Instituto Tecnológico y de Estudios Superiores de Monterrey

Design of Chemical Reactors

IQ2011B.201

Lab Report: PFR

Team 6:

Melissa Alvarez Reyes A01282581

Fabiola Danae Rodríguez Canales A01284375

Raúl Barragán Godoy A01282445

Jimena Sofía Rodríguez Martínez A00831534

Jocelyn Garcia Gonzalez A01368290

Profesores:

Dr. Yatziri Rodriguez

11/10/2022

Campus Monterrey
Objective:
To determine the experimental conversion of ethyl acetate saponification in a plug flow
reactor.
● To verify the kinetic expression for saponification of ethyl acetate with sodium
hydroxide as a second-order irreversible reaction based on experimental data.
● To determine the kinetic constant of the rate of the homogeneous reaction in the liquid
phase of saponification of ethyl acetate with sodium hydroxide.
● To determine the experimental conversion of the reaction.
● To interpret and explain the procedure for the calculation of the concentration using
the conductivity of the reactive mixture. Include the sample calculation in the
report.
● To check and verify the validity of the results by comparing them with the values
reported in the literature.

Introduction:
In a chemical reaction the reactants are transformed into products at a certain rate.
Chemical kinetics is the study of the rate of a chemical reaction, that is, the change in
concentration of a substance with respect to time. The kinetic equation is based on the
mechanism of a reaction and is obtained based on experiments; it also presents a
reaction rate constant.

The tubular reactor normally operates at steady state. These types of reactors are most
often used for gas-phase reactions. In the tubular reactor, reagents are consumed
continuously as they flow throughout the reactor. When modeling the reactor, it is
assumed that the concentration varies continuously throughout the equipment. Therefore, the
reaction rate, which is a function of concentration, also varies throughout the reactor. For
practical purposes it shall be considered as a system in which the flow field is
represented by a model corresponding to a plug flow profile (uniform velocity as in
turbulent flow, see Figure 1). In general, in the plug flow reactor, there is no radial variation
in velocity, concentration, temperature or reaction rate.

Figure 1. Plug Flow Reactor.

The general mole balance equation is given by equation 1:

𝑉 𝑑𝑁𝑗
𝐹𝑗𝑜 − 𝐹𝑗𝑖 ± ∫ 𝑟𝑗𝑑𝑉 = 𝑑𝑡
(1)

The design equation for a plug flow reactor is as follows (A is a reagent):

𝑋
𝑑𝑋
𝑉 = 𝐹𝐴0 ∫ −𝑟𝐴
(2)
0

Materials and substances:

- 1 Stopwatch - 2-1 L volumetric - 1 graduated tube

- 1 Suction flasks of 50 mL
- 1 Funnel - 1 100 mL beaker - 1 graduated tube
- 1 Ribbed spatula - 2 1 L beakers of 100 mL
- 1 Watch glass - 1 Pipette

Apparatus:

Figure 2. PFR (Armfield Brand). Figure 3. Flow diagram of the PRF.

Experimental methodology:

1. Prepare 5 L of solution of each reagent (NaOH and Ethyl Acetate) with a

concentration of 0.05 mol/L.
2. Choose 2 reagent feed flows (Between 50 and 100 ml/min are recommended), and the
3 temperatures used in batch reactor practice (Ask the technician/instructor for
help with the operation of the water bath). In total there will be 6 runs.
*NOTE: Both pumps; Ethyl Acetate and NaOH, must deliver the same flow in a run.
3. The distilled water initially contained in the feed tanks will be used to adjust
the operating flows. It is recommended to follow these steps:
a. Turn on the pump by pressing the button on the front (lower right).
b. Adjust the revolutions of the pump in such a way that they deliver the selected
flow (use the graduated tube and stopwatch).
c. Write down the rpm for each selected flow.
4. Purge the distilled water from the feed tanks by opening the discharge valves.
5. Pour the prepared solutions into the corresponding feed tanks, making sure the
discharge valves are closed).
6. Turn on the pumps at the same time, and immediately start the chronometer.
7. Record the conductivity every minute until three constant values are obtained.
8. Continue with the other runs. 2 flows should be studied at 3 different
temperatures (preferably use the same as the Batch Reactor).
9. Clean the system with distilled water and turn off the pumps.
10. Wash and dry the material to deliver it to the warehouse.

Calculation methodology:
After obtaining the data from the three runs of the experiment, these values should be
interpreted in order to know the kinetic expression.

Calculation of the final concentration of NaOH

The electrical conductivity is reported in μS/cm and these values are the conductivity of the
mixture, which is the sum of each component from the reaction of production of sodium
acetate (NaAc) from ethyl acetate:

CH3COOC2H5 + NaOH → CH3COONa + C2H5OH

The conductivity of the mixture is represented by the next equation, taking into account that
the conductivities of ethyl acetate and ethanol are negligible, so the conductivity of the
reaction mixture is a function of the concentration of NaAc and NaOH.

𝑆𝑚𝑖𝑥 = 𝑆𝑁𝑎𝑂𝐻 + 𝑆𝑁𝑎𝐴𝑐 (3)

The conductivity of an electrolytic material is proportional to its molar concentration:

𝑆𝑖 = 𝑚𝑖𝐶𝑖 (4)

This equation can be used for the sodium hydroxide and the sodium acetate, so we can
determine the conductivity of the sodium hydroxide, first obtaining the proportionality
constant, with the next equations:

𝑆𝑁𝑎𝑂𝐻 𝑆𝑁𝑎𝐴𝑐
𝑚𝑁𝑎𝑂𝐻 = 𝐶𝑁𝑎𝑂𝐻
(5) 𝑚𝑁𝑎𝐴𝑐 = 𝐶𝑁𝑎𝐴𝑐
(6)

Knowing the constants for both components and the concentration of the sodium acetate at
the temperature of the experiment (with the Figure 4), we are able to determine the
concentration of sodium hydroxide with the netx equation:

𝑆𝑚𝑖𝑥−𝐶𝐴𝑚𝑁𝑎𝐴𝑐
𝐶𝑁𝑎𝑂𝐻 = 𝑚𝑁𝑎𝑂𝐻−𝑚𝑁𝑎𝐴𝑐
(7)

Figure 4. Sodium acetate conductivity as a function of temperature.

The dimensions of the reactor were provided by the laboratory assistant and can be observed
in table 1.
Table 1. Dimensions of the reactor.

Volume (L) 0.41

Length (m) 20.09

Inner diameter (mm) 5

Number of turns 43

Calculation for the specific reaction rate

The PFR has an specific design equation, which allows us to determine the volume of the
reactor knowing the initial molar feed, the conversion and the rate of reaction:
𝑋 𝑑𝑋
𝑉 = 𝐹𝐴0 ∫ 𝐴
−𝑟𝐴
(8)
0

The rate of reaction is given by the next equation:

α β
− 𝑟𝐴 = 𝑘𝐶𝐴 𝐶𝐵 (9)

The initial concentration of the sodium hydroxide and the ethyl acetate is the same (CA=CB),
as well as the volumetric flow, so it is possible for us to couple both concentration as only
one (CACB = CACA=CA2) and we get the next equation:

2
− 𝑟𝐴 = 𝑘𝐶𝐴 (10)

The concentration can also be expressed in terms of conversion as the equation:

𝐶𝐴 = 𝐶𝐴0(1 − 𝑋) (11)

The conversion can be calculated using the equation 12, knowing the initial and final values
of the sodium hydroxide:
𝐶𝐴0−𝐶𝐴
𝑋= 𝐶𝐴0
(12)
Replacing equation 11 in the equation for the rate of reaction (10), we obtain:

2 2
− 𝑟𝐴 = 𝑘𝐶𝐴0 (1 − 𝑋) (13)

Now the rate of reaction is in terms of the conversion, allowing us to replace it in the design
equation (8), and after some rearranging of the terms of the equation we get:

𝑋 𝑑𝑋𝐴 𝐹𝐴0 𝑋 𝑑𝑋𝐴 υ0𝐶𝐴0 𝑋 𝑑𝑋𝐴 υ0 𝑋 𝑑𝑋𝐴

𝑉 = 𝐹𝐴0 ∫ 2 2 = 2 ∫ 2 = 2 ∫ 2 = ∫ 2 (14)
0 𝑘𝐶𝐴0 (1−𝑋) 𝑘𝐶𝐴0 0 (1−𝑋) 𝑘𝐶𝐴0 0 (1−𝑋) 𝑘𝐶𝐴0 0 (1−𝑋)

In this lab practice we already know the volume of the reactor, but we don’t know the value
of the kinetic constant of the reaction, so we must isolate the equation to obtain the kinetic
constant (k). The integral is solved with the next formula:

𝑋
1 𝑋
∫ 𝑑𝑥 = ⎡ 1−𝑋 ⎤ (15)
0 (1−𝑋)
2
⎣ ⎦

The kinetic constant of the reaction is solved with the next equation, since we know the
values of the volumetric flow, the volume of the PFR, the initial concentration of the Sodium
hydroxide and the conversion:

υ0 𝑋
𝑘= ⎡ 1−𝑋 ⎤ (16)
𝑉𝐶𝐴0 ⎣ ⎦

Calculation of the specific rate of reaction equation:

Knowing the value of the kinetic constant at each run of the experiment we can obtain an
equation that will predict the value of this constant depending on the temperature of the
reactor, this equation is known as the Arrheius equation.

−𝐸/𝑅𝑇
𝑘𝐴(𝑇) = 𝐴𝑒 (17)

This expression can be calculated since we know the values of the temperature and kinetic
constant at each run of the experiment, and these values are the variables of the Arrhenius
equation. We can graph the values obtained of the specific rate reaction of each temperature,
first making it linear by plotting the natural logarithm of the specific rate of reaction and the
inverse of the temperature (ln(k) vs. 1/T) and obtaining a linear equation in the form y=mx+b
as shown in the figure below.

Figure 5. Plot to obtain the Arrhenius equation.

In the figure 5 we can see that the value of ‘y’ is the natural logarithm of the kinetic constant,
the ‘x’ value is the inverse of the temperature and the slope (‘m’ value) is the negative value
of the activation energy divided by the ‘R’ value for ideal gasses. After plotting these values
we can finally get the linear expression, and know the Arrheius equation.

Results:
After three runs of the experiment with different temperatures, changing the volumetric flow
for three different values at each temperature, we obtained the following results:

Table 2. Operating conditions for the PFR.

Run Temperature (ºC) Volumetric flow EtAc Volumetric flow NaOH

(L/min) (L/min)

1 24.1 0.05 0.05

2 0.075 0.075

3 0.1 0.1

4 35 0.05 0.05

5 0.075 0.075
 6 0.1 0.1

7 45 0.05 0.05

8 0.075 0.075

9 0.1 0.1

Table 3. Conductivity of each run.

Run 1 2 3 4 5 6 7 8 9

𝑉˙total 0.1 0.15 0.2 0.1 0.15 0.2 0.1 0.15 0.2
(L/min)

Time Conductivity (μS/cm)

(min)

0 0.08 4.33 4.57 2.9 4.5 4.77 3.15 4.52 4.83

1 4.37 4.45 4.63 3.09 4.61 4.84 3.16 4.67 4.91

2 4.37 4.58 4.49 3.08 4.78 4.82 3.15 4.85 4.93

3 4.35 4.59 4.28 3.06 4.78 4.45 3.13 4.84 4.48

4 4.34 4.57 4.27 3.65 4.77 4.45 3.64 4.83 4.47

5 4.33 4.57 4.26 4.51 4.77 4.45 4.61 4.83 4.47

6 4.51 4.58

7 4.53

8 4.52

Table 4. Conductivity constants for each temperature.

Temperature CNaOH,0 SNaOH SNaAC mNaOH mNaAc

(ºC) (mol/L) (μS/cm) (μS/cm)

24.1 0.025 11.03 3.59071 220.6 71.8142

35 0.025 11.9 4.0496 238 80.992

45 0.025 12.77 4.4706 255.4 89.412

Table 5. Conversion of each run.

Run CNaOH,final (mol/L) XNaOH

1 0.01704 0.31858

2 0.01865 0.25406

3 0.01657 0.33740

4 0.01583 0.36686

5 0.01748 0.30062

6 0.01545 0.38215

7 0.01376 0.44943

8 0.01563 0.37473

9 0.01346 0.46148

Table 6. Global Volumetric and Specific Rate.

Run Temperature (ºC) Total volumetric Specific rate

flow constant (k)
(L/min) (dm3/min·mol)

1 24.1 0.1 4.561

2 0.15 4.984

3 0.2 9.936

4 35 0.1 5.653

5 0.15 6.290

6 0.2 12.068

7 45 0.1 7.964

8 0.15 8.770

9 0.2 16.721
 Figure 6. graph of ln(k) vs 1/T.

Arrhenius Law: k=23,271.9e–295.79/RT

Discussion of results:
Analyzing the results obtained after the calculations, it can be concluded that the run with the
highest conversion was run 9 with a temperature of 45 ºC, a volumetric flow of 0.2 L/min.
The conversion obtained was 46% with a final concentration of NaOH of 0.013 mol/L and a
specific rate constant of 16.72 dm3/mol*min. Run 7, which was also at 45 °C but with a
volumetric flow of 0.1 L/min, had very similar results to run 9, and run 8 also behaved quite
well, meaning that carrying out this process at 45 °C may be a very good way to approach a
higher conversion. The other parameter also seemed to work better the higher it was, since, as
we can observe in the results, when the volumetric flow was increased, the conversion
became higher in every experiment executed.

Comparing the results with “A Comparative Study of Saponification Reaction in a PFR and
CSTR” we can conclude that the results obtained are valid since the graphs made matched the
behaviors presented in the graphs of the report and we can see how they follow the same
tendencies. It is also mentioned that the highest concentration was obtained at the highest
temperature in which the experiment was carried out while working under constant operating
conditions which was the same in the experiment presented in this report.
In the document “Aspen Plus Simulation of Saponification of Ethyl Acetate in the Presence
of Sodium Hydroxide in a Plug Flow Reactor”, it’s mentioned that the rate of reaction
increases as the reactor temperature does, this behavior can also be observed in the results of
the experiment presented in this report as the minimum specific rate constant was obtained at
the lowest temperature of 24.1 ºC while the highest specific rate constant was obtained at the
highest temperature of 45 ºC.

Finally, in the presentation “Saponification of Ethyl Acetate by Sodium Hydroxide in a Plug

Flow Reactor” it shows a kinetic rate constant of 0.24 L/mol·min was obtained and when the
units of time are changed form seconds to minutes a value of 14.4 L/mol·min is obtained
which is really close to the kinetic rate constant presented in this report which is 16
L/mol·min. The results may vary when taking the data because the precision may not be the
best, some values are rounded up and the values and calculations were taken and made
manually.

Conclusion:
Within this report of the second PFR reactor, the results of the three runs taken in the
laboratory were analyzed. These were set at different flow and operating temperatures
conditions which help to obtain the conversion and reaction rate constant. The main objective
was to obtain the kinetic parameters and the conversion of the saponification of ethyl acetate
with sodium hydroxide as a second-order irreversible reaction based on experimental data
and analyze the results by comparing them to the results reported in the literature. It was
shown that the results presented in this report are very similar to the ones reported in
scientific literature which may prove that the experiment was carried out correctly.
Bibliography:

Danish M. and Al Mesfer M. K. (2015). A Comparative Study of Saponification Reaction in a

PFR and CSTR. Retrieved October 11, 2022, from:
http://www.isca.in/rjcs/Archives/v5/i11/3.ISCA-RJCS-2015-137.pdf

Kato, L., Togioka, S. & Sugie, L. (2005). Saponification of Ethyl Acetate by Sodium
Hydroxide in a Plug Flow Reactor. Retrieved October 11, 2022, from:
https://www.slideserve.com/johana/saponification-of-ethyl-acetate-by-sodium-hydroxide-in-a
-plug-flow-reactor

Wijayarathne UPL and Wasalathilake KC. (2014). Aspen Plus Simulation of Saponification of
Ethyl Acetate in the Presence of Sodium Hydroxide in a Plug Flow Reactor. Retrieved
October 11, 2022, from:
https://www.longdom.org/open-access/aspen-plus-simulation-of-saponification-of-ethyl-aceta
te-2157-7048.1000205.pdf
Anexes:
Excel file:
https://tecmx-my.sharepoint.com/:x:/g/personal/a01284375_tec_mx/EYawUgQ1f5dKshyBch
JcGsQB6cSOqzRMdcigied9IHlgmQ?e=KBr0wZ