University of San Carlos

School of Engineering
Talamban, Cebu City, Philippines

CHE 512L
Chemical Engineering Laboratory 2

REACTION RATE KINETICS, TEMPERATURE EFFECTS AND

PERFORMANCE OF A PLUG FLOW REACTOR
(Tubular Flow Reactor)

A laboratory report submitted to

Engr. Ramir Jarabis

CHE 512L Instructor

by

John Christopher Torrefiel

August 7, 2017
1. Introduction
A tubular flow reactor is a pipe-shaped tank where a chemical reaction takes place with walls
coated with a catalyst and an inlet flow of pure reactant. It consists of a cylindrical pipe and is
normally operated at steady state (Fogler, 2004). The tubular flow reactor has an inlet flow
composed of the reactants. The reactant flows into the reactor and is then converted into the
product by a certain chemical reaction. The product flows out of the reactor through the outlet
flow. A simple illustration of a plug flow reactor is shown in Figure 1. The long tube and the
lack of stirring mechanism prevent complete mixing of the fluid in the tube. Hence the properties
of the flowing stream will vary from one point to another, namely in both radial and axial
directions (Levenspiel, 1999).

Feed Product

Figure 1. Simple schematic for a tubular flow reactor

In the ideal tubular reactor, commonly known as plug flow reactor, specific assumptions are
made about the extent of mixing:
1. No mixing in the axial direction, i.e., the direction of flow
2. Complete mixing in the radial direction
3. A uniform velocity profile across the radius.

The absence of longitudinal mixing is the special characteristics of this type of reactor. It is an
assumption at the opposite extreme from the complete mixing assumption of the ideal stirred
tank reactor.

The validity of the assumptions will depend on the geometry of the reactor and the flow
conditions. Deviations, which are frequent but not always important, are of two kinds:

1. Mixing in longitudinal direction due to vortices and turbulence

2. Incomplete mixing in radial direction in laminar flow conditions

This experiment focuses on the saponification of ethyl acetate using sodium hydroxide, given by
the reaction:
( ) ( ) ( ) ( )

Determination of the reaction order, n and kinetic rate constant, k for ethyl acetate NaOH
reaction system is usually done by reacting sodium hydroxide (A) with ethyl acetate (B) in a

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constant volume batch reactor. However, in this experiment a tubular flow reactor was used
instead of a constant volume batch reactor. A tubular flow reactor, or also known as plug flow
reactors (PFR) consist of a cylindrical tube with openings at both ends wherein the fluid flows
from one end to the other. Plug flow reactor is characterized by the flow pattern of the fluid
moving inside the reactor wherein it is similar to that of a plug.

In a plug flow reactor, the composition of the fluid varies along the direction of flow. The
performance equation for ideal plug flow reactors is developed by applying a general material
balance over a differential element of volume (dV) with the assumptions that: i. the reaction is
done at steady state operation, ii. no back mixing in the axial direction, iii. complete mixing in
the radial direction, and iv. a uniform velocity profile across the radius.
(1)
| | (2)
Where i is the component being monitored in the system

Since the ethyl acetate NaOH reaction is a liquid reaction, we can assume it to be
incompressible (meaning no expansion in happening) to make the density constant. For constant
density reaction systems, the performance equation of an ideal tubular flow reactor is the same as
with the constant volume batch reactor given by:
Ideal tubular flow reactor Constant volume batch reactor
(3)

As the reactant flows through the reactor, the concentration of A decreases and is being
consumed over time ( ). In terms of component A, the performance equation then
becomes:
(4)

The basis of calculation is most always the limiting reactant. The conversion of species A in a
reaction is equal to the number of moles of A reacted per mole A feed.

(5)

Conversion is an improved way of quantifying exactly how far has the reaction moved, or how
many moles of products are formed for every mole of A has consumed. Conversion X A is the
number of moles of A that have reacted per mole of A fed to the system. Thus, irreversible
reaction is the maximum values of conversion, X is that for complete conversion is X=1.0.
Meanwhile for reversible reactions where the maximum value of conversion, X is the
equilibrium conversion is X=Xe.

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2. Objectives of the Experiment
1. Determine the reaction order and the rate constant for the ethylacetate NaOH reaction
system using plug flow reactor data.
2. Determine the variation of conversion with respect to the residence time.
3. Verify the temperature dependence of the reaction rate constant.

3. Methodology
3.1. Methodological Framework
Objective 1: Determine the reaction order and the rate constant for the ethylacetate-NaOH
reaction system using plug flow reactor data.

Obtain data on the volume of reactor (Vr), volumetric flow rates of NaOH (v,A/NaOH)
and ethylacetate (v,B/EtOAc), concentrations of standardized HCl (CHCl) and NaOH
(CNaOH) used to titrate the effluent sample, and the volume of standardized NaOH used to
titrate the effluent sample to its endpoint (VNaOH).
Plot the NaOH concentrations (CA) versus residence time () for 0th, 1st, and 2nd order
reactions.

Vr
@ n with the highest
v,A R2

v,B
CA n
Tubular Flow Reactor Raw Data Processing
CHCl Experiment (Linear regression)
CA,0 k

VNaOH

Objective 2: Determine the variation of conversion with respect to the residence time.
Set constant:
Temperature, T = 30C
Initial Concentration of NaOH, CA,0 0.1 M
Initial concentration of EtOAc, CB,0 0.1 M

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 Set variable:
Volumetric flow rate of NaOH, V,A (10 250 mL/min)
Volumetric flow rate of ethyl acetate, V,B (10 250 mL/min
Convert the initial and final concentrations of NaOH (C NaOH) in terms of conversion
(XNaOH)

Vr

v,A XA
1) Experimental runs at
Plotting of XA vs.
v,B different V
2) Conversion

CA,0

CA

Objective 3: Verify the temperature dependence of the reaction rate constant.

Set constant:
Volumetric flow rate of NaOH, V,A
Volumetric flow rate of EtOAc, V,B
Initial concentration of NaOH, CA,0 0.1 M
Initial concentration of EtOAc, CB,0 0.1 M
Set variable:
Temperature, T = 30C, 40C, and 50C
Vr

v,A
k
Experimental runs
v,B Plotting of ln(k) vs. 1/T
at different T
T
CA,0

CB,0

5
3.2. Materials
In this experiment, sodium hydroxide (NaOH) and ethyl acetate (EtOAc) solutions were
used as feed to the tubular flow reactor. Hydrochloric acid was also used to determine the
concentration of NaOH in the effluent. Phenolphthalein was the indicator used for the
titration.

3.3. Equipment

Figure 2. Armfield Tubular flow reactor (a) front view, (b) rear view

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3.4. Procedures

3.4.1. Feed Preparation

For the feed to the tubular flow reactor, sodium hydroxide (NaOH) and ethyl acetate (EtOAc)
solutions were used. 18 L of 0.1 M NaOH and EtOAc solutions were prepared. About 74 g of
solid NaOH pellets were dissolved in a 1 L beaker and diluted with distilled water until 500 mL
of solution was obtained. The solution was transferred to a large container and diluted to 18 L
with measured amount of distilled water. To prepare the ethyl acetate solution, 176.70 mL of
99.5%wt ethyl acetate was measured in a graduated cylinder and diluted to 500 mL in a beaker.
The solution was then transferred to a large container and diluted to 18 L with measured amount
of distilled water.

3.4.2. Equipment Pre-startup

Before performing the experiment proper, pre-startup procedures were performed to the tubular
flow reactor. First, the main water supply valve was fully opened and the two power supply
circuit breakers were switched on. Then, water bath drain was closed and the main power switch
for the tubular flow reactor was turned on. The temperature was then set to 30C using the
temperature control dial. Lastly, the sampling beaker was removed and the feed pumps were
switched on and the flow rates were set to maximum to purge the air inside the reactor.

3.4.3. Experiment Proper

During the experiment proper, the feed flow meters were set to get the desired feed flow rates.
The actual temperature reading was recorded and samples of the effluent were collected for
titration. The same procedure were performed for the three other flow rate settings. The
temperature dial was adjusted to 40C. The actual temperature was recorded and effluent
samples were collected for titration. The same procedure was repeated for the 50C setting.

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3.4.4. Shutdown Operation

The feed pumps and stirrer were switched off and the storage compartments were drained and
rinsed with distilled water. The reactor was drained by filling the storage compartments with
distilled water and turning on the feed pumps to run the distilled water through the reactor. The
water bath was then drained and the power supply and the circuit breakers were switched off.

4. Results and Discussions

4.1 Reaction order and rate constant for ethylacetate NaOH reaction system
The data obtained in the experiment is processed using the integral method of analysis where a
particular rate equation is put to the test by integrating and comparing the predicted C A vs t curve
with the experimental CA vs t data. If the fit is not satisfactory, another rate equation is guessed
and tested until the best fit is obtained. Table 1 shows the degree of fit of the experimental data to
different reaction order models.
Table 1. Degree of fit of experimental data to different reaction order

Kinetic rate constant,

Order of reaction Linear equation R2
k
Zero Order reaction 0.0022 mol/L-min 0.8200

First Order reaction 0.0534 min-1 0.8441

Second Order
1.3088 L/mol-min 0.8628
reaction

Comparing the degree of fit, R2 we can see that a second order reaction best fit the experimental
data with an R2 of 0.8628. This is because the reaction is a special case for irreversible
bimolecular second order reaction wherein the reactants A and B are introduced in equal
concentrations resulting to a reaction of the form: 2 products. This results in a differential
d 2
equation of -r - k . Thus, the reaction then follows a second order reaction with a kinetic
dt
rate constant of 1.3088 L2/mol2-min.

4.2 Variations of conversion with respect to the residence time

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In objective 2, the change of the conversion A with residence time is being studied. Conversion
is defined as the fraction of any reactant converted to anything else or the fraction of the reactant
that reacted away. At constant density, conversion is the change in the concentration of A over
the concentration of A initially present. It is given by the equation:
(6)

A similar step is still done in objective 2. The tubular flow reactor is operated isothermally
( 30 ) and at different space time values (varying the flow rates). The resulting effluent
concentration was also calculated for each space time values using acid base titration. Lastly,
conversion was calculated using Equation 13 for each space time values. This is shown in Table
2.

Table 2. Coversion of A at different residence time

Theo
vNaOH,in vtotal,in CA,in CA,out
vEtOAc,in XA (min)
(cm3/min) (cm3/min) (mol/L) (mol/L)
(cm3/min)
160.0 165.4 325.44 0.0508 0.0494 0.03 2.42
120.0 124.1 244.08 0.0508 0.0420 0.17 3.22
80.0 82.7 162.72 0.0508 0.0347 0.32 4.84
40.0 41.4 81.36 0.0508 0.0316 0.38 9.67

From table 3, we can see that the highest conversion, XA = 0.38, was achieved at a residence
time of 9.67 min while the lowest conversion, XA = 0.03, at a residence time of 2.42 min. This
tells us that conversion is at greatest when more time is allotted for reaction. Allowing more
time for the reaction increases the chance for collision between reacting molecules (Smith,
1982). Greater chance of collision also means greater amount of conversion to products.

4.3 Temperature dependence of rate constant

Reaction rate constants at different temperatures were obtained and tabulated in Table 3 and
values of ln k vs. 1/T were plotted in Figure 3.

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Table 3. Rate constant at different temperatures

Temperature
T k (L/mol-
Actual Actual 1/T (K-1) ln k
Setting min)
(C) (K)
1 32.0 305.15 2.5328 0.00328 0.9293
2 41.0 314.15 5.3054 0.00318 1.6687
3 51.0 324.15 6.3844 0.00308 1.8539

2.0000

1.8000

1.6000
ln k (L/mol-min)

1.4000
y = -4790.7x + 16.727
R = 0.8849
1.2000

1.0000

0.8000
0.00305 0.00310 0.00315 0.00320 0.00325 0.00330
1/T (K)

Figure 3. Arrhenius Plot

From the Figure 5, it can be seen that the rate constant increases with increasing temperature. An
R2 of 8849 would mean that the temperature dependency of the reaction rate agrees with the
Arrhenius Law. This is due to the fact that at higher temperature molecules tend to move at a
higher rate (greater kinetic energy). At a higher kinetic energy, the frequency of collisions
between reacting molecules also increases.

From the plot, the activation energy and frequency factor can be estimated. The slope of the
fitted curve would also tell us an estimate of the activation energy. Larger slopes have larger
activation energies while lower slopes have lower activation energies. Activation energy is a
measure of the required energy needed to be overcome in order for a reaction to proceed.
Reactions with high activation energies are temperature sensitive. Another data estimated also is

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the frequency factor or pre-exponential factor. Frequency factor is independent of temperature
and it is a measure of the frequency of collision between individual reactant molecules.
Table 4 Activation energy and pre-exponential factor of the reaction
Slope, - E/R 4790.7
Activation Energy E, kJ mol-1 39.830
Pre-exponential factor A, 10-7 L mol-1 min-1 1.84

The activation energy is obtained from the slope of the line while the frequency factor is
obtained from the y-intercept of the line.

5. Conclusions

From this experiment, we can see that reaction between two reactants (sodium hydroxide and
ethyl acetate) that is fed inside a reactor with equal flowrates and initial concentration follows a
second-order irreversible reaction with an R2 = 0.8628.

Also, it can be concluded that conversion increases in a nonlinear manner with the space time
inside the reactor. This is because of the longer time allotted for the reaction to take place.
Longer time would mean there is a higher possibility of collision between individual reacting
molecules flowing through the plug flow reactor. If the residence time is allowed to increase, the
conversion is expected to get higher until all of the reactants are converted to products.

Also, we can conclude from the experiment that the reaction rate is a function of two
components: i) composition and ii) temperature. Varying the composition of your fed reactants
can affect the rate of the reaction. Also, through the Arrhenius plot we can see that increasing the
temperature of the reaction system also increases the rate of reaction exponentially. Increasing
temperature would increase the kinetic energy of the reacting molecules allowing them to collide
with each other more frequently.

Hence, we can say that the rate law is a function of composition and temperature. The
temperature dependent term in the rate law is the reaction rate describe by the Arrhenius Law.
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Also, the pre-exponential factor is independent of temperature and it is a measure of how
frequently molecules collide with each other

References
Fogler, S. (2004). Elements of Chemical Reaction Engineering (Third). Prentice Hall Press.

Levenspiel, O. (1999). Chemical Reaction Engineering (Third). New York: John Wiley & Sons,

Inc.

Smith, J. M. (1982). Chemical Engineering Kinetics (Third). McGraw - Hill.

ANNEX

Data Processing & Analysis Report

Table A5 Effluent concentrations at different space time values

Average
Temper Theo Average CNaOH, Residence
total
ature (mol/L (mol/L NaOH effluent ime,
(cm3/min) (cm3/min)
(C) (cm3/min) ) ) titrated (min)
(mol/L)
30 160.0 165.4 325.44 0.0508 0.0525 3.58 0.0494 2.42
30 120.0 124.1 244.08 0.0508 0.0525 4.30 0.0420 3.22
30 80.0 82.7 162.72 0.0508 0.0525 5.00 0.0347 4.84
30 40.0 41.4 81.36 0.0508 0.0525 5.30 0.0316 9.67

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 0.0250
y = 0.0022x
R = 0.82
0.0200

CA, in - CA (mol/L)
0.0150

0.0100

0.0050

0.0000
0.00 2.00 4.00 6.00 8.00 10.00
(min)

Figure A4 Linearized plot of the concentration data versus space time for zero order

0.6000
y = 0.0534x
R = 0.8441
0.5000

0.4000
ln (CA,in/CA)

0.3000

0.2000

0.1000

0.0000
0.00 2.00 4.00 6.00 8.00 10.00
(min)

Figure A5 Linearized plot of the concentration data versus space time for first order

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 14.0000
y = 1.3088x
12.0000 R = 0.8628

(1/CA,in)-(1/CA) (L/mol)
10.0000

8.0000

6.0000

4.0000

2.0000

0.0000
0.00 2.00 4.00 6.00 8.00 10.00
(min)

Figure A6 Linearized plot of the concentration data versus space time for second order

0.45
0.40 R = 0.7695
0.35
0.30
0.25
XA

0.20
0.15
0.10
0.05
0.00
0.00 2.00 4.00 6.00 8.00 10.00
(min)

Figure A7 Conversion of A versus time

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Annex 2.1 Calculation of the NaOH effluent concentration and residence time at varying reactant flow rates
Temperature Volume of NaOH used
(C) Trial 1 Trial 2 Average Average Residence
Flow CA,in CB,in
Trial Trial NaOH CA Time,
Setting (cm3/min) (cm3/min) (cm3/min) (mol/L) (mol/L)
1 2 dispensed (mol/L) (min)
Target Actual Initial Final Initial Final

1 30.0 32.0 160.0 165.4 325.44 0.0508 0.0525 0.00 3.70 3.70 7.15 3.70 3.45 3.58 0.0494 2.42
2 30.0 32.0 120.0 124.1 244.08 0.0508 0.0525 0.00 4.20 4.20 8.60 4.20 4.40 4.30 0.0420 3.22
3 30.0 32.0 80.0 82.7 162.72 0.0508 0.0525 8.60 13.50 13.50 18.60 4.90 5.10 5.00 0.0347 4.84
4 30.0 32.0 40.0 41.4 81.36 0.0508 0.0525 0.10 5.60 5.60 10.70 5.50 5.10 5.30 0.0316 9.67

Annex 2.2 Concentration data versus residence time for different reaction order
n=0 n=1 n=2
CA ln(CA) 1/CA
0.00 0.0000 0.0000 0.0000

2.42 0.0014 0.0271 0.5406

3.22 0.0088 0.1914 4.1520

4.84 0.0161 0.3806 9.1177

9.67 0.0192 0.4742 11.9414

Annex 2.3 Calculated conversion at a particular residence time

Flow CA,in CA XA
 Setting (mol/L) (mol/L) (min)

1 0.0508 0.0494 0.03 2.42

2 0.0508 0.0420 0.17 3.22
3 0.0508 0.0347 0.32 4.84
4 0.0508 0.0316 0.38 9.67

Annex 2.4 Determination of Activation Energy and Frequency Factor

Temperature
T
k (L/mol-min) 1/T (K) ln k
Setting Actual Actual
(C) (K)

1 32.0 305.15 2.5328 0.00328 0.9293

2 41.0 314.15 5.3054 0.00318 1.6687
3 51.0 324.15 6.3844 0.00308 1.8539

slope (m) (E/R) 4790.7

Activation Energy E (KJ/mol) 39.830
y-intercept (b) ln A 16.727
Frequency Factor A 1.8384E+07

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