ABSTRACT

This experiment is conducted to carry out manual conversion determination on

experiment samples to verify the conductivity measurement values ,to carry out a

saponification reaction between NaOH and Et(Ac) in CSTR and determine the effect of

residence time onto the reaction extent of conversion also determine the reaction rate

constant .In order to accomplish the objective, the unit being used to perform this

experiment is CSTR 40L. The design of the reactor is very important to the success of the

production. In this experiment sodium hydroxide and ethyl acetate react in continuous

stirred tank reactor. Both of reactants feed to the reactor at equimolar flow rate for a

certain time.From Graph 1 it show that conductivity is decrease proportionally with

conversion.The result show that, when residence time is increase, conversion also

increase by lowering the flow rate. The higher conversion is 98.8% at 45 min residence

time and 0.2 mL/min total flow rate of solution.It can be conclude that the higher the flow

rate , the smaller the reaction rate constant and rate of reaction become highest. From the

calculation , it was obtained that the value of conversion is increase when the volumetric

flow rate decrease.This prove the theory from calibration curve.The rate of reaction is

higher which is ra=2.63x10-3 at the lower rate constant which is k = 68.35. The entire

objectives have been achieved and related to the theory of study .Therefore the

experiment is success.

1
INTRODUCTION

In the industrial chemical processes,mostly a reactor is the key item of equipment in

which raw materials undergo a chemical change to form desired products. The design and

operation of chemical reactors is thus crucial to the whole success of the industrial

operation. There are many types of reactor depending on the nature of the feed materials

and products. Understanding non-steady behavior of process equipment is necessary for

the design and operation of automatic control systems. The rate of reaction is most

important thing will be consider in the reactor because it showed the effectiveness of the

processing of the reactor. One particular type of process equipment is continuous stirred

tank reactor (CSTR).

In a continuous-flow stirred-tank reactor (CSTR), reactants and products are

continuously added and withdrawn from the reactor. In practice, mechanical or hydraulic

agitation is required to achieve uniform composition and temperature, a choice strongly

influenced by process considerations. The CSTR is idealized opposite of the weel - stirred batch

and tubular plug flow reactor. Analysis of selected combination of these reactor types can be

useful in quantitatively evaluating more complex gas , liquid and solid-flow behaviour.

In this experiment , the CSTR (model :BP143 ) unit is suitable for student experiment on

chemical reaction in liquid phase which is under adiabatic and isothermal condition. The unit

consist of jacketed reaction fitted in the agitator and condenser. The unit comes complete with

vessels for raw material and product,feed pumps and thermostat . (www.labequip.com) The

reactor is modeled in order to perform the saponification reaction where the reaction is occur

between the sodium hydroxide , NaOH and ethyl acetate , Et(Ac) . The saponification process

between this compounds produced sodium acetate in a batch and the continuos stirred tank

2
reactor evaluate the rate data needed to design a production scale reactor.

AIMS

In this experiment, there are a few objectives to achieve:

1. To carry out manual conversion determination on experiment samples to verify the

conductivity measurement values

2. To carry out a saponification reaction between NaOH and Et(Ac) in CSTR

3. To determine the effect of residence time onto the reaction extent of conversion

4. To determine the reaction rate constant

THEORY

Saponification is a process by which triglycerides are reacted with sodium or potassium

3
hydroxide (NaOH or KOH) to produce glycerol and fatty acid salt called “soap”. Lipid

that contain fatty acid ester linkages can undergo hydrolysis. (Helmenstine,2001) . The

equation below shows the saponification process between sodium hydroxide and ethyl

acetate ( irreversible reaction) to produce sodium acetate and by product ethanol.

C2H5O2CCH3 + NaOH → CH3CO2Na + H3CCH2OH

Ethyl acetate sodium hydroxide sodium acetate ethanol

Continuous Stirred Tank Reactor(CSTR)

Figure 1

stirred tank

CSTR is used

primarily for

liquid phase reaction. It is normally operated at steady state with continuos flow and is

assumed to be perfectly mixed;consequently, there is no time dependence or position

dependence of the temperature , the concentration or the reaction rate inside the CSTR

(Fogler,2006). The feed assumes a uniform composition throughout the reactor , exit

stream has the same composition as in the tank.

General Mole Balance Equation

FAO – FA + 0
V
∫ rA dv = dNa/dT

4
 Assumptions:

For steady state dNA / dt = 0.

Well mixed, therefore rA is the same throughout the reactor.

v v

∫a
0
r dv = ra∫ dv = ra v
0

v = ( Fao − Fa ) / − ra
Rearranging the generation,

5
x = ( Fao − Fa ) / Fao
In terms of conversion,

v = ( Fao x) / − ra
Preparation of Calibration Curve for Conversion vs Conductivity

A calibration curve is a method used in analytical chemistry to determine the

concentrations an unknown sample solution. It is a graph generated by experimental

means,with the concentration of solution plotted on the x-axis and the observable variable

The reaction to be studied is the saponification reaction of ethyl acetate Et(Ac) and

sodium hydroxide (NaOH) . Since this is a second order reaction , the rate of reaction

depends on both concentration of Et (Ac) and NaOH . However for analysis purposes ,

the reaction will be carried out using equimolar feeds of Et(Ac) and NaOH solutions with

6
the same initial concentration . This ensures that both concentration are similar

throughout the reaction .

NaOH + Et(Ac) → Na(Ac) + EtOH

In this experiment , it is required to calibrate the conductivity measurement of conversion

values for the reaction between 0.1M ethyl acetate and 0.1M sodium hydroxide.

Residence Time

The reactor`s residence time is defined as the reactor volume divided by the total feed

flow rated

7
 vCSTR
=
FO
Residence time, τ

There are some assumption have been made in order to using residence time

equation, in this experiment to reduce the complexity of the system being modeled. These

8
assumption include , but are not limited to :steady state in flow and out flow, constant

volume constant temperature and uniform distribution of the substance throughtout the

volume of the system. It also assume that chemical degradation does not occur in the

system in question and the particles do not attach to surfaces that would hinder the flow.

If there are chemical degradation occur in a system, the substances that originally entered

the system may react with other existing compounds and causing the residence time to be

significantly shorter since substance would be chemically consumed and effectively be

removed from the system before it was able to naturally flow out of the system.

(http://en.m.wikipedia.org/wiki/residence_time)

Rate of Equation and Rate Law

The rate of reaction for a reactant and products in a particular reaction can be defined as

how fast or slow the reaction takes place .

Consider the chemical reaction as below:

aA + bB → cC + dD ............(eq 1)

The lowercase letter which a,b, c and d refer to the stoichiometric coefficient while the

capital letter which A,B,C,D refer to the reactant and product.

According to the IUPAC`s Gold Book definition the rate of reaction , r in the

chemical reaction is occur in a closed system which is under a constant - volume

conditions, without build up of reaction intermediates,is defined as :

9
 1 d [ A] 1 d [ B ] 1 d [C ] 1 d [ D]
r=− =− = =
a dt b dt c dt d dt

Where [A],[B],[C],[D] are referred to the molarity of the substances . Based on IUPAC

the times must be in second and the rate of reaction in a positive sign.

The mass balance for a system in general is:

IN -OUT + GENERATION- CONSUMPTION = ACCUMULATION

Mass is conservative entity , hence given a control volume V the sum of mass flows

entering the system will be equal to the sum exiting minus (plus) the consumed

(generated) or accumulated fractions.

10
APPARATUS

Continuos stirred tank reactor: Model BP143

50ml burrete

200ml beaker

Conical flask

100ml measuring cylinder

Conductivity probe

Solution:

-sodium hydroxide , NaOH (0.1M)

-Ethyl acetate , Et (Ac) (0.1M)

-Deionised water

11
-Phenolphtalein

Figure 1: CSTR (model:BP

143)

PROCEDURES

General Start-Up

Procedures

1. The following solution were prepared

a) 40 L of sodium hydroxide , NaOH (0.1M)

b) 40 L of ethyl acetate , Et (Ac) (0.1M)

c) 1 L of hydrochloric acid , HCL (0.25M) , for quenching

2. All valves were ensure initially closed.

3. The feed vessels were charged as follows:

a) The charge port caps for vessels B1 and B2 were opened.

b) The NaOH solution was carefully poured into vessel B1 and Et (Ac) solution was

poured into vessel B2

c) The charge port caps for both vessels were closed.

4. The power for the control panel was turned on.

5. Sufficient water in thermostat T1 tank was checked. Refill as necessary.

6. The overflow tube was adjusted to give a working volume of 10 L in the reactor R1.

12
7. Valves V2, V3 , V7, V8 and V11

8. The unit was ready for experiment.

General Shut- Down Procedures

1. The cooling water valve V13 was kept open to allow the cooling water to continue

flowing.

2. Both pumps P1 and P2 were switched off. Stirrer M1 was switched off.

3. The thermostat T1 was switched off. T he liquid in the reaction vessel R1 was let to

cool down to room temperature.

4. The cooling water valve V13 was closed.

5. Valves V2, V3 , V7, V8, were closed. Valves V4 , V9 and V12 were opened to drain

any liquid from the unit.

6. The power for the control panel was turned off.

13
Preparation of Calibration Curve for Conversion vs. Conductivity

1. The following solution were prepared:

a) 1 L of sodium hydroxide , NaOH (0.1M)

b) 1 L of sodium acetate , Et (Ac) (0.1M)

c) 1 L of deionised water , H2O

2. The conductivity and NaOH concentration for each conversion value were determined

by mixing the following solution into 100ml of deionised water.

a) 0% conversion :100ml NaOH

b)25% conversion:75ml NaOH + 25 ml Et(Ac)

c)50% conversion: 50ml NaOH + 50ml Et(Ac)

d)75% conversion: 25ml NaOH + 75ml Et(Ac)

e)100% conversion: 100ml Et(Ac)

Back Titration Procedures for Manual Conversion Determination

1. A burette was filled up with 0.1 M NaOH solution

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

14
3. A 50ml sample was obtained from the experiment and immediate the sample was

added to the HCl in the flask to quench the saponification reaction.

4. A few drops of pH indicator were added into a mixture

5. The mixture was titrated with NaOH solution from the burrete until the mixture was

neutralized. The amount of NaOH titrated was recorded.

Effect of Residence Time of the Reaction in a CSTR

1. The general start up procedures was performed.

2. Both pumps P1 and P2 were switched on simultaneously and valves V5 and V10 were

opened to obtain the highest possible flow rate into the reactor.

3. The reactor was filled up with both of the solution until it is just about to overflow.

4. The valves V5 and V10 were readjusted to give a flow rate of about 0.1L/min . Both

flow rate must be same. The flow rate was recorded.

5. The stirrer M1 was switched on and the speed was set about 200rpm.

6. The conductivity value at Ql-401 was started monitoring until it does not change over

time. This is to ensure that the reactor has reached steady state.

7. The steady state conductivity value was recorded and the concentration of NaOH

extent of conversion in the reactor was found out from the calibration curve.

8. Sampling Valve V12 was opened and a 5oml sample was collected. A back titration

procedure was carry out to determine the concentration of NaOH in the reactor and the

15
extent os conversion .

9. The experiment (steps 5 to 9) was repeated for different residence times by adjusting

the feed flow rates of NaOH and Et(Ac) to about 0.15, 0.20. 0.25, 0.30. Both flow rates

must be same.

RESULTS:

Table 1: Preparation of calibration curve

16
 Graph 1:Calibration curve (conductivity vs conversion )

Table of experiment 1

Reactor Volume = 9L
Concentration of NaOH in feed vessel= 0.1M
Concentration of Et(Ac) in feed vessel = 0.1M

Volume of 24.7 23.8 23.0 22.5 21.9

NaOH titrated,
Temperature 27.6 27.6 27.8 27.9 27.9
(oC)V1(mL)
Residence
Flow rate of 50.00 33.33 25.00 20.00 16.67
time, τ (min)
NaOH
(mL/min) 0.10 0.15 0.20 0.25 0.30
Volume of
unreacted
Flow rate of
Etquenching
(Ac) 9.88 9.52 9.20 9.00 8.76
HCl, V2 (mL)
(mL/min) 0.10 0.15 0.20 0.25 0.30

Volume
Total of
flowrate ‘
, HCl reacted
Fo (mL/min)
with NaOH , 9.88
0.20 0.48
0.30 0.8
0.40 1.0
0.50 1.24
0.60
V3 (mL)
Conductivity 2.53 2.43 2.23 2.11 1.99
Conservation 98.8 95.2 92.0 90.0 87.6
, X (%)

Rate Constant
,k
2744.44 247.94 115.00 90.00 68.35
(M-1s-1)

Rate of
reaction , -ra
(M/s) 9.9x10-4 1.43x10-3 1.84x10-3 2.25x10-3 2.63x10-3

Table 2: Result effect residence time of reaction in CSTR

17
Graph 2: graph conversion X vs residence time

18
CALCULATION

Sample Calculation

Known quantities:

Volume of sample , Vs = 50 ml

Concentration of NaOH in the feed vessel, CNaOH,f =0.1mol/L

Volume of HCl for quenching , VHCl,s = 10mL

Concentration of HCl in standard solution, CHCl,s = 0.25mol/L

Concentration of NaOH used for titration, CNaOH,s = 0.1 mol/L

Volume of titrated NaOH , V1 =24.7 mL

Total flow rate of solution , Fo = 0.1 mL/min

A) Concentration of NaOH entering the reactor , CNaOH,o

19
1
C NaOH , f
2 CNaOH,O=

20
1
(0.1)
2=

= 0.05 mol/L

21
 B) Volume of unreacted quenching HCl, V2

C NaOH , s
V1
C HCl , s
V2 =

22
 0.1
x
0.25
= 24.7mL

= 9.88 mL

23
 C) Volume of HCl reacted with NaOH in sample , V3

VHCl , s − V2
V3 =

= 10 – 9.88

= 0.12 ml

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

24
(C HCl , s xV3 )
n1 =
1000
=

(0.25x0.12)/1000

0.00003 mol

E) Moles of unreacted

NaOH in sample , n2

n2 = n1

= 0.00003 mol

25
F) Concentration of unreacted NaOH in the reactor , CNaOH

n2
x1000
Vs
CNaOH =

=(0.00003/ 50)x1000

= 0.0006 mol/L

G)Conversion of NaOH in the reactor , X

26
 C 
1 − NaOH  x100%
 C 
 NaOH , 0 
X =

= (1- 0.0006/0.05) x 100%

= 98.8%

H)Residence time ,τ

27
VCSTR
FO
28
 τ =

= 10/0.2

= 50min

I) Reaction rate constant , k

29
 C Ao − C A 
 
 τC 2 
 A 
k =

= ( 0.05 - 0.0006) / (50 x 0.00062)

= 2744.44 M-1 min-1

J) Rate of reaction , -rA

-rA = kCA2

=2744.44 x 0.00062

30
 = 9.9x 10-4 mol/L.min

DISCUSSION

In this experiment we are investigate about saponification reaction by using

Continuos Stirred Tank Reactors (CSTR) 40L (model:BP 143). This experiment has been

conducted to carry out saponification reaction between NaOH and Et(Ac) to determine

the effect of residence time onto the reaction extent of conversion and the reaction rate

constant , beside to compare with manually conversion. The CSTR model is used to

predict the behaviour of chemical reactors, so the key reactor variables such as the

dimensions of the reactor, can be estimated. Saponification process, it is one kind of

process to make a soap and it is continuos reaction . In this experiment , the reaction of

31
saponification is quenching with hydrochloric acid to stop the reaction. The reaction

rapidly reacts and back titration is done to investigate the volume reacted.

From the data collected , two graph had been plotted which are conductivity versus

conversion for manually conversion experiment and conversion X versus residence time

for reaction in CSTR. The calibration curve is plotted to determine the conductivity of the

reaction between NaOH and Et (Ac) at certain percentage of conversion. From graph 1,

we can conclude that the conductivity is decrease proportionally with conversion. It show

that the conductivity is decreased when the volume of NaOH is decreased. When both

reactant with different moles was used, it will give a significant difference of

conductivity .Because of ethyl acetate as reactant and ethanol as product are not electric

conductor , the conductivity of the mixture measurement can be used to measure the

concentration of unreacted NaOH that remains solution that relate to conversion.

Volumetric flow rate is related to the residence time therefore an experiment is

conduct in varies flow rate which is 0.1, 0.15, 0.20, 0.25 and 0.30 L/min. .From the data

collected , we can conclude that the conversion is increase as the volumetric flow rate is

decrease. Fluid entering the reactor at time t and will exit at time t + τ . Residence time , τ

is time that the fluid elements spend within reactor. At high flow rate, the velocity of

fluid moving inside the reactor is high means the reactant spend less time within the

reactor.From graph 2, we can conclude that conversion is linearly increase with residence

time. It can be conclude that the longer the residence time , the more conversion of the

reactant . The higher conversion is 98.8 % at higher residence time which is 45min.

The equimolar reaction between NaOH and Et(Ac) with the same initial reactant`s

32
concentration is the second order reaction. The rate law is -r A=kCACB .The rate of reaction

is L/mol.s. Relate to the rate constant for this order of reaction ,when the `k` value is

increase means more volume of NaOH require to convert a mole of NaOH in 1 second.

From the calculated result, the reaction rate constant is increase as the volumetric flow

rate is decrease.And when the reaction rate constant decrease , the rate of reaction will

increase. The rate of reaction is higher which is r a=2.63x10-3 at the lower rate constant

which is k = 68.35 . There is more moles of NaOH converted for a less volume of NaOH

solution require. This is very important key design to have a high conversion for large

scale production.

In this experiment , there are some zero error and parallax error occur while taking

the measurement of each data.When taking the reading, the position of eye must be

perpendicular to the reading scale of burette and measuring cylinder. Besides, we have to

rinse all the apparatus before we use it to ensure that all apparatus is clean so that any

chemical put into it does not react with any others chemicals. And the most important is ,

need to immediately added to the HCl in the flask that contain the sample to quench the

saponification reaction also to make sure , the sample does not react with others

chemical.By doing all precaution , we can get better results.

From the all calculation , it was obtained that the value of conversion is increase

when the volumetric flow rate decrease. This proved , the theory from the calibration

curve from the first experiment . Therefore the experiment is success.

33
CONCLUSION

As for the conclusion,the purpose of this experiment to determine the reaction rate

constant and as well as the effect of residence time on the conversion of sodium

hydroxide. CSTR is used in order to achieve the objective of this experiment. By done

this experiment , all purposes are met and the result are collected . From the result it show

the conversion is decrease from 98.8% to 87.6% when the flow rate is increase from 0.20

mL/min to 0.60 mL/min.From the graph conversion versus residence time , it can be

conclude that conversion is increase proportionally with residence time. This proved , the

theory from the calibration curve from the first experiment .When increasing the flow

34
rate , the reaction rate constant become smaller and the rate of reaction become

higher.The experiment is successful because the entire objectives have been achieved and

related to the theory of study .

RECOMMENDATIONS

1. Divide into two teams which is the first team in charge of the CSTR 40L machine

while the second team would carry out the back titration procedures.

2. Make sure all of the valves closed and open as needed and there is no leaks from the

reactor in order to make sure CSTR 40L machine is running appropriately to prevent

harm to the machine and individual that used the machine.

3. Controlled the valve carefully and slowly when adjusting the flow rate to make sure

flow rate will stabilize and the experiment will run smoothly.

35
4. During titration , use the suitable apparatus with appropriate size and scale to the

amount to be measured.

5. Make sure all the error is avoided to get more accurate result.To avoid parallax error ,

make sure the position of eye must be parallel to reading scale.

6. Hydrochloric acid for quenching should be prepared early and added to the samples as

soon as possible so that the reaction between NaOH and Et(Ac) cannot proceed because

the NaOH that`s not reacted will neutralized by HCl.

7. The samples that already mix with HCl should be titrated as soon as possible.

8. Take conductivity reading when the conductivity not changes in time because it change

rapidly in short time.

REFERENCE

1.Fogler, Scott H.Elements of Chemical Reaction Engineering , 4th ed. Englewood Cliffs,

NJ:Prentice hall,2006. Page 12,40

2.Levenspiel,O,Chemical Reaction Engineering , 3rd ed, John Wiley and Sons , New

York , 1999.page 35

3.Thomas, Charles E.Process Technology Equipment and System 3rd edition .Clifton

Park, NY: Delmarcangage Learning , 2011.

36
4.Gilbert F.Froment and Kenneth B.Bischoff.,`Chemical Reactor Analysis and Design,

John wiley &sons , 2th ed ,1990

5.Molarities and dilutions access on 21/03/2015 at [ www.microbiologybytes.com]

6.Mass-mole concentration access on 21/03/2015 at [www.ausetute.com.au]

7.Saponification Definition access on 20/03/2015 at [ chemistry.about.com]

8.Continuos Stirred Tank Reactor access on 20/03/2015 at [www.labequip.co.za]

9.CSTR 40L -CPE554 access on 20/03/2015 at [www.coursehero.com]

10.CSTR 40L access on 19/03/2015 at [www.scribd.com]

11.Residence time access on 19/03/2015 at h ttp://en.m.wikipedia.org/wiki/residence_time

APPENDICES

37