Manipal University

Department of Chemical Engineering

CE 1732- Chemical Reaction Engineering Laboratory

IV YEAR, VIITH SEMESTER, 2018

EXPERIMENT #5
Study of a non-catalytic reaction in a Plug Flow Reactor

INSTRUCTORS:
Dr. Gaurav Bhaduri
Dr. Abhishek Sharma

GROUP #2
Akriti Agarwal - 159110003

Experiment carried on: September 21, 2018

Report submitted on: September 28, 2018

PRELAB (10) ______

EXECUTIVE SUMMARY (10) ______
INTRODUCTION/OBJECTIVES/SCOPE/PROCEDURE (30) ______
RESULTS & DISCUSSION (30) ______
a) Data analysis and interpretation of information
b) Presentation of relevant information (including results on graphical, tabular or equation
forms)
CONCLUSIONS (5) ______
REFERENCES (5) ______
APPENDIX
a) Original data, sample calculations, Excel sheets (5) ______
GENERAL COMPLETENESS
a) Conciseness and neatness (5) ______
TOTAL (100) ______
Table of Contents
List of Figures.......................................................................................................................................3
List of Tables.........................................................................................................................................3
Executive Summary...............................................................................................................................1
Introduction...........................................................................................................................................2
Objective...............................................................................................................................................2
Chemicals Used.....................................................................................................................................2
Experimental Set-up..............................................................................................................................3
Procedure...............................................................................................................................................3
Preparation of chemicals....................................................................................................................3
Standardization..................................................................................................................................3
Experimental procedure.....................................................................................................................4
Observations and Calculations...............................................................................................................4
Results and Discussion..........................................................................................................................5
Conclusion and Recommendation.........................................................................................................7
References.............................................................................................................................................7
Acknowledgement.................................................................................................................................7
Appendix A5.........................................................................................................................................8
Original Data Obtained......................................................................................................................8
Detailed Calculations.........................................................................................................................9
Sample Calculation..........................................................................................................................10
Error Calculation.............................................................................................................................10

List of Figures
Figure 1: Experimental Set-up...............................................................................................................3
Figure 2: Plot showing how conversion varies with flowrate in the PFR..............................................6
Figure 3: Plot showing rate constant v/s flowrate..................................................................................6

List of Tables
Table 1: Standardization of NaOH.........................................................................................................5
Table 2: Standardization of HCl............................................................................................................5
Table 3: Observation for flow rate of 0.7 LPH......................................................................................8
Table 4: Observation for flow rate of 1.4 LPH......................................................................................8
Table 5: Observation for flow rate of 2.6 LPH......................................................................................8
Table 6: Observation for flow rate of 5.4 LPH......................................................................................8
Table 7: Detailed calculation for 0.7LPH..............................................................................................9
Table 8: Detailed calculation for 1.4LPH..............................................................................................9
Table 9: Detailed calculation for 2.6LPH..............................................................................................9
Table 10: Detailed calculation for 5.4LPH............................................................................................9
Table 11: Error in readings at 0.7LPH.................................................................................................10
Table 12: Error in readings at 1.4LPH.................................................................................................10
Table 13: Error in readings at 2.6LPH.................................................................................................10
Table 14: Error in readings at 5.4LPH.................................................................................................11
Executive Summary
The objective of the experiment was to study the non-catalytic homogeneous reaction
between NaOH and CH3COOC2H5 in a Plug Flow Reactor. A 0.5L PFR filled with beads was
used. The experiment was performed at four different flowrates (0.7LPH, 1.4LPH, 2.6LPH,
5.4LPH).For each flowrate 10ml sample was taken from the PFR after 25minutes and
quenched into 20ml HCl to kill the reaction. The sample and HCl mixture was titrated with
NaOH to find the amount of NaOH that reacted with ethyl acetate. The conversions obtained
were 99%, 93.33%, 89.33% and 79% at a flowrate of 0.7LPH, 1.4LPH, 2.6LPH and 5.4LPH
respectively. Thus, the conversion increased with the decrease in the flowrate. Rate constant
for this first order reaction was calculated using the rate equation for a first order reaction in a
PFR and it was found to be 0.107min -1, 0.126min-1, 0.194-1 and 0.281min-1 at a flowrate of
0.7LPH, 1.4LPH, 2.6LPH and 5.4LPH respectively. Since the rate constant is not constant
with the change in flowrate it was concluded that the data obtained does not fit a Plug Flow
Reactor.

1
Introduction
A PFR is an ideal steady state flow reactor in which no axial mixing takes place and a
uniform velocity profile is maintained across the radius. [1] The necessary and sufficient
condition for plug flow is that residence time in the reactor should be same for all the
elements of fluid.[1] In a plug flow reactor the composition of the fluid varies from point to
point along a flow path. Mass balance for a plug flow reactor over a small element is given as
follows[1]:
Input=Output + disappearance by reaction+accumulation
Accumulation = 0
F A =F A +d F A + (−r A ) dV … … … ..(5.1)

d F A =d [ F A 0 ( 1−X A ) ]=−F A 0 d X A … … ..(5.2)

XA
τ v d XA
= =∫ … … … … … ( 5.3 )
C A 0 F A 0 0 −r A

The objective of the experiment is to study the reaction between CH3COOC2H5 and NaOH in
a PFR. It is a second order saponification reaction as follows[2]:
C H 3 COOC 2 H 5 + NaOH →C H 3 COONa+ C2 H 5 OH
In this experiment we take equal normality of NaOH and C H 3 COOC 2 H 5 solution and
even maintain equal volumetric flowrates. Due to this the molar flowrate of NaOH is quite
high as compared to that of CH3COOC2H5. Due to the appreciable difference between the
molar flowrates we can consider the reaction to be a pseudo first order reaction and hence
write the following equation for a constant density system in a PFR[1]:
1
k τ =ln … … … … … … ..(5.4)
1−X A

Objective

The objective of the experiment was to study a non-catalytic homogeneous reaction of NaOH
and CH3COOC2H5 using a PFR.
Chemicals Used

 99.5 % Ethyl acetate which is an analytical reagent manufactured by Loba Chemie

Pvt. Ltd.

2
  98% Pure Sodium Hydroxide Pellets which is an analytical reagent manufactured by
Loba Chemie Pvt. Ltd.
 99% Oxalic Acid reagent manufactured by Loba Chemie Pvt. Ltd.
 37 wt% Hydrochloric acid which is an an analytical reagent manufactured by Loba
Chemie Pvt. Ltd.
Experimental Set-up

The experimental set-up is as shown in Fig. 1. The set-up is manufactured by Leiesil

Innovative System. There are two storage tanks at the top to store the two reactants, NaOH
and Ethyl Acetate. The storage tanks are connected with individual rotameters to adjust the
flowrates. The two reactants enter the PFR which is filled with beads and having a volume of
0.5L. The outlet is connected to a valve to drain the liquids contained in the PFR.

Figure 1: Experimental Set-up

Procedure

Preparation of chemicals

Ethyl acetate: To prepare 15L of 0.01N of ethyl acetate add 13.625g of it to 15 L of water.
Sodium hydroxide: To prepare 16L of 0.01N NaOH add 6.4g of NaOH To 16L of water.
Oxalic acid: To prepare 1L of 0.02N C2H2O4 add 1.8 g to 1L of water.
Hydrochloric acid: To make 2L 0.05N HCl add 6ml of 37.5 wt% HCL to 2L of water.

3
Standardization
1. Standardization of NaOH
 NaOH is standardized because it is hygroscopic.
 It is standardized using standard Oxalic acid.
 Fill the NaOH in the burette upto the 0 level mark.
 Take 10mL of Oxalic acid in a conical flask
 Add 2 drops of phenolphthalein indicator to it.
 Pour the NaOH from the burette drop by drop into the conical flask until end
point is reached.
 Note down the volume of NaOH consumed.
 Repeat the steps 3-4 times to get accurate results.
2. Standardization of HCl
 HCl is standardized using standardized NaOH
 Fill the NaOH in the burette up to the 0 level mark.
 Take 10mL of HCl in a conical flask
 Add 2 drops of phenolphthalein indicator to it.
 Pour the NaOH from the burette drop by drop into the conical flask until end
point is reached.
 Note down the volume of NaOH consumed.
 Repeat the steps 3-4 times to get accurate results.

Experimental procedure
a. Fill the NaOH and CH3COOC2H5 in the feed tanks.
b. Set the flowrates of NaOH and Ethyl Acetate to 700 MLPH using the rotameters
provided.
c. Remove all the air bubbles in the pipe.
d. The mixture is allowed to flow into the PFR.
e. After 25 minutes, take out 10 mL of reaction mixture from the reactor and quench it
into 20 mL of the standardized HCl solution.
f. Divide the 30ml solution into three equal samples of 10ml each.
g. Titrate 10 mL of the reaction mixture with standardized NaOH using phenolphthalein
as an indicator

4
 h. Repeat the same procedure for different flowrates (1400, 2600, 5400 MLPH) of
NaOH and Ethyl Acetate.
Observations and Calculations

 For standardization of NaOH:

Table 1: Standardization of NaOH

Volume of Oxalic acid taken (ml) Volume of NaOH consumed(ml)

10 8.1
10 8.0
10 7.8

Average volume of NaOH required = 7.96ml

Normality of Oxalic acid= 0.02N
So, Normality of NaOH = 0.025N
 For standardization of HCl:
Table 2: Standardization of HCl

Volume of HCl taken (ml) Volume of NaOH consumed(ml)

10 25.3
10 25.5
10 26.9

Average volume of NaOH required = 25.9ml

Normality of NaOH = 0.025N
So, Normality of HCl = 0.065N
 The flowrate of the reactants were fluctuating because of the presence of air bubbles
in the pipelines.
Results and Discussion

To find the conversion of NaOH we add HCL to the mixture obtained from each CSTR. Two
reactions occur simultaneously:
NaOH + CH3COOC2H5 → CH3COONa + C2H3OH (1)
NaOH + HCl → NaCl + H2O (2)
We add HCl because it interferes with the NaOH an Ethyl Acetate reaction. HCl reacts with
NaOH to form NaCl and H2O and hence it kills the first reaction. When we titrate the HCl
and reaction mixture with NaOH, the concentration of HCl we obtain gives the concentration

5
of HCl that is left un-reacted at the end of reaction 2. The concentration of reacted HCl in
reaction 2 is calculated by subtracting the initial HCl concentration from un-reacted HCl
concentration. The concentration of reacted HCl gives the concentration of un-reacted NaOH
in reaction 1, and hence the conversion of NaOH can be calculated. The calculations can be
found in Appendix A.5. Using this concept the results obtained for a PFR are shown in Fig. 2
and 3.
120
99
100 89.33
93.33 79
80
Conversion

60

40

20

0
0 1 2 3 4 5 6
Flow rate (LPH)

Figure 2: Plot showing how conversion varies with flowrate in the PFR

Fig. 2 shows that in a PFR as the flowrate increases the conversion decreases this is because
the residence time decreases. The data set obtained and the calculation performed can be seen
in Appendix.
0.300 0.281

0.250
0.194
0.200
k(min-1)

0.150 0.126
0.107
0.100

0.050

0.000
0 1 2 3 4 5 6
Flow rate (LPH)

Figure 3: Plot showing rate constant v/s flowrate

6
Fig. 3 shows that the rate constant varies with the flowrate. The rate constant (k) was
calculated using equation 5.4. The calculation can be found in Appendix Rate constant should
be constant for a reaction and should not vary with the flowrate. Since k varies with the
flowrate we might infer that the data obtained does not fit the PFR. In this case since the PFR
used in the experiment is filled with beads it might be behaving as a fixed bed reactor instead
of a PFR.
Conclusion and Recommendation

The objective of the experiment was to study the non-catalytic homogeneous reaction
between NaOH and CH3COOC2H5 in a Plug Flow Reactor. A 0.5L PFR filled with beads was
used. The conversions obtained were 99%, 93.33%, 89.33% and 79% at a flowrate of
0.7LPH, 1.4LPH, 2.6LPH and 5.4LPH respectively. Thus, the conversion increased with the
decrease in the flowrate. Rate constant for this first order reaction was calculated to be
0.107min-1, 0.126min-1, 0.194-1 and 0.281min-1 at a flowrate of 0.7LPH, 1.4LPH, 2.6LPH and
5.4LPH respectively. Since the rate constant is not constant with the change in flowrate it can
be concluded that the data obtained does not fit a Plug Flow Reactor.
References

1. O. Levinspiele, “Chemical Reaction Engineering” 2nd edition, John Wiley and Sons,
2007, 319-421
2. Wijayarathne UPL, Wasalathilake KC(2014) Aspen Plus Simulation of Saponification
of Ethyl Acetate in the presence of Sodium Hydroxide in a PFR, J Chem Eng. Process
Technol 5:205, doi:10.4172/2157-7048. 1000205.
Acknowledgement

I would like to thank all my group members namely Bodawar Narendra, Yash Gupta, Roneit
Punamiya, Ananta Bhatnagar and Pawas Pandey for their co-operation and contributions
while performing the experiment.

7
Appendix A5
Original Data Obtained

Table 3: Observation for flow rate of 0.7 LPH

time Volume of sample Sr. No, Volume of NaOH consumed

taken(ml)
25 10 1 17.3
10 2 17.3
10 3 17.1
Average 17.23

Table 4: Observation for flow rate of 1.4 LPH

time Volume of sample Sr. No. Volume of NaOH

taken(ml)
25 10 1 16.6
10 2 16.9
10 3 16.5
Average 16.66666667

Table 5: Observation for flow rate of 2.6 LPH

time Volume of sample Sr. No. Volume of NaOH

taken(ml)
25 10 1 16.2
10 2 16.2
10 3 16.4
Average 16.26666667

Table 6: Observation for flow rate of 5.4 LPH

time Volume of sample Sr. No. Volume of NaOH

taken(ml)
10 10 1 15.2
10 2 15.4
10 3 15.1
Average 15.23333333

8
 Detailed Calculations
Table 7: Detailed calculation for 0.7LPH

time Volume of Titration Volume of N of Initial N Unconverted Conversion τ(min k

sample No. NaOH HCl Of HCl NaOH )
taken(ml) consume
d
25 10 1 17.3 0.0432 0.0433 0.0001 99.6667 42.86 0.13
5 3
10 2 17.3 0.0432 0.0433 0.0001 99.6667 42.86 0.13
5 3
10 3 17.1 0.0427 0.0433 0.0006 97.6667 42.86 0.08
5 8
Average 17.23 0.0430 0.0433 0.0002 99 42.86 0.10
8 7

Table 8: Detailed calculation for 1.4LPH

time Volume Titration Volume of N of Initial N Unconverted Conversion τ(min) k

of No. NaOH HCl Of HCl NaOH
sample consume
taken(ml) d
25 10 1 16.6 0.0415 0.0433 0.0018 92.667 21.429 0.12
2
10 2 16.9 0.0422 0.0433 0.0011 95.667 21.429 0.14
5 6
10 3 16.5 0.0412 0.0433 0.0021 91.667 21.429 0.11
5 6
Average 16.67 0.0416 0.0433 0.0017 93.333 21.429 0.12
7 6

Table 9: Detailed calculation for 2.6LPH

tim Volume Titration Volume of N of HCl Initial Unconverted Conversion τ(min) k

e of samle No. NaOH N Of NaOH
taken(ml) consumed HCl

25 10 1 16.2 0.0405 0.043 0.0028 88.667 11.53 0.189

3 8
10 2 16.2 0.0405 0.043 0.0028 88.667 11.53 0.189
3 8
10 3 16.4 0.041 0.043 0.0023 90.667 11.53 0.206
3 8
Average 16.27 0.04066 0.043 0.0027 89.333 11.53 0.194
7 3 8

9
 Table 10: Detailed calculation for 5.4LPH

time Volume Titration Volume of N of HCl Initial Unconverted Conversion τ(min k

of samle No. NaOH N Of NaOH )
taken(ml) consumed HCl
25 10 1 15.2 0.038 0.043 0.0053 78.667 5.556 0.278
3
10 2 15.4 0.0385 0.043 0.0048 80.667 5.556 0.296
3
10 3 15.1 0.03775 0.043 0.0056 77.667 5.556 0.270
3
Average 15.233 0.03808 0.043 0.0053 79.000 5.556 0.281
3 3

Sample Calculation
Example for 0.7LPH
Average volume of 0.025 NaOH consumed during titration = 17.23ml
Normality of HCl = (0.025*17.23)/10 = 0.04308
Actual Normality of HCl = 0.065N
Initial Normality of HCl in the 30ml sample = (0.065*20)/30= 0.0433N
Converted HCl = Unconverted NaOH in 1st reaction = 0.04308-0.0433 = 0.0002N
Initial Concentration of NaOH = 0.025N
Conversion =1-(0.0002/0.025) = 0.99
Conversion = 99%
τ = V/v0 = 0.5*60/0.7 = 42.89 min
k= ln(1/(1-Xa))/τ = ln(1/0.01)/42.89 = 0.107 min-1

Error Calculation
Table 11: Error in readings at 0.7LPH

Titration Volume of Error %

No. NaOH
consumed
1 17.3 0.40626
8
2 17.3 0.40626
8
3 17.1 -0.7545

10
Table 12: Error in readings at 1.4LPH

Titration Volume of Error%

No. NaOH
consumed
1 16.6 -0.41992
2 16.9 1.37972
4
3 16.5 -1.0198

Table 13: Error in readings at 2.6LPH

Titration Volume of Error%

No. NaOH
consumed
1 16.2 -0.18484
2 16.2 -0.18484
3 16.4 1.04744
3

Table 14: Error in readings at 5.4LPH

Titration Volume of Error%

No. NaOH
consumed
1 15.2 -0.19698
2 15.4 1.11621
8
3 15.1 -0.85358

11