TABLE OF CONTENTS

CONTENTS PAGE
ABSTRACT
INTRODUCTION

OBJECTIVE

THEORY

APPARATUS

PROCEDURE

RESULT

SAMPLE OF CALCULATION

DISCUSSION

CONCLUSION

RECOMMENDATION

REFERENCE

APPENDICES
 ABSTRACT

This experiment is done to carry out saponification reaction between

NaOH and Et(Ac) in tubular flow reactor, to determine the reaction rate
constant (k) and to determine the effect of residence time on the conversion in
tubular flow reactor. Two solution are feed into the reactor which are 20 L of
0.1 M sodium hydroxide, NaOH and 20 L of 0.1 M ethyl acetate, Et(Ac). There
3 part procedure in this experiment which for the first part is the general start-up
procedure. Second is for effect of residence time on the reaction in a tubular
flow reactor and thirdly is for the back titration. For the first part is to feed the
both tank, tank B1 and tank B2 with the solution. Also want to set up the flow
rates. In this part we want to allow the both solution to flow through the reactor
R1 and overflow it into the waste tank B1. In the second part, we want to take
the reading for inlet and outlet conductivity, Q. We also want to take the sample
during this part. Flow rates in this part must be reduce to take difference
residence time. Lastly, for the back titration. The sample that we have take in
the second part, we must added the HCl immediately. HCl is use for quenching
which is for stop any further reaction. After added the HCl, the sample must be
titrate with NaOH solution until is neutralized.
 INTRODUCTION

Plug flow reactor is used to describe chemical reactions in continuous. It is

also used to model the chemical transformation of compounds as they are
transported in systems resembling ‘pipes’. The pipes can represent a variety of
engineered or natural conduits through which liquids or gases flow.

An ideal plug flow reactor has a fixed residence time: any fluid that enters
the reactor at time t will exit the reactor at time t + τ, where τ is the residence
time of the reactor. A real plug flow reactor has a residence time distribution
that is narrow pulse around the mean residence time distribution. The
characteristics of ideal plug flow are perfect mixing in the radial dimension
(uniform cross section concentration) and no mixing in the axial direction or
axial dispersion(segregated flow).

A typical plug flow reactor could be a tube packed with some solid material
(frequently a catalyst). Typically these types of reactors are called packed bed
reactors. Sometimes the tube will be a tube in a shell and tube exchanger.

Plug flow reactors have a high volumetric unit conversion, run for long
periods of time without maintenance, and the heat transfer rate can be
optimized by using more, thinner tubes or fewer, thicker tubes in parallel. The
disadvantages of this reactor are that temperature is hard to control and can
result in undesirable temperature gradients.

Plug flow reactors are used for some following application such as large-
scale reactions, fast reactions, homogeneous or heterogeneous reactions,
continuous production and high temperature reactions.

OBJECTIVES

1- To carry out a saponification reaction between NaOH and Et(Ac) in TFR.

2- To determine the reaction rate constant.
3- To determine the effect of residence time on the conversion in a TFR.

THEORY

In a tubular reactor, the feed enters at one end of a cylindrical tube and the
product stream leaves at the other end. The long tube and the lack of provision
for strirring prevents complete mixing of the fluid in the tube. Hence the
properties of the flowimg stream will vary from one point to another, namely in
both radial and axial directions.

In the ideal tubular reactor which is called plug flow reactor, specific
assumptions are made about the extent of mixing:

a) No mixing in the axial direction

b) Complete mixing in the radial direction
c) A uniform velocity profile across the radius

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 two kinds:

a) Mixing in longitudinal direction due to vortices and turbulence

b) Incomplete mixing in radial direction in laminar flow conditions.

In ideal tubular flow there is no axial mixing and the fluid elements leave in the
same order they arrived. Therefore, fluid entering the reactor at time t will the
reactor at time t +τ, where τ is residence time of the reactor.

The reactor’s residence time is defined as the reactor volume divided by the
total feed flow rates.

Residence time, τ = VTFR / VO

For a second order equipmolar reaction with the same initial reactants
concentration ( CAO – CBO), the rate law shown to be:

-rA = k CACB = k CA2 = k CAO2 (1 – X )2

- rA = FAO (dX / dV ) = vo CAO (dX / dV )

VTFR =
 Where : X = extent of conversion

CA = exit concentration of reactant NaOH [M]

Vo = total inlet flow rate of solution [ ml/min]

CAO = inlet concentration of reactant NaOH in the reactor [M]

For constant tubular reactor volume, flow rate and initial concentrations, the
reaction rate constant is,

k =

Saponification reaction:

NaOH + CH3COOC2H5 → CH3COONa + C2H3OH

Sodium Hydroxide (A) + Ethyl Acetate(B) → Sodium Acetate (C) + Ethyl

Alcohol(D)
The reaction can be considered equimolar and first order with respect to both
sodium hydroxide and ethyl acetate i.e. second order overall, within the limits

of concentration (0-0.1M) and temperature (20- 400C) studied.

 APPARATUS & CHEMICAL REAGENT

1- Tubular reactor equipment

2- Burette
3- Conical flasks
4- 50 mL beaker
5- 0.25 M HCl
6- 0.1 M NaOH solution
7- 0.1 M Et(Ac) solution

PROCEDURE

A)GENERAL START-UP

1) All valves was ensured initially closed except valves V8,V4 and V17.
2) The following solutions was prepared:

a) 20 liter of sodium hydroxide, NaOH (0.1 M)

b) 20 liter of ethyl acetate, Et(Ac)(0.1M)

c) 1 liter of hydrochloric acid, HCl(0.25M), for quenching

3) The NaOH solution was feed in tank B1 while for the tank B2 with Et(Ac)
solution.

4) The water jacket B4 and pre-heater B5 was filled with clean water.

5) The power for the control panel was turn on.

6) Valves V2, V4,V6,V8,V9 and V11 was opened.

7) Both pumps P1 and P2 was switched on. P1 and P2 was adjust to obtained
flow of approximately

300 ml/min at both flow meters Fl-01 and Fl-02. Make sure both flow rates
are the same.

8) Both solutions are allowed to flow through the reactor R1 and overflow into
the waste tank B3.

9) Valves V13 and V18 was opened. Pump P3 was switch on to circulate the
water through

Pre-heated B5. Stirrer motor M1 was switch on and the speed was set about
200 rpm to ensure

homogenous water jacket temperature.

B) EFFECT OF RESIDENCE TIME ON THE REACTION IN A TFR.

1- Valves V9 and V11 was opened.

2- Both the NaOH and Et(Ac) solutions was allowed to enter the plug reactor
R1 and empty into the waste tank B3.

3- P1 and P2 was adjusted to give a constant flow rate of about 300 ml/min at
flow meters Fl-01 and Fl-02. Make sure the flow rates are the same. The
flow rates was recorded.

4- Monitoring the inlet (Ql-01) and outlet (Ql-02) conductivity values was
started until they do not change with time. This is to ensure that the
reactorhas reached steady state.

5- both inlet and outlet steady state conductivity values was recorded. The
concentration of NaOH exiting the reactor ant extent of conversion from the
calibration curve was find.

6- Optional : Sampling valve V15 was opened and 50 mL of sample was

collected. A back titration procedure was carried out to manually determine
the concentration of NaOH in the reactor and extent of conversion.

7- Step 3 to 6 was repeated for different residence times by reducing the feed
flow rates of NaOH and Et(Ac) to about 250,200,150 and 50 ml/min. Make
sure that both flow rates are the same.

C)BACK TITRATION

1) 0.1 m NaOH solution was fill up a burrete.

2) 10 mL of 0.25 M HCl was measured in a flask.

3) 50 mL of sample was obtained from the experiment and immediately added

the sample to the HCl in the flask to quench the saponification reaction,

4) A few drop of pH indicator was added into the mixture.

5) The mixture was titrate with NaOH solution from the burette until the
mixture is neutralized. The amount of NaOH titared was record.

SAMPLE CALCULATION

Reactor volume, VTFR = 0.4 L

Concentration of NaOH in feed tank, CAO = 0.1 M

Concentration of Et(Ac) in feed tank = 0.1 M

1) Total flow rate of solutions, Vo

Vo = flow rate of NaOH + flow rate of Et(Ac)

= 304 + 295
= 599 mL/min

2) Residence time, τ

τ = VTRF / Vo
= 400 / 599
= 0.667 min

3) Conversion, X

Volume of sample, Vs = 400 ml

Concentration of NaOH in the feed vessel, CNaOH,f = 0.1 mol/L
Volume of HCl for quenching, VHCl,s = 10 ml
Concentration of HCl in standart solution, CHCl,s = 0.25 mol/L
Concentration of NaOH used for titration, CNaOH,s = 0.1 mol/L

First value for volume of titrated NaOH, V1 = 13.6 ml

A) Conc. Of NaOH entering the reactor, CNaOH,0

CNaOH,0 = (CNaOH,f) / 2
= 0.1 / 2
 = 0.05 mol/L

B) Volume of unreacted quenching HCl, V2

V2 = ( CNaOH,s / CHCl,s ) x V1
= ( 0.1 / 0.25 ) x 13.6
= 5.44 ml

C) Vol. of HCl reacted with NaOH in sample, V3

V3 = VHCl,s - V2
= 10 - 5.44
= 4.56 ml

D) Moles of HCl reacted with NaOH in sample, n1

n1 = CHCl,s x V3
= 0.25 (mol/L) x 4.56 (mL)
= 1.14 x 10-3 mol

E) Moles of non-reacted NaOH in sample, n2

n2 = n1 = 1.14 x 10-3 mol

F) Conc. of unreacted NaOH in the reactor, CNaOH

CNaOH = n2 / (Vs / 1000 )

 = (1.14 x 10-3) / ( 400 / 1000 )

= 2.85 x 10-3 mol/ L

G) Conversion , X = ( 1 - ( CNaOH / CNaOH,0 ) ) x 100 %

X = ( 1 – (2.85 x 10-3 / 0.05 )) x 100 %

= 94.3 %

4) Reaction rate constant , k

K = ( Vo / VTFR CAO) ( X / 1-X )

= ( 0.599 / (0.4)(0.1) ) ( 0.943 / ( 1- 0.943 ))
= 247.744 L / mol.min

5) Rate of reaction, -rA

-rA = k CACB = k CA2 = k CAO2 ( 1 – X )2

-rA = k CAO2 ( 1 – X )2
= ( 247.744) (0.1)2 ( 1 – 0.943 )2
= 0.00805 mol / L. min

DISCUSSION
To run the this experiments we prepared large quantities of equimolar mixtures
of ethyl acetate and sodium hydroxide and they were placed at the inlet tubes to
the reactor.The pumps were set so that they were at flow rates. This required us
to interpolate, because when calibrating the pumps did not have equal
volumetric flow rates.The conductivity meter was connected to the PFR, so that
reading could be taken during the experiment.Reading were taken during the
entire experiment, and were stopped once a steady state had been reached. We
were only interest in the steady state value for the reactor, but for our data
collection we wanted to see how the conductivity was changing with time.

During this experiments, we must take the value of conductivity for

every each flow rates that we set up. Conductivity for the inlet and outlet does
not same. That’s why we must take the reading of conductivity to compare it for
each flow rates. Conductivity inlet have the greater value from the outlet
conductivity. This is because at the outlet conductivity, reaction between NaOH
solution and Et(Ac) solution have been occur. Reaction between this solution
will produce soap. The present of soap will effect the conductivity outlet which
is it reduce the conductivity. When the outlet conductivity reduce, we know that
the reaction have been occur.

Deionizer water has been used all over in this experiment. It is

because deionizer water will not effect the conductivity of the solution. The
deionizer water didn’t contain any other substance, that’s why it not effect the
reading of conductivity. Before taking the value of conductivity, we must leave
the value for 5 minutes and make sure that the value is in stable and constant at
the lower value.

From the graph, we will see that there are some mistake that we have
done during this experiment. The graph shown a conversion vs residence time.
The graph is not smoothly increase. There is an error that we have made. While
taking the sample from the reactor, we use the 50 mL beaker. This is wrong
because we must use the measuring cylinder. The reading of measuring
cylinder is more accurate compare to the beaker.

During the titration, there is an parallax error when we want taking the
reading of burette. The parallax error will effect the value that have taking. It
also will effect the other calculation that involve the value that we take. That’s
why the graph that we have get is not smoothly increase. Therefore, to get the
smoothly increase graph, we must take the reading in the correct way to reduce
the parallax error.

There are others mistake take we have do during this experiment such
as we didn’t get the same flow rates for both pump P1 and pump P2. The flow
rates is not easy to controlled it. The flow rates always changing, and we must
always change back to the flow rates that we want.

CONCLUSION

1) Saponification reaction :

NaOH + CH3COOC2H5 → CH3COONa + C2H3OH

Sodium Hydroxide (A) + Ethyl Acetate(B) → Sodium Acetate (C) + Ethyl

Alcohol(D)
2) Reaction rate constant, k for every flow rates of solution has been
determined.

Total flow Reaction

rate of Rate
solution, Vo Constant
(mL/min) (L/mol.min)
599 247.744
499 195.442
399 162.008
3) 287 136.325 From this experiment, we found that the
92 47.700 effect of residence time was
perpendicular to the conversion. When the value of
residence time increase, the value for conversion also increase.

RECOMMENDATIONS

a) Use the measuring cylinder when want to collect the sample. This is
because it will give an accurate value for the reading.
 b) Reduces the parallax error when take the reading of NaOH in the
burette. Make sure that your eyes is parallel with the burette when you
want to take the reading.
c) Adjust the flow rate for the both pump to the same value or nearly
same.
d) Make sure that HCl solution must immediately added to the sample
after the sample was collected from reactor.
e) Ensure that the reactor has reached steady state before start monitoring
the conductivity.

REFERENCES

1- http://en.wikipedia.org/wiki/Plug_flow_reactor_model
2- http://www.solution.com.my/
3- www.metal.ntua.gr/~pkousi/e-learning/bioreactors/page_07.htm
4- classes.engr.oregonstate.edu/cbee/.../Saponification%20-%20Kato.ppt
5- http-server.carleton.ca/~dkarman/81302/PFR.pdf
6- civil.colorado.edu/.../IDEAL%20PLUG%20FLOW%20REACTOR.pdf
7- www.metal.ntua.gr/~pkousi/e-learning/bioreactors/page_07.htm

time: 10 pm, date: monday 7/2/11

APPENDICES
Plug flow reactor.

Tubular reactor