Name

CH3COOC2H5 (A) Ethyl Acetate

NaOH (B) Sodium Hydroxide
CH3COONa Sodium Acetate
C2H5OH Ethanol

Subscripts

A – Ethyl Acetate
B – Sodium Hydroxide
EXECUTIVE SUMMARY
The aim of this experiment was to study the kinetics of a saponification reaction in a plug flow
reactor. In order to achieve this, the reaction was performed at different stock concentrations of
NaOH and CH3COOC2H5. The reaction was found to be second order elementary reaction as the
data fit the best to second order. Initial concentrations, final concentrations and conversion for
reactants were calculated and a graph was plotted between a function of conversion and the
product of initial concentration of ethyl acetate and time. The slope of the graphs obtained
showed an increasing trend. And the slope of the graph gave the value for the rate constant.
Calculations were done for different flow rates of the reactant for 2 sets of stock concentrations.
For two sets of readings, k values were obtained as 2.08 litre/mol.min and 3.72 litre/mol.min.
The average value of k was calculated to be 2.72 litre/mol.min, and finally the rate of second
order elementary reaction can be written as -rA = 3.72CACB. Some error values were seen in the
plots and it is recommended that the stock concentrations of the reactants be taken carefully.
INTRODUCTION
In any chemical industry, reactors are the most important equipment used to carry out a specific
reaction in which a desired product is created from raw materials. Three major types of reactors
used in industries, batch reactor , continuous stirred tank reactors (CSTR) and plug flow reactors
(PFR).
A PFR or an ideal tubular reactor is a long, straight, pipe-shaped tank in which the reactive fluid
transits at steady state (no accumulation). In a PFR, the concentration of the reactant changes
from point to point in the direction of the flow. PFRs are an idealized scenario where there is no
axial mixing involved in the reactor. It is the opposite of the CSTR, where the reaction mixture is
perfectly mixed. It is assumed there is no mixing axially and complete mixing in radially.
Each plug of differential volume is considered as a separate entity, effectively an infinitesimally
small batch reactor, limiting to zero volume. As it flows down the tubular PFR, the residence
time ( ) of the plug is a function of its position in the reactor. Residence time in the reactor is
equal to the space time if the conditions in the reactor like pressure and temperature are same as
those at the entrance. In the ideal tubular reactor, which is called the “plug flow” reactor.
On applying a material balance : Mass in – mass out + generation - consumption = accumulation.
This gives us, V XA V
= . Also, the design equation for a PFR is given by τ = = C XAF XA
.
AO
∫
FAO −rA vo 0 −rA

The reaction carried out in the experiment is between sodium hydroxide, NaOH (B) and ethyl
acetate, CH3COOC2H5 (A) to give sodium acetate, CH3COONa and ethanol, C2H5OH.

CH3COOC2H5 + NaOH CH3COONa + C2H5OH

From literature we know, it is second order saponification reaction. It is assumed it is an

irreversible reaction with no back mixing. The rate of reaction is given by -rA= kCACB

So, for the reaction, performance equation ca be written as 1

M−XA ) = kτ.
CAO(1−M) ln (M(1−XA)

There are two procedures for analyzing kinetic data, the integral and the differential methods. In
order to determine the kinetics of the reaction using integral method, various graphs are plotted
by assuming certain orders of the reaction. For PFR, (M>1) we can use the following graph to
determine the rate constant.

Figure 1. Slope for second order reaction

OBJECTIVE
The object of this experiment is to study the rate kinetics in a plug flow reactor.

SCOPE
The scope of the experiment includes calculation of inlet and final concentrations of reactants,
calculation of space time, find the value of the rate constant, and finally get an expression for the
rate of reaction.

EXPERIMENTAL SETUP

Figure 2. Experimental Setup for Plug Flow Reactor

The Figure 2. shows the experimental set up for a plug flow reactor. It consists of two storage
tanks for sodium hydroxide and ethyl acetate. The storage tanks are connected with individual
rotameters to adjust the flowrates. The two reactants are made to enter into the PFR. The outlet
of PFR is connected to a valve to drain and collect the liquid product stream. The conductivity
meter probe shows the readings at different values of flowrates and stock concentrations.
PROCEDURE
1. Standardize the NaOH stock solution and not down the values of CAS and CBS.
1.1. Fill the HCl in the burette up to the 0-level mark
1.2. Take 10mL of NaOH in a conical flask
1.3. Add 2 drops of phenolphthalein indicator to it.
1.4. Add the HCl from the burette drop by drop into the conical flask until end point is
reached.
1.5. Note down the volume of HCl consumed.
1.6. Repeat the steps 3-4 times to get accurate results.
1.7. Apply N1V1 = N2V2 to find the normality of NaOH
2. The reaction temperature is set to be 30oC.
3. Set the volumetric flow rates of ethyl acetate (A) and sodium hydroxide (B) so that the value
initial molar ratio, M is 1 or more than 1.
4. Take readings at different values of volumetric flowrates of A and B.
5. The readings are taken till a steady state value is achieved for the conductivity meter probe.
6. Determine the final concentrations for the reactants from the conductivity readings.
7. Repeat reading for different values of stock solution.

RESULTS AND DISCUSSION

The aim of this experiment was to study the reaction between sodium hydroxide and ethyl
acetate in a plug flow reactor. Also, to study the kinetics of the reaction. Different stock
concentrations were taken for the set of readings at 30 oC for different flow rates of the reactants.
Final concentrations and conversions were calculated to plot a graph between f(x)
1 𝑀−𝑋𝐴 )) vs 𝛕.
(
𝐶𝐴𝑂(1−𝑀)
𝑙𝑛 (𝑀(1−𝑋𝐴)

Figure 3. Plot between f(x) and 𝛕 for CAS/CBS = 0.03/0.025

 Figure 4. Plot between f(x) and 𝛕 for CAS/CBS = 0.04/0.035

Figure 3. and figure 4. show the plots for different stock concentrations for sodium hydroxide
and ethyl acetate. The graph shows linear increasing trend (along with error values) which
confirms the second order reaction. The slope gives the value of rate constant k. For first set of
readings, CAS = 0.03 mol/l and CBS = 0.025, the slope gives value of k = 2.08 litre/mol.min and
second set gives a value of k = 3.35 litre/mol.min. The average value of k comes out to be 2.72
litre/mol.min

Figure 5. Plot between Flowrate and Conversion

We know that on increasing flowrate, the residence time in the reactor increases because of
which the reactants get enough time to react and hence, the conversion should increase.But we
observe that conversion is decreasing with increase in flowrate.
All these errors in results show that there were great experimental errors involved with it. A
plausible reason for this could be that the concentration of NaOH and ethyl acetate taken were
high. Because of these high concentrations, there was a very fast conversion at the operating
flowrates. The reactions were probably complete even before the first set of readings was taken
and hence, the results show no trend.
CONCLUSION AND RECOMMENDATIONS
The aim of this experiment was to study the kinetics of a saponification reaction in a PFR. In
order to achieve this, the reaction was performed at different stock concentrations of NaOH and
CH3COOC2H5 and reading were taken at different flow rates of NaOH and CH 3COOC2H5. The
reaction was found to be second order elementary reaction as the data fit the best to second order.
Initial concentrations, final concentrations and conversion for reactants were calculated and a
graph was plotted between a function of conversion and time. The slope of the graphs obtained
showed an almost increasing trend (error values included). The rate constant was determined
from the slope of the graphs and the average value of k was found to be 2.72 litre/mol.min, and
finally the expression for rate of reaction can be written as -rA = 2.72CACB. While doing the
kinetic study we see, with increase in volumetric flowrate of reactants, the conversion decreases
but it shouldn’t be the case. It can be said that the errors in the calculations is due to high stock
concentrations of NaOH and ethyl acetate.
It is recommended that lower stock concentrations of the reactants and in particular stock
concentration of sodium hydroxide should be less than that of ethyl acetate.

REFERENCES
1. O. Levenspiel, “Chemical Reaction Engineering” 3rd edition, John Wiley and Sons, 2016.
2. http://uorepc-nitk.vlabs.ac.in/exp9/index.html# 28/12/2020
 APPENDIX
A1. Raw Data
 Coil Diameter – 33cm
 Tube Diameter – 1.1cm
 Number of Turns – 5
 Temperature – 30oC

A2. Observations and Calculations

1. CAS = 0.03 mol/l CBS = 0.025 mol/l
vA vB YT Y28 vT 𝛕 (hr.) 𝛕 (m) CAO CBO M CB CA XA f(x)
2.5 3.75 54.64 56.224 6.25 0.025 1.505 0.012 0.02 1.25 0.014 0.012 0.026 1.8134
2.5 5 60.29 62.038 7.50 0.021 1.254 0.010 0.02 1.67 0.016 0.010 0.047 2.9541
2.5 6.25 65.96 67.872 8.75 0.018 1.075 0.009 0.02 2.08 0.017 0.008 0.017 0.9741
2.5 7.5 69.49 71.505 10.00 0.016 0.941 0.008 0.02 2.50 0.018 0.007 0.012 0.6863
2.5 8.75 72.24 74.334 11.25 0.014 0.836 0.007 0.02 2.92 0.019 0.007 0.008 0.4216
Table 1. Observations and Calculations for CAS/CBS = 0.03/0.025

2. CAS = 0.04 mol/l CBS = 0.035 mol/l

vA vB YT Y28 vT 𝛕 (hr.) 𝛕 (m) CAO CBO M CB CA XA f(x)
2.5 3.75 75.66 77.854 6.25 0.025 1.505 0.016 0.02 1.31 0.020 0.015 0.043 2.8745
2.5 5 83.71 86.137 7.50 0.021 1.254 0.013 0.02 1.75 0.022 0.012 0.065 2.9640
2.5 6.25 91.79 94.451 8.75 0.018 1.075 0.011 0.03 2.19 0.024 0.011 0.033 2.8745
2.5 7.5 95.28 98.043 10.00 0.016 0.940 0.010 0.03 2.63 0.025 0.009 0.069 2.7849
2.5 8.75 100.1 103.04 11.25 0.014 0.836 0.009 0.03 3.06 0.026 0.009 0.041 2.6745
Table 2. Observations and Calculations for CAS/CBS = 0.04/0.035

Reading Slope, k (litre/gmol.min)

1 2.080314239

2 3.352694838
Table 3. Values of k for different set of readings
A3. Sample Calculations
Calculation for volume of reactor
dcoil = 33cm dtube = 1.1 cm no. of turns, n = 5
2
VR = π dtube dcoiln = 156.7 cm3 = 0.157 liters
4

Calculation for Initial concentrations and Space time

For CAS = 0.03 mol/l, CBS = 0.025 mol/l, YT = 54.64 mS/cm, vA = 2.5 l/hr vB = 3.75 l/hr
CBS𝑣B
vA +vB = vT =6.25 l and M = = 1.25
CASvA
CASvA CBSvB
Now, C = = 0.012 mol/l and C = = 0.02 mol/l
AO 𝑣𝑇 BO 𝑣𝑇
𝑉𝑅
𝛕= = 0.025hr. = 1.505 min
𝑣𝑇

Calculation of Final Concentrations and Conversion

Y28 = YT (1+ 0.0145 (T-28)) = 56.22 mS/cm
CB = 0.00026Y28 – 0.000063 = 0.0147 mol/l and CA = CAO – (CBO – CB) = 0.012 mol/l
CA 1
XA = 1 − = 0.026 and f(x) =
𝑀−𝑋𝐴 ) = 1.813
CAO 𝐶𝐴𝑂(1−𝑀) ln (𝑀(1−𝑋𝐴)

The graph is plotted between f(x) and CAO𝛕 and the slope gives us the value of k
f(x)2−f(x)1
Slope = = 2.08
t2−t1

Finally, k = 2.08 litre/mol.min