Table of Contents

Table of Contents...................................................................................................1 ABSTRACT.............................................................................................................. 2 OBJECTIVES............................................................................................................4 THEORY.................................................................................................................. 4 APPARATUS............................................................................................................ 7 METHODOLOGY...................................................................................................... 7 CALCULATION....................................................................................................... 13 DISCUSSION..........................................................................................................15 CONCLUSION........................................................................................................ 16 RECOMMENDATIONS............................................................................................16 REFERENCES........................................................................................................17 APPENDIX.............................................................................................................17

ABSTRACT
A CSTR approximation used to describe the behavior of a homogeneous reactor and a heterogeneous catalyst bed is analyzed under transient conditions. When uniformity in reactant concentration exists, the volume of the heterogeneous CSTR is defined as the equivalent volume in the gas phase of intermediates that are adsorbed on the active catalytic surface at the reactor operating condition. Several reaction models are tested to determine the conditions under which a first-order response can be used directly to predict kinetic information useful for modeling. The relaxation time constant is obtained from the transient response of the reaction product subsequent to a step change of the reactant by using a firstorder assumption. In this experiment, there are indicate two experiment which are a batch reaction procedure and effect of temperature on the reaction rate constant. The value of the 1/CA, reaction rate constant, k and rate of the reaction. The volume if the titration in experiment A is increase when the time is increase. For the experiment B, the volume of the titration is decrease when the time is increase in all temperature. The rate of reaction at the temperature 40 0C in first minute is -0.00014 mol/L.min. For the value of reaction rate
constant at temperature 40 0C is -0.4921 min-1mol-1.

INTRODUCTION
The CSTR (Continuously Stirred Tank Reactor) is a define as reactor model in which the reactor content is assumed single phase and well mixed. It has one inlet and one outlet. Before running the CSTR, it needs to know about reactions. A reaction package must therefore be assigned to the CSTR reactor. From the assigned reaction package, you can specify equilibrium reactions as well as kinetic reactions. It have a reaction rate that is specified either as homogeneous (mol/s/m3) or heterogeneous (mol/s/kg catalyst). The CSTR is implemented a single phase reactor. The reactor phase must be specified. Only reactions that take place in the specified phase can be selected. If you want to calculate the reactions in combination with the phase equilibrium and you have only equilibrium reactions, you can use the Equilibrium Reactor. For single-phase equilibrium systems in which the equilibrium constants are not known in advance, you can use the Gibbs minimization reactor. If homogeneous kinetic reactions are selected, the reactor volume needs to be specified. If heterogeneous kinetic reactions are selected, either the catalyst mass needs to be specified, or the catalyst density and volume must be specified. The catalyst mass is then calculated as the product of catalyst density and catalyst volume. If both homogeneous and heterogeneous reactions are selected, the reactor volume needs to be specified. Also, two out of three must be specified for catalyst volume, catalyst density and catalyst mass (the third one will be calculated from the relation catalyst mass = catalyst density times catalyst volume). The catalyst volume will be substracted from the reactor volume to obtain the effective reaction volume. There is no specification for catalyst porosity; if the reactive phase exists inside the catalyst pores, catalyst density or volume must be specified to reflect this.

Energy balance The CSTR can be modeled either as an isothermal process, or as process with external heating or cooling. In the first case, outlet temperature is specified. In case of specified heat duty, the reactor temperature is calculated from the energy balance:

where H denotes the mixture enthalpy, Q the specified heat duty, rj the reaction extents and (HR,j) the heat of reaction for the j-th reaction (see enthalpy balance details below for heat of reaction). For the enthalpy balance, three options are available to use enthalpy and heat of reaction, or use enthalpy and do not use heat of reaction. See reaction enthalpy for details. The heat duty can be specified directly or via an energy inlet stream. If heat duty is not specified via an energy inlet stream, an energy outlet stream can be connected that will receive the heat duty for the reactor. After the reactor is solved, the outlet will be flashed at specified pressure (after pressure drop) and at the specified (in case of isothermal) or calculated temperature. If the phase equilibrium is such that phases appear that are not the specified reaction phase, warnings are generated. In this case, the specified heat duty will not be met, as the reactor was solved for enthalpy of a single phase. The enthalpy change resulting from the flash will cause the enthalpy not to be balanced.

OBJECTIVES
1) To study and learn about the CSTR process.

2) To determine the reaction rate constant, k at room temperature

3) To determine reaction rate constant, k at the effect of temperature. 4) To measure the reaction rate, rA throughout time.

THEORY
Flowing Reactors There are two types of flowing reactors in common use in the chemical industry. The continuous stirred tank reactor (CSTR) is configured much like a batch reactor except reactants and products continuously flow in and out of the reactor. A plug flow reactor (PFR) is little more than a pipe into which reactants are injected into one end and products flow out the other. While both of these reactors seem relatively simple the equations that govern the design of the reactors are quite different. A schematic of a CSTR is shown below,
4

Note: these reactors are also referred to as mixed flow reactors. Using the same nomenclature as is shown in the figure in the general balance equation we get
FA0 FA + rAV = dNA dt

There are some basic assumptions made in analyzing CSTR reactors. These are: 1) The reactor runs at steady state i.e. all of the time derivatives go to zero.
2) None of the variables (temperature, concentration, reaction rate, etc) are functions of

position, i.e. all of the spatial derivatives go to zero.

3) The conditions that exist at the exit are the same as those everywhere in the reactor.

Since steady state is assumed, the dNA/dt term is equal to zero. Setting the rate term equal to a rA, the equation can now be solved for the volume to yield,
VCSTR = FA0 FA rA

Fi0, the molar flow rate can be expressed as the product of the concentration of the species and the volumetric flow rate (v0). For instance

FA0 = CA0 v0

Batch Stirred-Tank Reactor (BSTR)

The stirred tank batch reactor is still the most widely used reactor type both in the laboratory and industry. A batch reactor is one in which a feed material is treated as a whole for a fixed period of time. Batch reactors may be preferred for small-scale production of high priced products, particularly if many sequential operations are carried out to obtain high product yields. Batch reactors may also be justified when multiple, low volume products are produced in the same equipment or when continuous flow is difficult, as it is with highly viscous or sticky solids-laden liquids. Because residence time can be more uniform in batch reactors, better yields and higher selectivity may be obtained than with continuous reactors.

The rate of reaction of component A is defined as:

rA = 1 dN A V dt byreaction

(1)

By the definition, if A is a reaction product, the rate is positive where as if it is a reactant which is consumed, the rate is negative. Rearranging the equation 1:
(rA )V = N A0
(2)

dX A dt

Integrating equation 2 will gives,

t = N A0
(3)

dX A ( rA )V

Where t is the time required to achieve a conversion XA for either isothermal or nonisothermal operation.

APPARATUS
1. Continuous stirred tank reactor 2. Spatula 3. Feed tank 4. Flasks 5. Burette 6. Stop watch 7. Waste tank 8. Magnetic stirrer 9. 0.1M Ethyl Acetate 10. 0.1M NaOH 11. 0.25M HCl

METHODOLOGY
Experiment 1: Batch reaction procedure
1. The overflow tube in the reactor is adjusted in the reactor to begin a batch reactor to

give a desired working volume, say 2.5 liters. Pump P1 is switched on and started pumping 1.25 liters of the 0.1 M Ethyl acetate from the feed tank into the reactor. Pump P1 is switch off.
2. Pump P2 is switched on and started pumping 1.25 liters of the 0.05 M NaOH into the

reactor. The stirrer is switched on and the speed is set in the mid range say 180 rpm Pump P2 is stopped immediately and the timing reaction is started. The time is started to record.
3. 10 mL of the 0.25 M HCl in a flask is measured quickly.

4. 50 mL of a sample is collected after 5 minute of reaction by opening the sampling valve and 10 mL of 0.25 M HCL is added immediately prepared in step 3 and mix. The HCL will quench the reaction between ethyl acetate and sodium hydroxide.
7

5. The mixture is titrated with the 0.1 M NaOH to evaluate the amount unreacted HCl. 6. Steps 3 to 5 is repeated for reaction times of 5, 10, 15, 20 and 25 minutes.

Experiment 2: Effect of temperature on the reaction rate constant, k

1. The overflow tube in the reactor is adjusted to begin a batch reactor to give a desired

working volume, say 2.5 liters. Then, pump 1 is switched on and started pumping 1.25 liters of the 0.1 M ethyl acetate from the feed tank into the reactor. The heater is switched on. The cooling water is run.
2. Pump 2 is switched on and the valve is setted for maximum flow rate and started

pumping in 1.25 liters of the 0.1 M NaOH from the feed tank. Pump 2 is stopped and imediately started timing the reaction and time is started to record.
3. 10 ml of the 0.25 M HCL is measured quickly in a flask.

4. 50 mL of the sample is collected after 1 minute of reaction time by opening the sampling valve and 10 mL is added immediately prepared in step 3 and mix. The HCL will quench the reaction between ethyl acetate and sodium hydroxide.
5. The mixture is titrated with the 0.1 M NaOH to evaluate the amount of unreacted HCl.

6. Step 4 to 6 is repeated for reaction times of 5, 10, 15, 20, 25 minute.

7. Step 1 to 7 is repeated for the reaction temperature of 30, 35, 45 0C.

8. Graph C vs T, r vs T, r vs C is plotted. 9. All switches is switch off when finished with the experiment.

RESULT
8

Experiment 1: Batch reaction procedure Reactants CNaOH = 0.5 M CEA = 0.1 M Quenching HCl CHCl = 0.25 M VHCl = 10 mL Sample Vs = 50 mL

Time(Min) 1 5 10 15 20 25 V0 0 15.5 32.6 0 19.5 0

Volume Titration, NaOH(mL) Vf 15.5 32.6 49.9 19.5 39.0 20.3

V 15.5 17.1 17.3 19.5 19.5 20.3

Experiment 2: Effect of temperature on the reaction rate constant, k Temperature: 30 Time(Min) 1 5 10 15 20 25 V0 15.4 0 15.2 0 16.8 0 Volume Titration, NaOH(mL) Vf 31.1 15.2 34.0 16.8 34.1 19.7 V 15.7 15.2 18.8 16.8 17.3 19.7

Temperature: 35 Time(Min) V0 1 5 19.7 0

9

Volume Titration, NaOH(mL) Vf 41.8 23.5

V 22.1 235

10 15 20 25 Temperature: 45 Time(Min)

23.5 0 0 0

47.9 25.2 26.5 27.0

24.4 25.2 26.5 27.0

V0 1 5 10 15 20 25 0 22.3 0 21.5 0 21.3

Volume Titration, NaOH(mL) Vf 22.3 42.0 21.8 43.0 21.3 40.0

V 22.3 19.7 21.8 21.2 21.3 18.7

10

Graph of determining k value Experiment 1 T=250C k=0.6077

Experiment 2 T=400C k= -0.4921

11

T=500C k= -0.3718

T=600C

k= -0.3931

12

Graph of the rate of reaction

CALCULATION
CNaOH : 0.1 mol/liter; CEtAc : 0.1 mol/liter; CHCl : 0.25 mol/liter; VHcl : 10 mL Vsample : 50 mL For the T=400C
Ti me (m in) 1 VNaOH titrat ed (L) (1) 0.016 5 VHCL, unreact ed with sample s NaOH (L) (2) 0.0066 VHCL, unreacte d with samples NaOH (L) (3) 0.0034 Mole HCL reacted with samples NaOH (mol) (4) 0.00085 Mole unreacted NaOH in sample (mol) (5) 0.00085 CNaOH unreacte d with EtAC (mol/L) (CA) 0.017 Steady state NaOH conversion fraction (XA) 0.83 58.82 1/CA

(2)

= (CNaOH / CHcl)x(1) 13

=(0.1/0.25)x 0.0165 =0.0066 (3) = VHcl (2) =0.01-0.0066 =0.0034 (4) = CHCl x(3) = 0.25 x 0.0034 =0.00085 (4) ( CA) =(5) =0.00085 = = = ( XA)= = = (5)/ Vsample 0.00085/0.05 0.017 1 ({ CA}/ CNaOH) 1 (0.017/0.1) 0.83

Others calculation use the same method as the above.

Calculation for the rate of reaction For the T=400C

Time (min) 1 Steady state NaOH conversion fraction , XA 0.83 Rate of reaction, r (mol/L.min) -0.00014

- r = kC NaOH (1 - X A )
2

k= -0.4921 min-1mol-

CNaOH : 0.1 mol/liter r = -0.4921 x (0.1)2 x (1-0.83)2 = -0.00014 mol/L.min Others calculation use the same method as the above. 14

DISCUSSION
Based from the data experiment, for the experiment A which is in batch reaction procedure, the volume of the titration is increase when increasing the time. For the first minute, the volume of the titration is 15 mL and for the 25 minute, the volume of the titration is 17.5 mL. For the experiment B which is effect of the temperature on the reaction rate constant, there is use 3 different temperatures. For the temperature at 40 0C, the volume of the titration should get decreasing when increasing the time. But, from the data of the experiment, the volume of the titration are not stable which fluctuate is occur. The volume of the titration decrease, increase and then decrease back. For the first minute, the volume of the titration is 16.50 mL and for the 25 minute, the volume of the titration is 13.10 mL. For the temperature at 50 0C, the volume of the titration shows increasing when the time is increase. For the first minute, the volume of the titration is 16.60 mL and for the 25 minute, the volume of the titration is 14.20. For the temperature at 60 0C, based from the data of the experiment, the result are not followed the theory which is the volume of the titration should decrease when the time is increasing. It is because there is an error occurs during the experiment. The error that occurs is the temperature at the machine is not stable. It is not fixed as the temperature is setting. It can cause the result inaccurate because the when the sample are taken the temperature as not as the temperature is setting. Besides that, during the titration process, the volume of the NaOH is exceed enter the solution. The solution should change to the light pink but, it become to purple. It is because the result inaccurate. For the first minute the volume of the titration is 16 mL and at 25 minute, the volume of the titration is 14.40 mL.

Based from the experiment A, the experiment is not use any effect and the as the result, the volume of the titration NaOH is increase. For the experiment B, it is use the effect of the temperature. When, the temperature is increasing, the volume of the titration is decrease. Based from the data to determine the rate of constant, the value of 1/CA is increased when the time is increase at the experiment A. Besides that, for the experiment B, the value of the 1/CA is decreasing when the time is increase. It is follow the theory which is when the volume of the titration NaOH is decrease, the value of the 1/CA also decreases. For the table of the rate of reaction, in the experiment A, the value rate of reaction is decrease when the time is increase. For the first minute, rate of reaction is 0.000243 mol/L.min and when the time at 25 minute, the value rate of reaction is 0.00014 mol/L.min. For the experiment B, the rate of the
15

reaction is increase when the time is increase. For the temperature at 40 0C, at the first minute, the value rate of reaction is -0.00014 mol/L.min and at 25 minute, the value rate of reaction is -0.00028 mol/L.min. Besides that, for the temperature at 50 0C, for the first minute, the value of the rate of reaction is -0.000104 mol/L.min and for the 25 minute, the value rate of reaction is -0.00017 mol/L.min. For the temperature at 60 0C, at first minute, the value rate of reaction is -0.00013 mol/L.min and at the 25 minute is -0.00018 mol/L.min. Based from the graph, in experiment A, the graph shows 1/CA is increase proportional to the time and the value of the k that get from the graph is 0.6077 min-1mol-1. For the experiment B, all of the graph shows decreasing. For the temperature at 40 0C, 50 0C and 60 0C, the value of the k are -0.4921, -0.3718 and -0.03931 min-1mol-1 respectively. For the graph rate of reaction versus time, all of the graph shows decreasing.

CONCLUSION
For the experiment in A, the volume of the titration NaOH is increasing when the time is increasing. It is because there is no other effect in this experiment. Besides that, for the experiment B, for the temperature at 40, 50 and 600C is decrease when the time is increasing. Based from the experiment, when the temperature is increase, the volume of the titration is decrease. Based from the 1/CA versus time, all of the temperature show decreasing experiment the graph in the experiment A which is shows proportional increase. For the reaction rate constant, it shows decreasing when the temperature is increase. There are also have some errors occur during the experiment. Firstly, the temperature at the machine is not stable. It is not fixed as the temperature is setting. It can cause the result inaccurate because the when the sample are taken the temperature as not as the temperature is setting. Besides that, during the titration process, the volume of the NaOH is exceed enter the solution. The solution should change to the light pink but, it become to purple. It is because the result inaccurate. This experiment is successfully.

RECOMMENDATIONS
1) The feed tank should always be full of the reactants to avoid pulse occurs during the experiment.
16

2) When taken out the sample, the flask should be flowed with the reactant in the stirrer tank to rinse the dirt inside the flask that might affect the reactions. 3) Gather sufficient technical information about experiment. 4) use the different concentration but same substances to see the result of the volume titration NaOH. 5) Leave more time for CSTR data collection Flow rate calibrations Temperature adjustment

REFERENCES
http://ocw.mit.edu/NR/rdonlyres/Chemical-Engineering/10-37Spring2007/F04D1AB5-8825-4049-A01EC92C96B058DB/0/lec05_02212007_g.pdf http://wiki.biomine.skelleftea.se/wiki/index.php/Well-stirred_batch_reactors Theodore L. Brown, H. Eugene Lemay, Jr. , Bruce E. Bursten, Chemistry, The Central Science, Tenth Edition, 2006 Robert H.Perry, Don W.Green, Perrys Chemical Engineers Handbook, McGraw Hill,1998
http://www.ijsimm.com/Full_Papers/Fulltext2009/text8-3_145-155.pdf

APPENDIX

17

Figure 1 Continuously Stirred Tank Reactor

18