S.no.

Name of the Experiment Date of Date of

Conduction Submission

P1 Coil Type Plug Flow Reactor February 2, 2021 February 4, 2021

GROUP NUMBER: 9

GROUP MEMBERS:

OINDRILA GHOSH (2018A1PS0080G)

NISHANT HINGE (2018A1PS0385G)
ADITYA GOEL (2018A1PS0054G)
DEEPSHIKA DUTTA (2018A1PS0312G)
GANESH BHARATWAJ (2018A1PS0991G)

OBJECTIVE: ​The study of a non-catalytic homogeneous reaction in a coil type plug

flow reactor under ambient conditions.

AIM:
1. To carry out a saponification reaction between ethyl acetate and sodium hydroxide
in a coil type PFR.
2. To determine the rate constants for saponification of ethyl acetate with sodium
hydroxide at ambient temperature.
3. To determine the effect of residence time on the conversion in the PFR.

THEORY:

● If we consider an ideal ​plug flow reactor (PFR​), there is no mixing along the direction
of flow, and the mixing is complete only along the perpendicular direction of flow, in the
radial direction.
● In case of coil type PFR, we expect a higher value of rate constant. This is because
turbulence is introduced due to frequent change in direction of flow and presence of
secondary flow.
● For a PFR, at steady state,
 XA
V
F A0
= ∫ dx
−rA
0

XAF
V
F A0
= 1
kC 2 A0
∫ dx
(1−X A )2
0

F​A0 →
​ molar flow rate of NaOH
F​A0​=V​0​C​A0
V​0​ → Volumetric flow rate of feed (in LPM)
V​R​→Volume of the PFR (in L)
● Residence time ( τ )​: ​Residence time is the average amount of time that a particle spends
V X
in a particular reactor. τ = V R = kC1 (1−XAF )
0 A0 AF

● In this experiment we consider a ​bimolecular reaction (reacting species are ethyl acetate
and sodium hydroxide):

​ CH​3​COOC​2​H​5 ​ + NaOH = CH​3​COONa + C​2​H​5​OH (1)

(B) (A)

-r​A​= k C​A​C​B

Where, A represents NaOH and B represents CH​3​COOC​2​H​5

The initial concentrations of the reacting species are the same C​A0​= C​B0 ​(neglecting
change in density). Thus, if take this into account, we have
2
-r​A =
​ kC​A​
C​A​= C​A0​ (1- X​A​)
Where X​A​ is the conversion of species A
● The above reaction is a ​saponification reaction, ​which is the base hydrolysis of a fat or
oil, resulting in the formation of a soap and an alcohol as a byproduct, is known as
saponification. Saponification is used in the soap industry, in fire extinguishers, etc.
● Rate constant (k): ​It is the proportionality constant in the rate law expression, at a given
temperature.

EXPERIMENTAL SET-UP

The reactor is made up of SS tubes. The tube is bent in the helical form. The air
compressed feed reactants are given through rotameters. The flow rate can be adjusted by
operating the needle valve provided on the respective rotameter. The compressed air is used
for circulation of feed. The concentration of feed and the product coming out from the
reactor are analyzed by chemical titration and check the effect and the performance of the
reactor.

PROCEDURE

1) Prepare 10 L of N/5 NaOH solution by dissolving 80 gm of NaOH in 10L of

water.
2) Prepare 10 L of N/5 ethyl acetate solution by dissolving 176 gm of ethyl acetate in
10L of water.
3) Check the drain valves of both feed tanks are closed and pressure regulator reads
zero pressure. Fill the tank A and B with appropriate reactants while keeping air
releasing valve open. Close the air releasing valves and tank feed inlet valves.
4) Open air inlet valve (from compressor), pull and adjust the pressure regulator to 1
kg/cm2.
5) Adjust the rotameter A and rotameter B to adjust the flow rate of the two streams
in the feed mixture CA0 = CB0
6) Pass equimolar mixture of Ethyl Acetate and NaOH into the PFR by allowing equal
volumetric feed rates of reactant into the reactor.
7) After about 10 min or time twice the residence time of the reactor (which ever is
greater) i.e. when steady state is achieved, collect exact 10 ml of sample of the
liquid at the outlet, in a graduated cylinder that already contains 10 ml of (chilled)
N/10 HCl. Transfer this solution (20 ml) in a 250 ml or 100 ml clean and dried
titration flask.
8) Titrate this solution against the N/10 solution of sodium hydroxide adding 1 drop
of phenolphthalein as an indicator. When the endpoint of titration has been reached,
read the used volume of NaOH from the burette (VNaOH).
9) Note the volumetric flow rate of liquid at the end of the reactor. Note the reaction
temperature.
10) Repeat all the steps for five to seven for different flow rates of feed at the same
temperature.

OBSERVATION TABLE:

S no. V​o​ (LPH) V​NaOH​ (ml)

1 2.5 7.5

2 5.0 6.9

3 7.5 6.4
4 10.0 5.7

5 15.0 4.9

Calculations Table:

Flow rate V(NaOH) C​A τ X​A 1/C​A

2.5 7.5 0.025 8.4 0.83333 40

5 6.9 0.031 4.2 0.793333 32.25806

7.5 6.4 0.036 2.8 0.76 27.77778

10 5.7 0.043 2.1 0.713333 23.25581

15 4.9 0.051 1.4 0.66 19.60784

SAMPLE CALCULATIONS:

Run #4:
GRAPHS:

Graph of Conversion vs Residence Time:

Graph of Concentration vs Residence time:

 Graph of (inverse of Concentration) vs Residence time:

Thus, from the graph of best-fit line, we obtain k = 2.7574 l/min.mol

DISCUSSIONS:

1. OINDRILA GHOSH: ​The base hydrolysis of a fat or oil, resulting in the

formation of a soap and, an alcohol as a byproduct, is known as saponification​.
Saponification is used in the soap industry, in chemical fire extinguishers and in the
production of grease removers, herbicides, etc. In this experiment, we use sodium
hydroxide as the base, which reacts with ethyl acetate to give sodium acetate (soap) and
ethanol (an alcohol).

In accordance with the power law model of rate law, the rate equation can be expressed as
follows: ​-r​A​= k C​A​C​B​, where, A is NaOH and B is Et(Ac). Here, we take the same flow rate of
both the reactants (regulated using the rotameter) and thus, the initial concentration of both
reactants are the same (​C​A0​= C​B0​). From the equation of the reaction, we know that reactants A
and B react in the stoichiometric ratio 1:1. This means that at every instant, ​C​A​= C​B​. The rate law
reduces to: ​-r​A =
​ kC​A​ . Thus, this is a ​bimolecular second order reaction​.
2​

The calculations corresponding to run 2 (that is, a ​volumetric flow rate of 5 LPH​) are as
follows:
It is important that the ​pressure does not change​ during the experiment as this will affect the
flow rates. Before taking the first 10 ml sample from the reactor, we wait for about ​twice the
calculated residence time​, so that the reactant mixture fills up the reactor, reacts and reaches
steady state. ​Chilled HCl​ is added to the sample extracted as this stops the reaction and reacts
with the unreacted NaOH. In non-ideal reactors like in this experiment (coil type PFR), there is
turbulence due to the frequent change in direction of the reactants and the existence of a
secondary flow. Due to turbulence, the collisions increase and thus, the​ rate constant is
expected to be higher​.

From the conversion versus residence time graph, we notice that the ​conversion increases with
increase in residence time.​ The residence time is indicative of the amount of time that the
reactants spend inside the reactor. If reactants spend too much time in a reactor, they overreact
(products formed start reacting too). This is unlikely here as the reaction stops at the formation of
soap and alcohol. If reactants spend too little time, the contact time is reduced. This implies that
there are less number of successful collisions, resulting in less conversion. Thus, as residence
time increases, it is expected that the conversion increases too and this is seen in the plot.

From the concentration versus residence time graph, we notice that ​the concentration decreases
with increase in residence time.​ The concentration here is the concentration of the unreacted
reactant. In extension to the reasoning in the previous paragraph, as conversion increases with
residence time, more of the reactants are converted to products, and so, the concentration of the
reactant is expected to decrease.
The inverse of concentration versus residence time graph is plotted keeping the ​bimolecular,
homogeneous, constant volume, non-catalysed, second order​ nature of the reaction in mind,
which can be characterised using the equation: k τ = (1/​C​A​) - (1/​C​A0​)
Thus, the slope of the inverse of concentration versus residence time plot gives k (rate constant).
This value, as found from the best fit line from the plot, is ​2.7574 l/min.mol​. The deviations
from the expected straight line is due to ​experimental errors​.

Generally, PFRs are used in industries because of the higher volumetric unit conversion,
capability of continuous operation, less operation costs and good heat exchange capacity. The
main ​disadvantage​ is that undesired thermal gradients may exist and temperatures are hard to
control. In general, continuous reactors are used in applications where the rate of production has
to be maintained high and slight deviations in product quality is tolerable, like in most
petrochemical plants​ (oil cracking, gasoline production, etc).

2. NISHANT HINGE:
In this particular experiment, we worked with a Plug flow reactor which was
structured in a coiled tubular manner which gives it a helical appearance. A plug
flow reactor assumes that there is complete mixing of the fluid in the radial
direction and no mixing in the direction of flow, hence the name plug flow. The
volume of the reactor was roughly 0.7L and the reaction taking place inside the
reactor is a saponification reaction between 0.3N ethyl acetate and 0.3N sodium
hydroxide. Saponification is a reaction between a base and esters to give salts of
long chain fatty acids(soap) and alcohol.
Both the solutions are injected in equal volumetric proportions so as to make the
effective concentration as 0.15N. It's important to let the system achieve steady
state and hence, we should let out the first portion of the product mixture before
taking any sample.
In the coil type reactor, turbulent flow is purposefully introduced so as to obtain a
higher value of rate constant
The 10 ml sample taken is mixed with 10 ml of 0.1N HCL and two drops of
phenolphthalein. The HCL reacts with unreacted sodium hydroxide. This complete
mixture is titrated against 0.1N standard solution of NaOH in order to find the
concentration of unreacted ethyl acetate. The data obtained from different Runs is
analysed and plotted against different parameters in order to find the Rate law
constant.
 The reactor is fed with an equimolar mixture of both the reactants, hence the
reaction is first order with respect to individual reactants but overall second order
reaction.
From Graph 1, we can see that conversion increases with residence time. This is
because the reactants spend more time in the reactor and the reaction goes on for a
longer time.

From graph 2, we can see that concentration of the species decreases with
increasing residence time because reactants spend more time inside the reactor
thus giving more time for the reaction to occur.

From 3 is plotted for its main purpose of finding the reaction constant. Inverse of
concentration is plotted against residence time. The slope of the graph is the direct
value of reaction constant for this particular reaction. The value is found out to be
2.7574 litres per minute per mol.

Calculations: The residence time was calculated by dividing the volume of the
reactor by the total flow rate to the reactor. This will be double the individual flow
rates of the individual reactors. The initial concentration of the reactants will be
half the individual concentration of the reactants. This is because the reactants are
taken with equal concentration and mixed in equal proportion. The unreacted
NaoH from the reactor reacts with 10 ml 0.1N HCl. This is titrated against 0.1N
NaOH to find the amount of unreacted ethyl acetate in the reaction. Once the
concentration of unreacted ethyl acetate is found out, conversion is found out
using the formula (Ca0-Ca)/Ca0.

C​Ao​= 0.15N
For Vo=10 Lph
τ = T otalV olume of reactor
volumetric f low rate
= 0.7
2×10
= 0.035h = 2.1 min
V​NaOH​=5.7 mL
V HCl N HCl −V N aOH N N aOH 10×0.1−5.7x0.1
C​A​= V sample = 10 = 0.043N
x​A =
​ (C​Ao​-C​A​)/C​Ao​= (0.15-0.043)/0.15 = 0.71333 = 71.33%

3. DEEPSHIKA DUTTA:
Our aim here was to study coiled type plug flow reactors or PFRs. PFRs are systems of
cylindrical geometry. Fluid flowing can be considered as “Plugs” flow along the axial
direction of the reactors and each plug has a different composition from the ones before
and after it.

We have studied PFRs through a saponification reaction between ethyl acetate and
sodium hydroxide. Saponification reactions are conversion of fat, oil, lipid into soap in
presence of aqueous alkali (NaOH in our case). Saponification reactions are in general
irreversible second order reactions with rate rA = -kCACB where CA is concentration of
first reactant, CB is concentration of second reactant. We took 10 mL of the sample and
allowed 10 mL of 0.1N HCl to react with it. Now, it is titrated against 10 mL of 0.1N
NaOH to get the concentration of unreacted ethyl acetate.

Residence time is ​effectively the average length of ​time that an entity will remain in a
reactor.

In 1​st​ graph, conversion increases with increase in residence time. The more time
reactants spends in reactor, the more time it gets to convert into products. The
concentration of reactants decrease with increase in residence time and this is evident
from graph 2.

From graph 3, we found out, reaction constant The slope of concentration versus
residence time gives inverse of reaction constant.

Cao = 0.15N

For V = 7.5LpH

Tau = 2.8mins

CA from the given formula is 0.036 and conversion or X(​ (C​Ao​-C​A​)/C​A0​ ) is 76%

Usage of PFR :

● Large-scale production
● Fast reactions
● Homogeneous or heterogeneous reactions
● Continuous production
● High-temperature reactions
.

4. ADITYA GOEL: ​In this experiment, we studied a coil type plug flow reactor
through a saponification reaction between ethyl acetate and sodium hydroxide.
Here, we considered NaOH as species A and ethyl acetate as B. Saponification
reaction is the ​bimolecular second order reaction​ which means that it is first
order with respect to both A and B while it is second order overall. Hence, the
reaction rate can be represented as:
-r​A​=kC​A​C​B
Saponification reaction​ is the base hydrolysis of a fatty acid or oil to give soap(
in this case C ​ H​3​COONa)​ and alcohol( in this case C
​ ​2​H​5​OH)​ as a by-product. It is
used in herbicides, manufacture of soap, chemical based fire extinguishers etc.

We studied an ideal Plug Flow Reactor(PFR), which has certain assumptions. First
is that there is complete mixing of the fluid in radial direction, hence there is no
variation in the concentration in this direction. Second, is that there is no mixing in
the axial direction, ie, the direction of flow, hence the concentration varies only in
the axial direction. All molecules spend equal time in the reactor, characterized by
its residence time. The ​design equation for an ideal PFR is​ given by:
XA
V
F A0
= ∫ dx
−rA
, where x is the conversion, F​Ao​ is the initial flow rate, r​A​ is the rate of
0
reaction and V is the volume of the reactor.

We used a coil type PFR, where turbulent flow is purposefully introduced to have higher
value of k.

We took equimolar 0.3 N of pure ethyl acetate and NaOH for the reaction. Hence, the
concentration of both reactants in the reaction mixture (C​Ao​=C​Bo​) is 0.3/2=0.15N. The
volume of the reactor in consideration is 0.7 L and we calculate the conversion, final
concentration and k for different flow rates. We let the reaction proceed for twice the
residence time. This is because it takes 1 residence time to completely fill the reactor. We
then took 10 mL of the reaction mixture out of the reactor and reacted it with 10 mL of
 0.1N HCl which basically reacted with the remaining NaOH. Now,. this titrated solution
is titrated against 10 mL of 0.1N NaOH to get the ethyl acetate remaining.

In the first plot, we plotted conversion of A(x​A​) vs residence time ( τ ). ​We can see that
the ​conversion increases with increase in residence time,​ since the reactants get to
spend more time in the reactor to take place.

In the second plot, we plotted concentration of A vs the residence time.​ The final
concentration of A decreases with increase in residence time.​ This is because more
and more reactant is consumed when we allow more time for the reaction to take place,
hence decreasing the final concentration of A.

The third plot, between 1/C​A​ and τ is used to calculate the rate constant by getting the
best fit line. The rate constant, ​k is the slope of the line and is found out to be 2.7574
L/(min. mol).

Calculations(Run 1)​:
C​Ao​= 0.15N
For Vo=2.5 Lph
τ = T otalV olume of reactor
volumetric f low rate
= 0.7
2×2.5
= 0.14h = 8.4 min
V​NaOH​=7.5 mL
V HCl N HCl −V N aOH N N aOH 10×0.1−7.5x0.1
C​A​= V sample = 10 = 0.025N
x​A​=(C​Ao​-C​A​)/C​Ao​=(0.15-0.025)/0.15=0.83333=83.3%

5. GANESH BHARATWAJ: ​In the given experiment we studied a saponification

reaction in a coil type plug flow reactor (PFR). The reaction was between ethyl
acetate and sodium hydroxide, which we denote by species B and A respectively.
We considered an ideal PFR, where there is no mixing in the direction of flow,
and the mixing occurs only in the radial direction. Saponification reaction is the
name given to any reaction that produces soap. It involves the conversion of fat,
oil or lipid into soap and alcohol by action of heat and in the presence of an
aqueous alkali solution. In this experiment, the soap was sodium acetate and the
alcohol was ethyl alcohol.
 Although the reaction was second order overall, we consider the reaction as first
order with respect to the individual reactants since the reactor was fed with an
equimolar mixture of both reactants.
We first plotted a graph of conversion (X​A​) vs residence time ( τ ). From the plot,
we notice that the conversion increases with increase in residence time. This is
because as the reactants spend more time in the reactor, the reaction proceeds for
longer duration thus yielding greater conversion.
The second plot was a graph of concentration (C​A​) vs residence time ( τ ). Here, the
concentration of species A decreases as residence time increases because longer
duration of reaction implies more conversion of reactants to products, thus
decrease in concentration of species A.
The graph of 1/C​A​ vs Residence time was plotted to find the rate constant. It was
obtained as k = 2.7574 l/min.mol by finding the slope of the best-fit line.
Calculations:
For volumetric flow rate V​o​=15 LPH, and volume of reactor V​R​=0.7L,
V olume of reactor 0.7
τ= T otal volumetric f low rate = 2×15 = 0.0233 hours = 1.4 minutes
C​A0​=0.3/2=0.15N, V​NaOH​=4.9ml
V HCl N HCl −V N aOH N N aOH 10×0.1−4.9×0.1
C​A​= V sample = 10 = 0.051 N
0.15−0.051
X​A​=(C​A0​-C​A​)/C​A0 = 0.15
= 66%

CONCLUSION

The saponification reaction carried out in this experiment is a bimolecular second order
reaction. From the slope of the inverse of concentration versus residence time graph, we
obtain k = 2.7574 l/min.mol for the reaction.

REFERENCES

1. H. Scott Fogler “ Elements of Chemical Reaction Engineering” 4th Edition

2. Octave Levenspiel “Chemical Reaction Engineering “ 3rd ed, Wiley, NY, 2001
3. P1 lab presentation slides
4. P1 lab manual