ABSTRACT From this experiment, our objectives are to carry out the saponification reaction between NaOH and

Et(Ac) in plug flow reactor, to determined the reaction rate constant and the rate of reaction of the saponification process. First of all, the equipment is set up before started the experiment. After collecting the data, the value of reaction rate constant and rate of reaction is calculated. The reaction rate constant we get for 600ml/min flowrate is 17.25L/mol.min, for the 500mL/min reaction rate constant is 17.44L/mol.min, for the 400mL/min reaction rate constant is 15.93L/mol.min, for the 300mL/min reaction rate constant is 18.32L/mol.min, for the 200mL/min reaction rate constant is 25.58L/mol.min and for the 100mL/min reaction rate constant is 34.10L/mol.min. Besides that, we are also able to determine the rate of reaction for this process. The rate of reaction we get for flowrate of 600ml/min is 0.0373mol/L.min, for the 500mL/min the rate of reaction is 0.0304mol/L.min, for the 400mL/min the rate of reaction is 0.0237mol/L.min, for the 300mL/min the rate of reaction is 0.0155mol/L.min, for the 200mL/min the rate of reaction is 0.0068mol/L.min and for the 100mL/min the rate of reaction is 0.0016mol/L.min. Then, a graph of conversion factor against residence time is plotted. From the graph we can see that the conversion factor is directly proportional to the residence time. As the residence time increases, the conversion factor also increases.

INTRODUCTION In addition to the Continue Stir Tank Reactor (CSTR) and batch reactors, another type of reactor commonly used in industry is the tubular flow reactor. It consists of a cylindrical pipe and is normally operated at steady state, as is the CSTR[1]. Tubular flow reactors are usually used for gas phase-reactions. A schematic of industrial tubular reactors are shown in figure below:

Figure 1: Tubular reactor schematic. Longitudal flow reactor. Excerpeted by special permission from Chem. Eng., 63(10), 211(Oct.1956). Copyright 1956 by McGraw-Hill, Inc., New York

In the tubular reactor, the reactants are continually consumed as they flow down the length of the reactor. In the ideal tubular reactor, which is called the plug flow reactor, specific assumptions are made about the extent of mixing: 1. no mixing in the axial direction, i.e., the direction of flow 2. complete mixing in the radial direction 3. a uniform velocity profile across the radius. Plug flow reactor is an ideal tubular reactor with laminar flow behaviour. The reactants pass through the tube; the reactants are converted progressively along the length of reactor. The reactants are continuously consumed and the product is formed as the flow preceded the length of the reactor. There is no radial variation in concentration. Consequently, the reaction rate, which is function of concentration for all but zero-order reactions, will also vary axially.
Plug flow-no radial variations in velocity, concentrations, temperature, or reaction rate

Figure 2: Plug flow reactor

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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 of two kinds: 1. mixing in longitudinal direction due to vortices and turbulence 2. incomplete mixing in radial direction in laminar flow conditions Flow in tubular reactor can be laminar, as with viscous fluids in small-diameter tubes, and greatly deviate from ideal plug-flow behaviour, or turbulent, as with gases. Turbulent flow generally is preferred to laminar flow, because mixing and heat transfer are improved. For slow reactions and especially in small laboratory and pilot-plant reactors, establishing turbulent flow can result in conveniently long reactors or may require unacceptable high feed rates. For most chemical reactions, it is impossible for the reaction to proceed to 100% completion. The rate of reaction decreases as the percent completion increases until the point where the system reaches dynamic equilibrium (no net reaction, or change in chemical species occurs). The equilibrium point for most systems is less than 100% complete. For this reason a separation process, such as distillation, often follows a chemical reactor in order to separate any remaining reagents or by products from the desired product. These reagents may sometimes be reused at the beginning of the process, such as in the Haber process. Tubular flow reactors are usually used for this application which are: 1. Large scale reactions 2. Fast reactions 3. Homogeneous or heterogeneous reactions 4. Continuous production 5. High temperature reactions

OBJECTIVES The objectives of this experiment are: 1. To carry out the saponification reaction between NaOH and Et(Ac) in tubular flow reactor. 2. To determine the reaction rate constant. 3. To determine the effect of residence time on the conversion in the tubular flow reactor.

THEORY In a plug flow 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 stirring prevent complete mixing of the fluid in the tube. Hence the properties of the flowing stream will vary from one point to another, namely in both radial and axial directions. The rate expression can be shown to be -rA = k [A] [B] Where if [A] is equal to [B], this simplify to -rA = k [A]2 In the general case the order of the reaction is not known and is shown by -rA = k [A] If the inlet concentration, [A] is known, k can be determined. The reaction: NaOH + CH3COOC2H5 Ethyl Acetate CH3COONa Sodium Acetate + + C2H5OH Ethyl Alcohol

Sodium Hydroxide +

can be considered equal-molar and first order with respect to both sodium hydroxide and ethyl acetate i.e. second order overall, within the limits of the concentration (0-0.1M) and temperature (20-40oC) studied.

The steady state conditions will vary depending on concentration of reagents, flowrate, volume of reactor and temperature of reaction. For this experiment, we will let the flowrate as the vary component. For a time element t and a volume element V, the mass balance for species i at the reactor is given by the following equation: Q C t- Q C
A A v A A v+v

t - r Vt = 0
A

where Q : molar feed rate of reactant A to the reactor, mol/sec A C : concentration of reactantA
A

r : rate of disappearance of reactant A, mol/ltsec

A

The conversion, X, is defined as: X = (initial concentration - final concentration) / (initial concentration) Since the system is at steady state, the accumulation term in Equation (3.1) is zero. Equation (3.1) can be written as: -Q C - r V = 0
A A A

Dividing by V and taking limit as V 0 dC /dV = -r /Q

A A A

This is the relationship between concentration and size of reactor for the plug flow reactor. Here rate is a variable, but varies with longitudinal position (volume in the reactor, rather than with time). Integrating, -dV/ Q = dC /r
A A A

At the entrance: V = 0 C =C
A R A0

At the exit: V = V (total reactor volume) CA = CA (exist conversion)

The new expression can be shown to be -rA = k CA2(1-X)2 -rA = FAO dX/dV = voCAO dX/dV ( )

For constant Tubular Flow Reactor volume, flow rate and initial concentrations, the reaction rate constant is: ( )

Where k vo CAO VTFR X

= reaction constant rate = total inlet flow rate of solutions (ml/min) = inlet concentration of reactant NaOH in the reactor (M) = volume for reactor (ml) = conversion

For a tubular reactor, the mass balance for a reactant a is represented by Arranging for initial concentrations of CA and CB and integrate the equation * +

Solving the integration will give you this equation

Where, is the residence time.

APPARATUS 1. Heater 2. Water bath 3. Coiled reaction tube 4. Agitator motor 5. Variable-area flow meter 6. Switch box 7. Steel tube support 8. Collecting tank

Figure 3: Plug flow reactor

PROCEDURES

SECTION A: SET UP THE EQUIPMENT 1. All valves were ensured closed at initial except for valves V4, V8 and V17. 2. The following solutions were prepared: a. 20 liter of sodium hydroxide, NaOH (0.1M) b. 20 liter of ethyl acetate, Et(Ac)(0.1M) c. 1 liter of hydrochloric acid, HCl(0.25M), for quenching. 3. The both feed tank B1 and tank B2 was filled with the NaOH solution and with the Et(Ac) solution. 4. The water jacket B4 and pre-heater B5 were filled with clean water. 5. The power was turned on at the control panel. 6. Valves V2, V4, V6, V8, V9 and V11 were opened. 7. Both pumps P1 and P2 were switched on. P1 and P2 were adjusted to obtain flow of approximately 300ml/min at both flow meters Fl-01 and Fl-02. Make sure both flow rates are the same. 8. Both solutions were allowed to flow through the reactor R1 and overflow into the waste tank B3. 9. Valves V13 and V18 were opened on pump P3 to circulate the water through pre-heater B5. The stirrer motor M1 was switched on and the speed was set to about 200 rpm to ensure homogeneous water jacket temperature.

SECTION B: START THE EXPERIMENT 1. Procedures for section A were performed. 2. Valves V9 and V11 were opened. 3. Both NaOH and Et(Ac) solutions was allowed to enter the plug reactor R1 and empty into the waste tank B3. 4. Both pumps P1 and P2 were switched on. P1 and P2 were adjusted to obtain flow of approximately 300ml/min at both flow meters Fl-01 and Fl-02. Make sure both flow rates are the same. The flow rates were record. 5. The inlet (Ql-01) and outlet (Ql-02) conductivity values were monitored until they do not change over time. This is to ensure that the reactor has reached steady state.
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6. Both inlet and outlet steady state conductivity values were recorded. The concentration of NaOH exiting the reactor and extent of conversion were found from the calibration curve. 7. Sampling valve V15 was opened and a 50ml sample was collected. A back titration procedure was carried out manually and the concentration NaOH in the reactor and the extent of conversion were determined. 8. Steps 4 until 7 was repeated for different values of feed flow rates of NaOH and Et(Ac). Make sure that both flow rates are the same.

RESULTS Experiment 1 Conversion (%) 0 25 50 75 100 Solution Mixture 0.1M NaOH (mL) 0.1M Na(Ac) (mL) 100 75 50 25 0 0 25 50 75 100 Water (mL) 100 100 100 100 100 Concentration Of NaOH (M) 0.0500 0.0375 0.0250 0.0125 0.0000 Conductivity (mS/cm) 6.94 5.79 4.64 3.57 2.58

Conductivity vs Conversion
8 7 Conductivity (mS/cm) 6 5 4 3 2 1 0 0 20 40 60 Conversion (%) 80 100 120 Conductivity (mS/cm) Linear (Conductivity (mS/cm)) y = -0.0438x + 6.892 R = 0.999

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Experiment 2 Reactor volume, VTFR = 0.4 L Concentration of NaOH in feed tank, CAO = 0.1 M Concentration Et(Ac) in feed tank, CBO = 0.1 M

Flow No rate of NaOH

Flow rate of Et(Ac)

Total flow rate Residence of solutions (ml/min) time, (min) Inlet Outlet Conversion X (%)

Reaction rate constant (L/mol.min)

Rate of reaction, (mol/L.min)

conductivity conductivity (mS/cm) (mS/cm)

(ml/min) (ml/min)

1 2 3 4 5 6

300 250 200 150 100 50

300 250 200 150 100 50

600 500 400 300 200 100

0.667

7.6 7.6 7.0 6.8 6.4 5.8

5.8 5.7 5.6 5.0 4.6 4.2

99.9

1485

1.485 x 10-3

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Residence time, (min)

0.67 0.80 1.00 1.33 2.00 4.00

1.13 1.38 1.56 2.45 5.25 13.29

Conductivity vs Conversion
8 7 Conductivity (mS/cm) 6 5 4 3 2 1 0 0 20 40 60 Conversion (%) 80 100 120 Conductivity (mS/cm) Linear (Conductivity (mS/cm)) y = -0.0438x + 6.892 R = 0.999

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Graph X/(1-X) against residence time

0.04 0.035 0.03 0.025 X/(1-X) 0.02 0.015 0.01 0.005 0 0 0.2 0.4 0.6 0.8 1 1.2 residence time Graph X/(1-X) against residence time Linear (Graph X/(1-X) against residence time)

Graph 1: Graph X/(1-X) against residence time

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SAMPLE CALCULATION Experiment 1: Slope = -0.043x Y-intercept = 6.892 Y = -0.043x + 6.892 Experiment 2: To find conversion of NaOH in the reactor For volume of titrated NaOH, V1 = 0.0185L 1. Conc. Of NaOH entering the reactor, CNaOH,0, Where concentration of NaOH in the feed vessel, CNaOH, f = 0.1 M CNaOH,0 = (CNaOH,f) / 2 = 0.1 M / 2 = 0.05 M 2. Volume of unreacted quenching HCl, V2, Where concentration of NaOH used for titration, CNaOH,s = 0.1 M; Concentration of HCl in standars solution, CHCl,s = 0.25 M; Volume of titrated NaOH, V1 = 0.0185L. V2 = (CNaOH,s / CHCl,s ) x V1 = (0.1M / 0.25 M) x 0.0185 L = 7.40 x 10-3 L

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3. Volume of HCl reacted with NaOH in sample, V3 Where volume of HCl for quenching, VHCl,s = 0.01 L V3 = VHCl,s V2 = 0.01 L 7.40 x 10-3 L = 2.6 x 10-3 4. Moles of HCl reacted with NaOH in sample, n1 n1 = CHCl,s x V3 = 0.25 M x (2.6 x 10-3 L) = 6.5 x 10-4 mol 5. Moles of unreacted NaOH in sample n2 = n1 = 6.5 x 10-4 mol

6. Conc. Of unreacted NaOH in the reactor, CNaOH Where: volume of sample, Vs = 0.05 L CNaOH = n2 / Vs = (6.5 x 10-4 mol) / 0.05 L = 3.25 x 10-5M 7. Conversion of NaOH in the reactor, X X = (1 (CNaOH / CNaOH,0 )) x 100% = (1 (3.25 x 10-5M / 0.05 M)) x 100% = 99.9 %

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To find residence time Where reactor volume, VTFR = 0.4 L and total feed flowrates, V0 = 0.593 L/min Residence time, = VTFR / V0 = 0.4 / 0.6 = 0.667 min To find reaction rate constant K = V0 (X) VPTRC (1-X) = 0.6 . 0.99 0.4 x 0.1 1- 0.99 = 1485 L/mol.min To find rate of reaction -rA = kCA02 ( 1 X )2 = 1485 ( 0.1 ) 2 x ( 1 0.99 )2 = 1.485 x 10-3 mol / L.min

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SAMPLE OF CALCULATION Reactor volume, o Flowrate of NaOH Flowrate of Et(Ac) = 0.4L = 300mL/min = 300mL/min Conversion, X = 53.49%

Inlet conductivity = 9.3mS/cm Outlet conductivity = 7.5mS/cm

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

Residence time, =V 0 = (0.4)/(0.6)

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= 0.67min

Reaction rate constant ( )

k = 0.6/ (0.4 x 0.1) [0.5349/(1 0.5349)] = 17.25 L/mol.min

Rate of reaction -rA = kC2AO(1-X)2 = (17.25) (0.1)2(1 0.5349) = 0.0373 mol/L.min

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DISCUSSIONS By doing this experiment, we are able to carry out the saponification reaction between NaOH and Et(Ac) in tubular flow reactor. At the end of the experiment, we are also able to determine the reaction rate constant by using the formula and to determine the effect of residence time on the conversion in the tubular flow reactor. The experiment is started by running up the equipment in order to start the saponification process. From Figure 3, the coiled reaction tube is where the saponification process to occur. The saponification process can be done in two ways whether variation in temperature or variation in contact time. In this experiment, we will let the flowrate of both solutions as the varying components because the flowrate of both solutions is controlled by the temperature of the reactor. At the end of the experiment, the saponification process is successfully done. After that, we are needed to determine the reaction rate constant and the rate of the reaction for the saponification process depends on the vary flowrate of both solution sodium hydroxide and ethyl acetate. NaOH + CH3COOC2H5 Ethyl Acetate CH3COONa Sodium Acetate + + C2H5OH Ethyl Alcohol

Sodium Hydroxide +

The overall reaction order for the saponification process is second ordered, the reaction rate constant can be determined by applied the equations below, where -rA = k CA2(1-X)2 -rA = FAO dX/dV = voCAO dX/dV ( )

For constant plug flow reactor volume, flow rate and initial concentrations, the reaction rate constant is: ( )

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The reaction rate constant we get for flowrate of 600ml/min is 17.25L/mol.min, for the 500mL/min reaction rate constant is 17.44L/mol.min, for the 400mL/min reaction rate constant is 15.93L/mol.min, for the 300mL/min reaction rate constant is 18.32L/mol.min, for the 200mL/min reaction rate constant is 25.58L/mol.min and for the 100mL/min reaction rate constant is 34.10L/mol.min. From the reaction rate constant we determined, we can see that the value is increase as the flowrate is decrease. Only for 400mL/min we can see that the value of reaction rate constant is decrease that is from 17.44L/mol.min to 15.93L/mol.min. This is maybe due to the same value of the flowrate and the volume of the tank reactor. When the volume and the flowrate is the same, this will give effect to the value of reaction rate constant as the both are equipped in the formula in calculate the reaction rate constant. The rate of reaction also can be determined after we had done find the reaction rate constant. The rate of reaction we get for 600ml/min flowrate is 0.0373mol/L.min, for the 500mL/min the rate of reaction is 0.0304mol/L.min, for the 400mL/min the rate of reaction is 0.0237mol/L.min, for the 300mL/min the rate of reaction is 0.0155mol/L.min, for the 200mL/min the rate of reaction is 0.0068mol/L.min and for the 100mL/min the rate of reaction is 0.0016mol/L.min. After all value of rate of reactions has been calculated, a graph of conversion factor against residence time is plotted. From the graph that had been plotted, we can say that the conversion factor is directly proportional to the residence time. Where, when the residence time increases, the conversion factor also increases. Although we had also done the titration in this experiment, but the data collected in the titration is quite useless because we doesnt use the data for any calculation. It is just like doing it without any reasons. But we are still thankful because we can improve our titration skill by doing this experiment.

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CONCLUSION From this experiment, we are able to carry out the saponification reaction between NaOH and Et(Ac) in tubular flow reactor. We are also able to determine the reaction rate constant for the saponification process. The reaction rate constant we get for flowrate of 600ml/min is 17.25L/mol.min, for the 500mL/min reaction rate constant is 17.44L/mol.min, for the 400mL/min reaction rate constant is 15.93L/mol.min, for the 300mL/min reaction rate constant is 18.32L/mol.min, for the 200mL/min reaction rate constant is 25.58L/mol.min and for the 100mL/min reaction rate constant is 34.10L/mol.min. Besides that, we are also able to determine the rate of reaction for this process. The rate of reaction we get for 600ml/min flowrate is 0.0373mol/L.min, for the 500mL/min the rate of reaction is 0.0304mol/L.min, for the 400mL/min the rate of reaction is 0.0237mol/L.min, for the 300mL/min the rate of reaction is 0.0155mol/L.min, for the 200mL/min the rate of reaction is 0.0068mol/L.min and for the 100mL/min the rate of reaction is 0.0016mol/L.min. A graph of conversion factor against residence time is plotted. From the graph that had been plotted, we can say that the conversion factor is directly proportional to the residence time. Where, when the residence time increases, the conversion factor also increases. This experiment was a success.

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RECOMMENDATIONS There are several recommendations that can be taken in order to get more accurate result that are: 1. Before carry out the experiment, please consult with technician on how to run the equipment so that you can save your time and energy while doing the experiment. 2. It is recommended that this experiment should be repeated at various other temperatures to investigate the relationship between the reaction rate constant and the rate of reaction. 3. It is further recommended that the experiment be repeated using dissimilar flow rates for the NaOH solution and ethyl acetate solutions to investigate the effect that this will have upon the saponification process. 4. For obtained more accurate results, run several trials on tubular flow reactor so we can take the average value from each different molar rates. 5. Be careful when doing the titration because we only want the last drop of NaOH that will convert the solution to light pale purple colour. The excess of drop of NaOH will give effect on the result in the calculations.

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REFERENCES 1. Fogler, H.S (2006). Elements of Chemical Reaction Engineering, 4th Edition, New Jersey:Prentice Hall 2. Perry, R. H., D. Green, Perrys Chemical Engineers Handbook, 6th edition, McGraw-Hill, 1988. 3. Instruction Manual Turbular Flow Reactor, Jan2006, at

http://eleceng.dit.ie/gavin/DT275/CET%20MKII%20manual%20issue%2016.pdf 8.00pm at 14 Feb 2011

4. http://en.wikipedia.org/wiki/Plug_flow_reactor_model at 8.30pm on 14 Feb 2011 5. http://www.che.boun.edu.tr/courses/che302/Chapter%2010.pdf at 9.45pm on 14 Feb 2011

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Figure 4

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Figure 5: Structure of reactor in plug flow reactor

Figure 6: Example graph conversion against residence time

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