Abstract

In this report, the expression of reaction rate, the effects of temperature and flow rates,
reaction order, and activation energy for a chemical reaction was investigated by using an
experimental setup in which saponification reaction was carried out by using the properties of
Continuous Stirred Tank Reactors (CSTR). Continuous stirred tank reactors are typically
operated at steady state and are assumed to provide perfect mixing; thus, there is no time or
position dependence on temperature, concentration, or reaction rate inside the CSTR. That is,
every variable stays the same at every point of the reactor, and in this case, because the
temperature and concentration are the same throughout the reaction vessel, they are also the
same at the exit/outlet. The used CSTR vessel has the following characterisation: a vessel
diameter of 0.153m, maximum vessel depth of 0.108m, maximum volume of 2.0L, minimum
vessel depth of 0.054m, and a minimum operating volume of 1.0L [1]. The used volume in
this experiment is 1.6L. The effect of temperature and flow rate on the reaction rate
expression developed for the saponification reaction carried and examined using CSTR using
0.1 N sodium hydroxide and 0.1 N ethyl acetate as reactants. Two experimental sets were
performed. For the first set, the temperature was kept constant (20°C) against three different
reactant flow rates (20, 40, and 60 cm3/min) to obtain an experimental that could explain the
effect how flow rate affects the reaction. For the second set, the flow rate was kept constant
(60 cm3/min), and the temperature was changed to obtain experimental data for three
different temperatures (25°C, 30°C, and 46°C); in this way, the effect of the temperature and
activation energy could be determined. Reverse titrations using 0.1 HCl and 0.1 NaOH were
performed to ensure the system reached steady state. All experimental sets were performed
under atmospheric conditions. The reaction order was found to be 1.977 which can be
accepted to be 2, meaning that our reaction is second order. Accepting the reaction to be
second order, the activation reaction was found to be 82207.29 J/mol.

I
Table of Contents

1. Theory................................................................................................................................1
1.1. Saponification..............................................................................................................1
1.2. Reactors.......................................................................................................................1
1.2.1 Reactor.................................................................................................................1
1.2.2 Continuous Flow Reactors...................................................................................3
1.2.3 Tubular Reactor....................................................................................................4
1.3. Material Balance İn Second Order Reactions.............................................................4
2. Procedure...........................................................................................................................6
2.1. Preliminary Process.....................................................................................................6
2.2. The Procedure of Experiment for Set 1.......................................................................6
2.3. The Procedure of Experiment for Set 2.......................................................................7
3. Experimental Data............................................................................................................7
4. Calculations.......................................................................................................................8
4.1. Set 1.............................................................................................................................8
4.2. Set 2...........................................................................................................................12
5. Discussion and Results....................................................................................................17
6. Conclusion.......................................................................................................................21
7. Recommendations...........................................................................................................21
References...............................................................................................................................22

II
List of Figures

Figure 1 –Simple Homogeneous Batch Reactor [2]..................................................................1

Figure 2 – Reaction Order Graph from Set 1 Data..................................................................11
Figure 3 – Activation Energy Graph for n=1.977....................................................................15
Figure 4 – Activation Energy Graph for n=2...........................................................................16

III
List of Tables

Table 1 – Experimental Data Obtained from Set 1 at Constant Temperature of 25°C..............7

Table 2 – Experimental Data Obtained from Set 2 at Volumetric Flow Rate of 60 cm3/min....7
Table 3 – Set 1 Results.............................................................................................................17
Table 4 – Set 2 Results.............................................................................................................17
Table 5 – Set 2 Results Continued for Reaction Order Accepted as 1.97746.........................18
Table 6 – Set 2 Results Continued for Reaction Order Accepted as 2....................................18

IV
 1. Theory

1.1. Saponification

The hydrolysis of a fat or oil in alkaline conditions produces soap for cleaning purposes, and
the reaction which occurs in alkaline conditions is called saponification. Saponification is a
process in which esters in fats are hydrolysed with sodium or potassium hydroxide (NaOH or
KOH) to produce a carboxylate anion which can act as a surfactant, i.e. soap. Although the
end product is not soap, hydrolysis of ethyl acetate by sodium hydroxide to produce sodium
acetate and ethanol is a saponification reaction.

where k indicates the reaction rate constant.

The specific rate constant (k) is the proportionality constant that relates the reaction rate to
the concentrations of the reactants and rate of reactions for a given chemical reaction is can
be defined as how fast or slow the reactions take place.

1.2. Reactors

There are several types of reactors used in chemical or biochemical

industries. Some of these are batch reactors, continuous stirred tank
reactors, and tubular reactors.

1.2.1 Reactor
Batch reactors are used for small-scale operation, to test new
processes that are not fully developed, for the manufacture of
expensive products, and for processes that are difficult to convert to
continuous operations. Batch reactors have the advantage of high
Figure 1 –- Simple Homogeneous
conversion that can be achieved by leaving the reactant in the reactor Batch Reactor [2]
for a long time. However, they also have the disadvantages of high
labour costs per batch, the variability of products from batch to batch, and the difficulty of
large-scale production [2].

1
A batch reactor has neither inflow nor outflow of reactants nor products while the reaction is
being carried out. The resulting general mole balance of species j is:

If we assume the reaction mixture is perfectly mixed and there is no variation in the rate of
reaction throughout the reactor volume, we can take r j out of the integral and integrate the
equation. The mole balance will be:

When we write material balance, assuming that a saponification reaction takes place in a
batch reactor and that the reaction is second order like our reaction in the experiment:

2
1.2.2 Continuous Flow Reactors
Continuous flow reactors normally operated at a steady state and are assumed to be perfectly
mixed; consequently, there is no time dependence or position dependence on the temperature,
concentration, or reaction rate inside the CSTR. Continuous flow reactors are modelled so
that the temperature and concentration at the output stream are the same as those inside the
reactor. That is, every variable is the same at every point of the reactor, and in this case, since
the temperature and concentration are the same everywhere in the reaction vessel, they are
the same at the exit point as they are elsewhere in the vessel. In systems where mixing is
highly nonideal, the well-mixed model is inadequate, and we must resort to other modelling
techniques, such as residence time distributions, to obtain meaningful results [2].

For the general mole balance equation:

Since CSTR operated at steady state:

And we know that

By putting this equation in our equation, the equation becomes:

The resulted equation is known as the design equation for a CSTR reactor.

The molar flow rate Fj is just the product of the concentration of species j and the volumetric
flow rate Q ;

3
Space time, τ, is the time required to process one reactor volume of feed measured at specific
reaction conditions.

1.2.3 Tubular Reactor

To mix different chemical ingredients, you need a continuous flow tubular reactor. The
tubular reactor's constant consumption of reactants causes continuous down-flow through the
length of the structure. This leads to consistent reaction rates across all but zero-order
reactions. To represent this scientifically, we assume that the reactor's axial concentration
changes continuously throughout its length. In plug-flow reactors, material processing occurs
in a streamlined manner. This method of material handling is represented in the data
presented here by plug-flow systems. Like turbulent flow, no reaction rate variation takes
place [3].

1.3. Material Balance İn Second Order Reactions

A+B Product

If Ca0=Cb0;

4
 If Ca0≠Cb0;

5
 2. Procedure

2.1. Preliminary Process

The molarity of the NaOH solution to be titrated to obtain accurate test results shall be
determined.

 The NaOH solution, whose molarity will be determined, is taken into a 50 ml

burette. In the general experimental procedure, the solution whose molarity will be
determined is taken into an erlenmeyer flask, but since NaOH solution will be
used for titration in the later process, it is directly taken into the burette to
facilitate the process.
 10 ml of 0.1 M HCl solution is taken into an erlenmeyer flask and titrated with
NaOH solution.
 The titration results are noted.

2.2. The Procedure of Experiment for Set 1

 NaOH and ethyl acetate solutions are filled into two separate compartments in the
CSTR. In these compartments, the solutions do not mix with each other and are
connected to the main part of the reactor by tubes. Through these tubes, the
compounds are fed into the reactor at the desired flow rate.
 The reactor is opened and the impeller inside the reactor is started to rotate. The
keys for solution feeds are also turned on. Desired flow rates are adjusted with
flow control knobs. The solutions begin to fill the main part of the reactor.
 The temperature is set to 25°C.
 0.1 M 10 mL HCl solution is added to 7-8 erlenmeyer flasks.
 After the reactor is full, the solution in the reactor is taken from the drainage outlet
at the bottom of the reactor where 10 mL sample is transferred to one of the
Erlenmeyer flasks containing 10 mL of 0.1 M HCl solution – the same flasks
mentioned in the previous step.
 Phenolphthalein is added to the erlenmeyer flask containing the two solutions and
back titrated with the NaOH solution in the burette.
 A sample solution is taken from the reactor every 3 minutes and the titration
procedure written above is repeated until steady state is reached.
 The amount of NaOH consumed in the titrations is noted.

6
  When the noted amount of NaOH is fixed at a value, it is understood that the
solution has become stable (steady state has been reached) and the next part of the
experiment is started.
 This experimental procedure is repeated for three different flow rates, 20 cm 3/min,
40 cm3/min, and 60 cm3/min in our case for both reactant solutions. With this
process, the effect of getting steady-state conditions on the flow rate is examined.
The temperature is kept constant at 25°C throughout the process.

2.3. The Procedure of Experiment for Set 2

 The same experimental procedure is repeated with a slight difference. For this set,
a constant flow rate of 60 cm3/min for both solutions throughout the process is set
while recording the changes in the reaction at three different temperatures.
Temperatures of 25°C, 30°C, and 46°C were selected for this set. With this
process, the effect of getting steady-state conditions on the temperature is
examined. Moreover, the activation energy of the reaction is calculated.


3. Experimental Data

The steady state titration values for both experimental sets can be found in the table below.
These data are the data that we will use for the calculation section of this report.

Table 1 – Experimental Data Obtained from Set 1 at Constant Temperature of 25°C

Volumetric Flow Volumetric Flow Amount of 0.1 M

rate of 0.1 M NaOH rate of 0.1 M ethyl NaOH added for
in cm3/min acetate in cm3/min back titration in mL
20 20 8.8
40 40 8.4
60 60 8

Table 2 – Experimental Data Obtained from Set 2 at Volumetric Flow Rate of 60 cm 3/min

Amount of 0.1 M
Temperature in °C NaOH added for
back titration in mL
25 8
30 8.6
46 9.3

7
 4. Calculations

For Component A;

At steady state condition:

where CA0 is initial concentration and initial volumetric flow rate.

; τ →

We know CA0 = 0.1 N = 0.1 M where CA can be found by titration.

4.1. Set 1

Volume of our reactor is 1.6 L.

 Flow rate: 20 cm3/ min

τ = constant minutes

8
  Flow rate: 40 cm3/ min

τ = constant minutes

 Flow rate: 60 cm3/ min

τ = constant minutes

Now, let’s find CAf for each flow rate. We need the steady state titration value.

For reverse titration, the amount of added NaOH for the steady state samples are

 For τ = 80 min  8.8 mL, 0.1 M NaOH

 For τ = 40 min  8.4 mL, 0.1 M NaOH

 For τ = 80/3 min  8.0 mL, 0.1 M NaOH

We added 10 mL 0.1 M HCl for each sample and reversal titrate the excess with NaOH.

HCl + NaOH → NaCl + H2O

8.8 mL * 0.1 M NaOH = 0.88 mmol NaOH

The ratio is one to one NaOH : HCl so, 0.88 mmol NaOH = 0.88 mmol HCl

We initially had 10 mL 0.1 M HCl.

10 mL * 0.1 M – 0.88 mmol = 0.12 mmol HCl

The sample taken was 10 mL in volume so,

9
8.4 mL * 0.1 M NaOH = 0.84 mmol NaOH

The ratio is one to one NaOH : HCl so, 0.84 mmol NaOH = 0.84 mmol HCl

We initially had 10 mL 0.1 M HCl.

10 mL * 0.1 M – 0.84 mmol = 0.16 mmol HCl

The sample taken was 10 mL in volume so,

8.0 mL * 0.1 M NaOH = 0.80 mmol NaOH

The ratio is one to one NaOH : HCl so, 0.80 mmol NaOH = 0.80 mmol HCl

We initially had 10 mL 0.1 M HCl.

10 mL * 0.1 M – 0.80 mmol = 0.20 mmol HCl

The sample taken was 10 mL in volume so,

Now let us find –rA

10
  For τ = 80 min  CA0 = 0.1 M and xA = 0.88

 For τ = 40 min  CA0 = 0.1 M and xA = 0.84

 For τ = 80/3 min  CA0 = 0.1 M and xA = 0.80

Now to find the rate constant (k) and order (n)

Plot ln(-rA) vs lnCA graph. Using y = mx + n equation of the graph, we found n and k values.

n = 1.977 ≈ 2 → Second order reaction ( )

and lnk = 1.9572 → k = 7.07 min -1

11

Figure 2 – Reaction Order Graph from Set 1 Data

 4.2. Set 2

-Volume of the reactor = 1.6 L

-Constant flow rate: 60 cm3/ min

τ = constant minutes

 Temperature (℃) = 25 ℃ and the amount of NaOH = 8 mL

8.0 mL * 0.1 M NaOH = 0.80 mmol NaOH

The ratio is one to one NaOH : HCl so, 0.80 mmol NaOH = 0.80 mmol HCl

We initially had 10 mL 0.1 M HCl.

10 mL * 0.1 M – 0.80 mmol = 0.20 mmol HCl

The sample taken was 10 mL in volume so,

 Temperature (℃) = 30 ℃ and the amount of NaOH = 8.6 mL

8.6 mL * 0.1 M NaOH = 0.86 mmol NaOH

The ratio is one to one NaOH : HCl so, 0.86 mmol NaOH = 0.86 mmol HCl

We initially had 10 mL 0.1 M HCl.

10 mL * 0.1 M – 0.86 mmol = 0.14 mmol HCl

The sample taken was 10 mL in volume so,

12
  Temperature (℃) = 46 ℃ and the amount of NaOH = 9.3 mL

9.3 mL * 0.1 M NaOH = 0.93 mmol NaOH

The ratio is one to one NaOH : HCl so, 0.93 mmol NaOH = 0.93 mmol HCl

We initially had 10 mL 0.1 M HCl.

10 mL * 0.1 M – 0.93 mmol = 0.07 mmol HCl

The sample taken was 10 mL in volume so,

Now let us find –rA and k

We calculate k values according to n = 1.977462

 For Temperature (℃) = 25 ℃  CA0 = 0.1 M and xA = 0.8

13
 For Temperature (℃) = 30 ℃ CA0 = 0.1 M and xA = 0.86

 For Temperature (℃) = 46 ℃ CA0 = 0.1 M and xA = 0.93

J
- Activation energy (EA) when n = 1.977462 and R = 8.314
mol . K

14
With using this equations we drew lnk vs 1/T graph. The slope of the graph gives us
value. Activation energy is constant for each temperature.

/mol

Figure 3 – Activation Energy Graph for n=1.977

J
- Activation energy (EA) when n = 2 and R = 8.314
mol . K

With using this equation, we drew lnk vs 1/T graph. The slope of the graph gives us
value. Activation energy is constant for each temperature.

/mol

15
Figure 4 – Activation Energy Graph for n=2

- We calculate k values according to n = 2 with this formula:

And then we check all of the k values with this formula:

 For Temperature (℃) = 25 ℃  CA0 = 0.1 M and xA = 0.8

 For Temperature (℃) = 30 ℃ CA0 = 0.1 M and xA = 0.86

16
  For Temperature (℃) = 46 ℃ CA0 = 0.1 M and xA = 0.93

5. Discussion and Results

Before discussing the resulted, we found it to more convenient to talk about the experimental
conditions and set up. This will help in understanding the how finding we found change with
the experimental parameters.

Table 3 – Set 1 Results

Results for Set 1

Volumetri
Caf
c Flow τ (min) Xa -ra ln(-ra) ln(Caf) k (min-1)
(M)
Rate Ratio
0.8
20:20 80 0.012 0.0011 -6.812445099 -4.422848629
8
0.8 7.079535886
40:40 40 0.016 0.0021 -6.165817934 -4.135166557
4
60:60 26.6666667 0.02 0.8 0.003 -5.80914299 -3.912023005

17
Table 4 – Set 2 Results

T (°C) Caf (M) Xa -ra τ (min)

25 0.02 0.8 0.003
30 0.014 0.86 0.003225 26.66667
46 0.007 0.93 0.003488

Table 5 – Set 2 Results Continued for Reaction Order Accepted as 1.97746

n = 1.9774623544
k (min-1) ln(K) T in K EA (J/mol)
6.8671 1.9267 298.15
14.9449 2.7044 303.15 81340.33
63.6432 4.1533 319.15

Table 6 – Set 2 Results Continued for Reaction Order Accepted as 2

n=2
k (min-1) ln(K) T in K EA (J/mol)
7.5000 2.0149 298.15
16.4541 2.8006 303.15 82207.29261
71.1735 4.2651 319.15

The process of ethyl acetate saponification with sodium hydroxide was selected for this
study.

NaOH + CH3COOC2H5 → CH3COONa + C2H5OH

Sodium Hydroxide + Ethyl Acetate (EtOAc) → Sodium acetate + Ethyl Alcohol

With both reactants having a concentration of 0.1 M, this saponification reaction is first order
when compared to sodium hydroxide and ethyl acetate; generally, it is a second-order
reaction. When the reactants are transformed into products at a specific rate, the reaction,
which is conducted in a continuous stirred reactor, enters a steady state.

18
The reactor volume, reaction temperature, reactant concentration, and flow values all affect
the reaction's steady state.

Aim:

1. Reaction rate expression development using continuous stirred reactor data

2. Using continuous stirred reactor data, the development of the reaction rate and the
temperature dependency of the reaction rate constant is examined.
3. Recognizing the performance of a continuous stirred reactor
4. Research into the relationship between mixing speed and reaction rate

In the experiment, liquid-phase mixed CSTR was used. A glass cylinder with a stainless steel
base serves as the reactor. Water flows through the submersible pipe that is installed inside
the reactor, and the temperature of the water may be changed using the temperature control
on the control panel to achieve the appropriate temperature. The height-adjustable upstream
pipe can be used to gauge the liquid level inside the reactor. The effluent tank collects the
reactor’s wastewater for the required pre-waste treatment. Each tank has two peristaltic
pumps fitted to deliver feed. The flow rate that is modified with the use of flow meters
determines the residence time in the reactor. On/off switches, pump switches, temperature
switches, conductivity scale switches, and mixer motor switches are all located on the front
panel and can be used to regulate the machinery.

A reactor is a piece of machinery that facilitates the reactional conversion of raw materials
into the desired product. Reaction rate is the rate at which a specific chemical component is
broken down to create a final product. A chemical reaction is an event that occurs when one
or more chemical substances lose their qualities, and a new chemical is created as a result of a
change in the number of atoms in the component and/or a change in the arrangement of these
atoms. The entire mass is considered to remain constant or not to decrease during the course
of the chemical reaction in this traditional method of chemical change. Chemical
manufacturing techniques are based on chemical kinetics and reactor architecture. Reactors,
which we might consider the most significant piece of equipment in the entire operation, are
used in industrial chemical processes to transform raw materials into desired products.
Therefore, the success of an industrial application depends greatly on the design and
operation of chemical reactors.

Depending on the rate of the reaction, the rate of the reaction is frequently expressed as
mol/L·time, with the unit of time being seconds, minutes, hours, days, etc. It might be a

19
device like Most reactions don't have a constant rate from the start until equilibrium is
attained; instead, it changes gradually over time. This is owing to the fact that as the reaction
progresses, the reactant concentration drops as a result of product production, which causes a
steady decrease in the originally high number of effective collisions between the reactants. In
contrast, the rate of the backward reaction grows as the reversible reaction proceeds from a
zero initial rate. When the rates of the forward and reverse reactions are equal, the reaction is
in equilibrium. The concentration of either one of the reactants or one of the products can be
used to calculate the rate of a reaction.

Temperature affects a reaction's rate as well as collisions per unit of time, collision
directions, the symmetry of species that collide, etc. It modifies the value of k, the rate
constant, which incorporates all variables influencing reaction rate; in addition, the Arrhenius
equation describes the relationship between the rate constant k and the absolute temperature
T.

−E −E
RT RT
k =k o∗e ∨k = A∗e

As can be seen, k and T have an exponential rather than a linear connection. In other words, a
little change in temperature results in a big change in k.

The most popular reactor design for processes is CSTR. These are tank-shaped reactors
where the reactants are continually fed into the system and the reaction products are
continuously removed. Since there is a very excellent mixture, it is presumed that every part
of the reactor contains the same component. They are typically utilized in liquid phase
processes with modest flow rates. Additionally, such reactors make temperature control
simple. At the majority of the time, they operate in a steady state with few variations in
temperature, concentration, or response rate across the tank.

The flow rates of 20, 40, and 60 cm 3/min were compared to the volume of our reactor in the
calculations for Set 1 to obtain the space time for each flow rate at steady state. The quantity
of NaOH supplied for the reverse titration was then verified. The final concentration of HCl
was determined by subtracting it from the original HCl ratio after multiplying the amount of
NaOH by the concentration. Following this procedure, the final concentrations and
conversions for each flow rate experiment was determined. The graph of ln(-r A) vs lnCA was
then created using the relevant calculations and operations after the x A's had been identified.

20
The reaction in this experiment was of the second order, and the rate constant was 7.07 min -1,
according to the equation of this graph that was obtained.

For Set 2, various temperatures have been taken into account while calculating the rate
constant. To find the activation energy, the Arrhenius equation was modified in a form to plot
lnk vs 1/T graph. We determined its value from the graph's slope. The activation energy was
determined to be 82207.293 J/mol as a result. All k values were then verified.

From set 1, the reaction order was found to be equal to 1.977 which is approximately 2.
Therefore, we can accept that the reaction is a second order reaction. As the flow rates
increased, the conversion decreased. However, the reaction rate increased. Moreover, it was
seen that as flow rate increases, space time decreases; this is a clear from the design equation.

From set 2, as temperature increased, conversion increased. This is clear from the behaviour
of the reaction as it is exothermic. Moreover, the activation energy of a chemical reaction is
closely related to its rate. Specifically, the higher the activation energy, the slower the
chemical reaction will be.  As this reaction occur at room temperature, and the found
activation energy was 82.2073 kJ/mol, therefore our results match with general knowledge.

6. Conclusion

At constant temperature, the conversion reduced as the flow rates rose. However, the pace of
response increased. Furthermore, when flow rate increases, space time reduces; this is
obvious from the design equation. Conversion increased as temperature increased at a steady
flow rate. This is evident from the reaction's exothermic behaviour. Furthermore, the
activation energy of a chemical process is proportional to its pace. In particular, the larger the
activation energy, the slower the chemical reaction. Because this reaction occurs at ambient
temperature, our findings are consistent with general kinetics knowledge.
7. Recommendations

In this experiment, numerous parameters should be considered. The solution in which

phenolphthalein drops are dispersed during titration should not be pink, and titration should
be discontinued as soon as the solution reaches equilibrium. You can maintain your balance
in this manner. Additionally, when titrating, measurement readings should be obtained with
caution. For the titration, the amount of CSTR sample obtained is crucial. Waiting periods
ought to be spaced out equally. It is important to take precautions to make sure the system is
leak-free. A specified amount of time should pass after the temperature adjustment is

21
completed. When testing, the adjustable flow component should also be considered. It is
crucial that it be at the flow rate that will be sampled then. Working with glassware and
solutions requires caution.

References

[1] Armfield. (n.d.). CEM MKII Manual Issue 14 - Tu Dublin. Retrieved October 10, 2022,
from https://eleceng.tudublin.ie/gavin/DT275/CEM%20MKII%20manual%20issue
%2014.pdf
[2] Fogler, H. S. (2017). Essentials of Chemical Reaction Engineering (Second). Pearson
Education (US).
[3 ]Levenspiel, O. (1999). Chemical Reaction Engineering. Wiley.

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