REPUBLIQUE DU CAMEROUN REPUBLIC OF CAMEROON

PAIX-TRAVAIL-PATRIE PEACE-WORK-FATHERLAND
*********** ***********
MINISTERE DE L’ENSEIGNEMENT SUPERIEUR MINISTRY OF HIGHER EDUCATION
*********** ************
UNIVERSITE DE MAROUA THE UNIVERSITY OF MAROUA
*********** ************
FACULTE DES MINES ET FACULTY OF MINES AND
INDUSTRIES PETROLIERES PETROLEUM INDUSTRIES
*********** ************

Département de raffinage et pétrochimie

Cycle : Ingénieurs de conception
LRP615 : TRAVAUX PRATIQUES DE GENIE DE LA REACTION
CHIMIQUE

Filière RPC

NIVEAU : 3

THEME: RAPPORT CHEMICAL REACTION ENGINEERING

SEMESTRE : 6

ETUDIANT : FOGANG OTIS Matricule : 15b348IM

CHARGE DE COURS: Pr ABDOUL WAHABOU

Année académique : 2017/2018

CHEMICAL REACTION ENGINEERING
TABLE OF CONTENT
LABORATORY SAFETY RULES…………………………………………….2
RESUME DES EXPERIENCES
Introduction
Experiment n01: Reaction kinetic studies in a batch reactor…………. 5
1 Objectives………………………………………………………………………………………………….

2 Theory……………………………………………………………………………………………………………

3 Apparatus……………………………………………………………………………………………………….

4 Procedure…………………………………………………………………………………………………..

5 Results and discussions…………………………………………………………………………………..

6 Conclusion and recommendations…………………………………………………………………

7 Literature cited……………………………………………………………………………………………..

Experiment No2. Reaction kinetic studies in a mixed flow reactor………..13

1 Objectives…………………………………………………………………………………………….

2 Theory………………………………………………………………………………………………………

3 Apparatus……………………………………………………………………………………………

4 Procedure…………………………………………………………………………………………..
5 Results and discussions……………………………………………………………………………
6 Conclusion and recommendations………………………………………………………….
7 Literature cited……………………………………………………

Experiment n03: Reaction kinetic studies in a plug flow

reactor.................19
1 Objectives……………………………………………………………………………………………….

2 Theory……………………………………………………………………………………………………….

3 Apparatus…………………………………………………………………………………………………..

Procedure……………………………………………………………………………………………………

5 Result and Calculation………………………………………………………………………………….

6 Conclusion and recommendations…………………………………………………………………

17
 7 Literature cited…………………………………………………………………………………..

CONCLUSION…………………………………………………………………………………………………26

LABORATORY SAFETY RULES

1. NO SMOKING IN THE LABORATORY:

2. Safety glasses will be worn at all times where applicable during laboratory periods. These glasses
will be kept between laboratory sessions in the racks provided.
3. Wear apron (lab overall) in the lab when running apparatus and
handling liquids.
4. Wear rubber gloves when handling liquids.
5. When dangerous chemicals are in use, a second person should be
within call.
6. Find out the location of First Aid Box.
7. Before operating any valve, switch, etc., know precisely what the effect of your manipulation will
be.
8. Turn off all the valves on cylinders of compressed or liquefied gas hen not in use.
9. Students are not allowed to open gas cylinders. Ask the technician.(iv)
10. Report all injuries to instructor and to KFUPM doctor immediately.
11. Attach a label "Please leave on" on fittings, you need "on" for long time.
12. Keep all inflammable liquids or gases away from open electrical equipment and other sources of
ignition.
13. Gas cylinders must be kept in a stand or chained vertically to a bench.
14. Avoid inhalation of gases or vapors of any kind, especially
Methanol Acetone Cyanides
Benzene Chlorine Metal Carbonyls
Aniline Bromine Carbon monoxide
Carbon bisulfide Chlorinated hydrocarbons Phosgene
Nitrobenzene Hydrogen sulfide Arsenic Compounds
Nitric acid (the higher the concentration, Org: compound of Cl, Br, I, the lesser the order)
Mercury NO2, NH2 & CN
Benzene
Oxalates
15. Do not leave cables trailing across the floor of lab.
16. Practice good housekeeping. Clean all spills at once. Return all equipment to proper storage when
not in use. Place all trash in appropriate receptacles.
17. Avoid direct blasts of air on the skin from high-pressure compressed air lines. Never play with air
hoses.
18. Use special vacuum cleaner from laboratory for immediate removal of
mercury spills. Arrangement should be made to contain mercury.
19. Make sure any system being heated is properly vented.
20. Know the location and use of all emergency, protective, and firefighting equipment.
21. Do not smell directly any chemical being heated.
22. Remember that, if a lab smells, do not use it. Inform instructor/lab technician.
23. Do not leave lab while apparatus is on, always inform instructor if you are in a situation to leave
the lab.
17
24. When working above others, be especially careful not to drop tools.
25. Do not wear loose clothing or neckties when working with machinery.
You will not be allowed to enter the lab if you are in loose dress or not wearing covered shoes.
26. Report to the instructor any conditions that are safety hazards.
27. All power wiring is to be installed by an approved electrician.
28. All forms of asbestos should be treated as dangerous.29. Keep the lab tidy.
30. Always remember: SAFETY IS GOOD TECHNIQUE!

ABSTRACT

Laboratory classes have become crucial parts of teaching science subjects. In chemical
engineering there are many unit operation : the mass transfer which describe the passage of a
component from a phase to another, separate from the first by an interface, heat transfer is one of the
most studied subjects of engineering because virtually every industrial process involves at least some
heat exchange, fluid mechanics ;different fluid move through pipe in the process and it is important to
determine the fluid properties and drop pressure for example .During many experiment in some
disciplines the results are obtained after manipulation.

17
 INTRODUCTION

Unit Operations labs are a core element in every Chemical Engineering. They
integrate many elements like (mass and energy balances, thermodynamics, heat transfer,
fluid mechanics, process modeling, problem-solving, analysis, and communication) and
are often the only place where students are exposed to pilot scale processes and get a
flavor of industrial-like equipment. Whereas industrial processes have been for years
governed by strict control principles and are
monitored through modern Supervisory Control and data. The details of experiments
(objective, theory, apparatus, and procedure) are presented in the following.

17
Experiment n01: Reaction kinetic studies in a batch
reactor

Aim:
Conduct a simulation experiment and determine the rate constant for the saponification of ethyl acetate
(A) with NaOH (B) in a batch reactor at a specified temperature. To study the effect of temperature on
the rate constant. To determine the frequency factor and activation energy.

CH3COOC2H5 (A) + NaOH (B)-> CH3COONa + C2H5OH It is an elementary reaction

Ethyl acetate is the limiting reactant

Theory
The Batch reactor is the generic term for a type of vessel widely used in the process industries. In
a batch reactor the reactants and the catalyst are placed in the reactor and the reaction is allowed to
proceed for a given time whereupon the mixture of unreacted material together with the products is
withdrawn. Provision for mixing may be required. In an ideal batch reactor, the concentration and
temperature are assumed to be spatially uniform. In practice, the condition can be approximately
realized by vigorous agitation or stirring. All the elements of the fluid spend the same amount of time
in the reactor, and hence have the same residence time. From the viewpoint of thermodynamics, a
batch reactor represents a closed system. The steady states of the batch reactor correspond to states of
reaction equilibrium.
Batch reactors are simple and needs little supporting equipment, and are therefore ideal for small
scale experimental studies on reaction kinetics. Industrially it is used when relatively small amounts of
material are to treat and when the product demand varies. Batch reactors are often used in the
pharmaceutical industry, where small volumes of high-value products are made.
Researchers typically use a batch reactor to study reaction kinetics under ideal conditions. A batch
reactor can be used to find the reaction rate constant, activation energy and order of the reaction. The
data reflect the intrinsic kinetics for the reaction being investigated.
A typical batch reactor consists of a tank with an agitator and integral heating/cooling system.
Liquids and solids are usually charged via connections in the top cover of the reactor. Vapors and
gases also discharge through connections in the top. Liquids are usually discharged out of the bottom.

17
The advantages of a batch reactor lies in its versatility. A single vessel can carry out a sequence of
different operations without the need to break containment. This is particularly useful when
processing, toxic or highly potent compounds. 

Material Balance:
rate of input - rate of output- rate of disappearance = rate of accumulation

A batch reactor has neither inflow nor outflow of reactants or products while the reaction is being
carried out.  F jo =F j=0 .The resulting general mole balance on species j is

If the reaction mixture is perfectly mixed so that there is no variation in the rate of reaction throughout
the reactor volume, rj can be taken out of the integral and the mole balance can be written as 

Consider an elementary reaction ...aA + bB --> cC + dD

Rate of disappearance of A = -rA= dNA/dt

Where NA is the number of moles in the reactor at any time Constant volume conditions can be
assumed for most of the liquid phase reactions or for gas phase reactions with no change in number of
moles Then NA=V*CA where CA is the concentration of A in the reactor.

Then -rA=dCA/dt

Then for the reaction given above

Where.... k= rate constant

a is the order of reaction w.r.t A and b is the order w.r.t B. If the order of the reaction w.r.t each
reactant are equal to the stoichiometric coefficients of these reactants, then the reaction is elementary.
Else it is non elementary.

17
 Order and the rate constants of the reaction can be obtained by experiments. Mainly two types of
analysis may be used for rate law determination. (a) Integral method of analysis
(b) Differential method of analysis.
Integral method of analysis
Consider a reaction A+B --> C+D 

Assume a rate equation.

Like   

where k is the rate constant.

In terms of conversion and using the 

Where M=CBo/CAo and XA is the conversion of A.

M is the initial ratio of concentrations of B (C Bo)to A(CAo) in the reactor.
After breakdown into partial fractions, integration and rearrangement, the final result is

Plot 

Where, t= time, M = CBo/CAo,

  XA is conversation of A at given time 

the above equation is valid for M>1.

If the data points fits well into a straight line then the assumption of second order kinetics is true. The

17
rate constant may be calculated from the slope of the line .

If M=1 then,

The rate equation may be approximated as 

1 1
Then the integrated form of the rate equation is  − =Kt
CA CAO

1 1
Then plot  − vst
CA CAO
If the rate equation assumed is right, then the plot fits well into a straight line with slope=k.
b) Differential method of analysis.

 Hypothesize a rate equation. Let this be . Where n is the assumed order.

 Obtain concentration (CA) vs. time data from the batch experiments. Draw CA vs. time. Draw
tangents at various points. Find the slopes. These slopes are dCA/dt are the rates of reaction (-
rA) at these concentrations.
 Taking logs on both sides of the rate equation will give ln(-rA)=lnk+n.ln(-C A ¿
Plot of in(-rA) vs. in(-CA) will give a straight line with slope n (order) if the assumed form of rate
equation is correct may be obtained from the intercept.
The reaction rate, r, is generally dependent on the reactant concentration and the rate constant (k).
The rate constant can be determined by using a known empirical reaction rates that is adjusted for
temperature using the Arrhenius temperature dependence. Generally, as the temperature increases so
does the rate at which the reaction occurs.
Temperature dependency of rate is given by Arrhenius equation.

 
17
Where k is the rate constant.k0 is the frequency factor. E is the activation energy, R is the gas
constant ,T is the absolute temperature.

Apparatus: Measuring cylinders, stop watch

Procedure for conducting the experiment:

1. Standardise the NaOH stock solution and note down its concentration. Note down the strength
of ethyl acetate stock solution.
2. Calculate the volume of NaOH (VB) and ethyl acetate (VA)( required to make the required
initial concentration ratio of M(a value equal to or greater than 1) and total reactor
volume(select the required volume batch reaction vessel). Choose initial molar ratio of B to A
(M) to be taken. Choose stock concentration of A and the stock concentration of B. Chose the
reaction temperature. Now calculate the volume of stock solutions of B and A to be taken so as
to maintain the chosen M and the total volume of the reactor.
VA +VB = VT... (1)
VT is the total reactor volume
M = (CBS*VB)/(CAS*VA) = moles of B/ moles of A
VB/VA = .. . (2)
From Eq (1) and (2) , VA =......mL , VB=......mL
Where VA and VB are the the volumes of ethyl acetate and NaOH stock to be added to the
reactor.
Cas and Cbs are the concentrations of stock solutions of A and B.
3. Add the calculated volume of NaOH into the reactor. Start the stirrer. Switch on the
conductivity meter.
4. Switch on the heater and set the temperature at the desired value. Pump the water from heating
tank for circulation in the jacket .So the temperature in the reactor is maintained at the required
temperature.
5. Add the required (calculated) volume of ethyl acetate solution (preheated to the required
temperature) to the reactor and at the same time start the stopwatch.
6. At different time intervals of 30s, 1, 2, 3,5,7,10,15 .min ,note down the conductivity meter
reading (conductivity in mS/cm) of the reaction mixture. Note: Some conductivity meters may
display conductance (mS) not the conductivity (mS/cm) [Refer theory for more information].
7. This procedure is continued until no change in the value of conductivity meter reading is
observed.
8. Determine the concentration of unreacted NaOH in the reaction mixture by using the
conductivity meter calibration equation. Since the conductivity meter calibration at 28°C is
only provided, calculate the conductivity meter reading at the required temperature using the
temperature compensation equation provided.
9. Repeat the experiment at different temperatures.
Proceed to calculations as explained in Section A.

Result ,Observations and Calculations (section A)

A -> ethyl acetate
B -> NaOH
Concentration of NaOH in the stock solution= gmol/L

17
Concentration of ethyl acetate in the stock solution=gmol/L

C BS ×V B
M= =¿  moles of B/ moles of A
C AS ×V A
C AS ×V A
Initial concentration of A in the reaction mixture,C AO= =.....gmol/L
V A +V B
C BS ×V
Initial concentration of B in the reaction mixture C Bo= B
=.....gmol/L
V A +V B
CAS and CBS are the concentrations of stock solutions of A and B.

Tabular column: For Temperature=

Calculations:
Concentration of unreacted NaOH in the reaction mixture= CB=gmol/L

(from conductivity meter calibration)

As the conductivity meter calibration is available only at 280C, the conductivity meter reading obtained
at a given temperature of reaction is to be corrected for 280C.
Temperature compensation for conductivity mete

Where, YT =conductivity meter reading at any temperature T in mS/cm

Y28 = conductivity meter reading at a temperature of 280c in mS/cm
Obtain Y28 corresponding to measured conductivity meter reading ( YT) using the equation above.
Conductivity meter is calibrated for concentrations of NaOH in the reaction mixture at a temperature
of 280.
Obtain the Concentration of NaOH at 280 using the calibration equation given below

Where, CB= Concentration of NaOH at time t

Y28= Conductivity meter reading for solution at time t, corrected for 280c
Concentration of ethyl acetate in the reaction mixture,
=gm. ol/L
Conversion of EA,

17
  

Since the reaction is elementary, the reaction rate is given by.

Where k is the rate constant.

In terms of conversion and for M>1,

Where
M=CBo/CAo and XA is the conversion of A.
After breakdown into partial fractions, integration and rearrangement, the final result is

Where 
t= time, M=CBo/CAo and XA,XA is conversation of A at given time
the above equation is valid for M>1.
Plot

the rate constant may be calculated from the slope of the line = .
If M=1, then
The rate equation may be approximated as −r A =K C2A
1 1
Then the integrated form of the rate equation is  − =Kt
CA CAo
1 1
then the plot f (Ca)= − vst
CA CAo
The plot will yield a straight line with slope=k.
or plot XA/1-XAthe slope of the line is kCA0. Obtain k
Rate constant =........ (Liter / gmol) min-1

Obtain the rate constant at three or more different temperatures.

Temperature Rate constant k
T in 0 k in (L/gmol)min-1

17
From Arrhenius Equation,

Plot lnk vs 1/T

Determine the activation energy (E) and the frequency factor (ko) from the slope and intercept of the
above plot.

Intercept= lnk0
Slope=-E/R
R is the gas constant
Activation energy= E=J/mol
Frequency factor, k0=min-1(liter/gmol)
Activation energy= E= J/mol

Result:
Discussion: if we change the conductivity in the rate expression by concentration, pressure the
method used for determination of constant rate is the same but it unit change .The value is identical
like the literature value otherwise the method is incorrect

Conclusion and recommendation

Literature cited

  Chemical Reaction Engineering (3rd Edition), Octave Levenspiel, 1999, John Wiley & Sons
Elements of Chemical Reaction Engineering (4th Edition), H. Scott Fogler, 2005, Prentice Hall
Chemical Reactor Analysis and Design (2nd Edition), Gilbert F. Froment and Kenneth B. Bischoff,
1990, John Wiley & Sons Fundamentals of Chemical Reaction Engineering (1st Edition), Mark E.
Davis and Robert J. Davis, 2003, The McGraw-Hill Companies, Inc. MIT Open Courseware Lecture
notes in Chemical and biological Reaction Engineering. http://ocw.mit.edu/courses/chemical-
engineering/10-37-chemical-and-biological-reaction-engineering-spring-2007/lecture-
notes/lec09_03072007_w.pdf

17
Experiment No2. Reaction kinetic studies in a mixed
flow reactor

Aim:
Conduct simulation based experiments to determine the rate constant for the saponification of ethyl
acetate with NaOH at different temperatures using a mixed flow reactor (continuous stirred tank
reactor). Also calculate the frequency factor and activation energy for the reaction. Discuss on
temperature dependency of rate constant
CH3COOC2H5 (A) + NaOH (B) ->CH3COONa + C2H5OH It is an elementary reaction
Ethyl acetate is the limiting reactant

Introduction
Flow Reactors: There are two types of flow reactors in common use in the chemical industry.
They are the continuous stirred tank reactor (CSTR) and the tubular reactors. CSTR or Mixed flow
reactor (MFR) is configured much like a batch reactor except reactants and products continuously flow
in and out of the reactor. Steady state flow reactors are ideal for industrial purposes when large
quantities of material are to be processed and when the rate of reaction is fairly high to extremely high.
Flow reactors need more supporting equipments like pumps. But good product quality can be obtained.
Theory:
The continuous stirred-tank reactor (CSTR), also known as backmix reactor, is a common ideal reactor
type in chemical engineering. Perfect mixing is assumed in case of Ideal CSTR.

In a perfectly mixed reactor, the output composition is identical to the composition of the material
inside the reactor, which is a function of residence time and rate of reaction. The ideal CSTR model is
often used to simplify engineering calculations and can be used to describe research reactors. In
17
practice it can only be approached, in particular in industrial size reactors.

Space time ( ) is the time required to process one reactor volume of feed at specified condition.

=V/volumetric flow rate of feed

MASS BALANCE EQUATION

rate of input - rate of output- rate of disappearance = rate of accumulation

There are some basic assumptions made in analyzing CSTR reactors. These are

 The reactor runs at steady state i.e. all of the time derivatives go to zero.
 None of the variables (temperature, concentration, reaction rate, etc.) are functions of position,
i.e. all of the spatial derivatives go to zero.
 The conditions that exist at the exit are the same as those everywhere in the reactor.

Since steady state is assumed, the dNj/dt term is equal to zero. Setting the rate term equal to a -rj, the
equation can now be solved for the volume to yield

Fj0 molar flowrate of reactant j

Fj :-output molar flowrate of reactant j
rj:-rate of reaction of reactant molecule j
V:-volume of the reactor
Nj :-number
Fi0 of moles of component j:- the molar flow rate can be expressed as the product of the concentration
of the species and the volumetric flow rate (V0).
Fj0=Cj0*v0
the design equation for CSTR is given by

(A)

Volume of a CSTR with given influent flow rate and feed composition to achieve a required
conversion may be obtained from the above equation, if the rate equation is known. -rA in the above
equation correspond to the exit conversion or concentration. Rate equation for a given reaction can be
obtained using a CSTR. For a single reaction say, A+B-->C+D
Assume the rate equation to be and a constant density system Experiments to be
performed with different space times in the reactor with the known ratio of reactant B to A (M) in the
inlet. Steady state concentration of A may be analysed for each run.

Now equation A can be written as

17
 (B)

for MFR

Plotting vs. yields a straight line passing through origin if the assumed
equation is correct. The slope=k. The equation holds good for M=1 or greater than 1.
If the data do not fit by a straight line assume different equation and proceed as above.

Apparatus: conductivity meter

Procedure:
1.Standardise the NaOH stock solution and note down its concentration.
2. Calculate the concentration of ethyl acetate in stock solution
3.Fill the reservoirs with NaOH and ethyl acetate stock solutions
4.Measure the volume of the reactor.
5. Switch on the pump and allow ethyl acetate to flow into the reactor at certain flowrate and measure
the flowrate (V A ) using rotameter.

6. Set the required temperature to be maintained in the reactor.Switch on the heater to heat the reactor
contents to the required temperature.
C Bo
7. Calculate the flowrate of NaOH (V B ) required to keep the desired value of M(M¿ ¿ . M may be
C AO
greater than or equal to one. Calculate the total flowrate (Q).
8. Adjust the flowrate of NaOH to the calculated value, without changing the EA flowrate.
9. Calculate the actual value of M obtained after adjusting the flowrates.
10. Calculate the space time using the total flow rate.
11. Start the stirrer in the reactor. Close the drain valve completely. Allow the reaction to proceed till
steady state is attained, as indicated by constant reading in the conductivity meter.
12. Note down the conductivity (in mS/cm) of the reaction mixture in, after steady state is attained.
Note: Some conductivity meters may display conductance (mS) not the conductivity (mS/cm) [Refer
theory for more information].
13. Determine the concentration of unreacted NaOH in the reaction mixture by using the conductivity
meter calibration equation.
14. Repeat steps (6) to (12) for different EA flowrates.
15. Conduct the experiment at different temperatures
Observations and calculations:
A Ethyl acetate
B NaOH
Strength of Ethyl acetate in stock = C AS= ------------------------ gmol/L

Strength of NaOH in stock solution=C BS= ------------------------ gmol/L

Diameter of the reaction vessel, d = -----------------------cm

Height of the vessel upto reactor outlet, h = -----------------------cm

17
 π D2 h
V = volume of the reactor= = = -----------------------cm3
4
=L

Calculations:
Ethyl acetate flow rate = V A = ------------------------------LPH
VB/VA = M(CAS/CBS) Flow rate of NaOH required to keep the desired M ,

Flow rate of NaOH set, = LPH Total flow rate Q= VA+VB = Space time , = V/Q = min Actual value of
V B ×C BS
M(obtained in the experiment) =
V A ×C AS
= Initial concentartion of ethyl acetate in the feed mixture,

CAo = --------------------gmol/L
Concentration of NaOH in the feed mixture,
CBo = (VB*CBS)/Q CBo = --------------------gmol/L
As the conductivity meter calibration is available only at 280C, the conductivity
meter reading obtained at a given temperature of reaction is to be corrected for 280C.
Temperature compensation for conductivity meter

17
Where ,
YT =conductivity meter reading at any temperature T in mS/cm
Y 28= conductivity meter reading at a temperature of 280C in mS/cm
Obtain Y 28corresponding to measured conductivity meter reading ( YT) using the equation above.
Conductivity meter is calibrated for concentrations of NaOH in the reaction mixture at a temperature
of 280C. Obtain the Concentration of NaOH at 280C using the calibration equation given below
Conductivity meter calibration equation for 280C.

Where,
C B= Concentration of NaOH in the reaction mixture at steady state
Y28 = Conductivity meter reading for solution, corrected for 280C
Concentration of unreacted NaOH in the reaction mixture at steady state,
CB=         gmol/L (obtained from the conductivity meter calibration graph)
Concentration of ethyl acetate in the reaction mixture at steady state,

= --------------------gmol/L
CA
Conversion of ethyl acetate, X A =1−
CAO
Performance equation for MFR with rate equation of the form −r A =k C A C B
can be written as = ( ) (B) for MFR
Plotting ( ) vs yields a straightline passing through origin. The slope=k. The equation holds good for

M=1 or greater than 1. Plot a graph of Vs. CAoT

From the graph get, k = -------------------------------liter/((gmol)(min)) Similarly the experiment may be

17
performed with different temperatures and the rate constants at these temperatures may be determined.
Obtain the rate constant at three or more different temperatures.

From Arrhenius Equation,

Plot lnk vs 1/T

Determine the activation energy (E) and the frequency factor (ko) from the slope and
intercept of the above plot.
Intercept= lnk0
Slope=-E/R
R is the gas constant
Frequency factor, ko=min-1(liter / gmol)
Activation energy= E=J/mol
Results:
The rate constant for the saponification of Ethy acetate with NaOH at a temp of ToC, k =
-------------------------------liter/((mol)(min)) Discuss and conclude on the temperature dependency of
rate constant. The activation energy (E) for the reaction=J/mol
the frequency factor (ko) =min-1(liter / gmol)

Discussion if we change the conductivity in the rate expression by concentration,

pressure the method used for determination of constant rate is the same but it unit
change. The value is identical like the literature value otherwise the method is incorrect.

Conclusion and recommendation

Literature cited

Chemical Reaction Engineering (3rd Edition), Octave Levenspiel, 1999, John Wiley & Sons Elements
of Chemical Reaction Engineering (4th Edition), H. Scott Fogler, 2005, Prentice Hall Chemical
Reactor Analysis and Design (2nd Edition), Gilbert F. Froment and Kenneth B. Bischoff, 1990, John
Wiley & Sons Fundamentals of Chemical Reaction Engineering (1st Edition), Mark E. Davis and
Robert J. Davis, 2003, The McGraw-Hill Companies, Inc. MIT Open Courseware Lecture notes in
Chemical and biological Reaction Engineering. http://ocw.mit.edu/courses/chemical-engineering/10-
37-chemical-and-biological-reaction-engineering-spring-2007/lecture-notes/lec09_03072007_w.pdf

17
Experiment n03: Reaction kinetic studies in a plug flow reactor

Aim:
To determine the rate constant for the saponification of ethyl acetate with NaOH at ambient
temperature of 280C using a Plug flow reactor.
CH3COOC2H5 (A)+ NaOH (B)-> CH3COONa + C2H5OH. It is an elementary reaction
Ethyl acetate is the limiting reaction

Theory
Tubular reactors are one category of flow reactors. These reactor have continuous inflow and outflow
of materials. In the 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 stirring prevents 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.

Ideal tubular reactor is referred as a plug flow reactor (PFR). PFRs are frequently referred
to as piston flow reactors. The key assumption is that as a plug flows through a tubular reactor, the
fluid is perfectly mixed in the radial direction but not in the axial direction (forwards or backwards).
Each plug of differential volume is considered as a separate entity, effectively an infinitesimally small
batch reactor, limiting to zero volume. As it flows down the tubular PFR, the residence time ( ) of the
plug is a function of its position in the reactor. In the ideal PFR, the residence time distribution is
therefore a Dirac delta function (small and tall) with a value equal to τ. The PFR model works well for
many fluids: liquids, gases, and slurries. An ideal plug flow reactor has a fixed residence time: Any
fluid (plug) that enters the reactor at time t will exit the reactor at time t + , where τ is the residence

17
time of the reactor.
Residence time in the reactor is equal to the space time if the conditions in the reactor like pressure and
temperature are same as those at the entrance. 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.
The absence of longitudinal mixing is the special characteristics of this type of reactor. It is an
assumption at the opposite extreme from the complete mixing assumption of the ideal stirred tank
reactor. 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

Mass Balance
Steady state molar balance over small elemental volume ΔV yields

The conversion, XA, is defined as:

XA = (inlet concentration - outlet concentration) / (inlet concentration)
Volume of a PFR with given influent flow rate and feed composition to achieve a required conversion
may be obtained from the above equation, if the rate equation is known. The 3rd term in the above
equation may be integrated if the rate equation is known. Rate equation for a given reaction can also be
obtained using a PFR. For a single reaction say, A+B->C+D
Assume the rate equation to be −r A =K C A C B and a constant density system

Experiments to be performed with different space times in the reactor with the known ratio of reactant
B to A (M) in the inlet. Steady state concentration of A at the reactor outlet may be analyzed for each
run.
Now equation A after integration with for M>1 , can be written as

XA
=vs τ
1−X A

Plotting

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yields a straight line passing through origin if the assumed equation is correct. The slope=k.
XA
For M=1, the performance equation is =K C Ao τ
1−X A
XA
so the plot of vs τ
CAO ¿ ¿

yields a straightline passing through origin if the assumed equation is correct. The slope=k.
If the data do not fit by a straight line assume different rate equation and proceed as above.
Note: For theory on conductivity meter, refer the «Theory Section «for Batch reactor

Procedure for conducting the experiment:

1) Note down the concentration of ethyl acetate(EA) and NaOH in stock solution
2) Fill the reservoirs with NaOH and ethyl acetate stock solution
3) Calculate the volume of the tubular reactor.
4) Switch on the pump and allow ethyl acetate to flow into the reactor at certain flowrate and
measure the flowrate (vA) using rotameter.
5) Set the required temperature to be maintained in the reactor. Switch on the heater to heat
the reactor contents to the required temperature.
6) Calculate the flowrate of NaOH (V B ) required to keep the desired value of¿). M may be
greater than or equal to one. Calculate the total flowrate (Q).

7) Adjust the flowrate of NaOH to the calculated value, without changing the EA flowrate.
8) Calculate the actual value of M obtained after adjusting the flowrates.
9) Calculate the space time using the total flow rate.
10) Start the stirrer in the reactor. Close the drain valve completely. Allow the reaction to
proceed till steady state is attained, as indicated by constant reading in the conductivity
meter.
11) Note down the conductivity (in mS/cm) of the reaction mixture in, after steady state is
attained. Note: Some conductivity meters may display conductance (mS) not the conductivity
(mS/cm) [Refer theory for more information].
12) Determine the concentration of unreacted NaOH in the reaction mixture by using the
conductivity meter calibration equation.
13) Repeat steps (6) to (12) for different EA flowrates.
14) Conduct the experiment at different temperatures

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Results Observations and calculations:

A -> Ethyl acetate

B -> NaOH
Strength of Ethyl acetate in stock solution = C AS= ------------------------ gmol/L

Strength of NaOH in stock solution= C BS= ------------------------ gmol/L

Diameter of the tube ,d = -----------------------cm

Coil diameter , Dc =        cm
Number of turns= Nt =
V = volume of tubular reactor = ( πd2/4)× Dc Nt = = -----------------------cm3
V =----------------------- L
Tabular columns:

Calculations:
Calculate the total flow rate Q=V A +V B + = LPM

Calculate the space time , = V/Q =       min

V B ×C BS
Set value of M =
V A ×C AS

Concentartion of ethyl acetate in the feed mixture,

CAo = --------------------gmol/L
Concentration of NaOH in the feed mixture,

CBo = --------------------gmol/L
As the conductivity meter calibration is available only at 280C, the conductivity
meter reading obtained at a given temperature of reaction is to be corrected for 280C.

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Temperature compensation for conductivity meter

Where,
YT =conductivity meter reading at any temperature T in mS/cm
Y28 = conductivity meter reading at a temperature of 280C in mS/cm
Obtain Y28 corresponding to measured conductivity meter reading ( YT) using the equation above.
Conductivity meter is calibrated for concentrations of NaOH in the reaction mixture at a temperature
of 280C.
Obtain the Concentration of NaOH at 280C using the calibration equation given below Conductivity
meter calibration equation for 280C.

Where,

CB= Concentration of NaOH in the reaction mixture at steady state

Y28 = Conductivity meter reading for solution, corrected for 280C

Concentration of unreacted NaOH in the reaction mixture at steady state,
CB= gmol/L (obtained from the conductivity meter calibration graph)
Concentration of ethyl acetate in the reaction mixture at steady state,

CA= --------------------gmol/L
CA
Conversion of ethyl acetate, = X A =1−
C AO
(CA/ CAo)= Performance equation for PFR with rate equation of the form

for M>1 , can be written as

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 1 M− X A
Plotting × ln ¿Vs C Ao τ yields a straightline passing through
M −1 M ¿¿
origin if the assumed rate equation is correct. The slope=k.
For M=1, the performance equation is
XA
So the plot of =K C Ao τ vs C Ao τ
1−X A
yields a straight line passing through origin. The slope=k.

Graph for M >1

From the graph we get,
Slope = k =.............. L/(g mole. min)
Similarly the experiment may be performed with different temperatures and the
rate constants at these temperatures may be determined.
Obtain the rate constant at three or more different temperatures.

From Arrhenius Equation,

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Plot lnk vs 1/T
Determine the activation energy (E) and the frequency factor (ko) from the slope and intercept of the
above plot.
Intercept= lnk0
Slope=-E/R
R is the gas constant
Frequency factor, ko=min-1(liter / gmol)
Activation energy= E= J/mol
Results:
The rate constant for the saponification of Ethy acetate with NaOH at a temp of ToC,
k = -------------------------------liter/((mol)(min)

Discussion if we change the conductivity in the rate expression by concentration,

pressure, the method used for determination of constant rate is the same but it unit
change. The value is identical like the literature value otherwise the method is incorrect.

Conclusion and recommendations

Literature cited

Chemical Reaction Engineering (3rd Edition), Octave Levenspiel, 1999, John Wiley & Sons Elements
of Chemical Reaction Engineering (4th Edition), H. Scott Fogler, 2005, Prentice Hall Chemical
Reactor Analysis and Design (2nd Edition), Gilbert F. Froment and Kenneth B. Bischoff, 1990, John
Wiley & Sons Fundamentals of Chemical Reaction Engineering (1st Edition), Mark E. Davis and
Robert J. Davis, 2003, The McGraw-Hill Companies, Inc. MIT Open Courseware Lecture notes in
Chemical and biological Reaction Engineering. http://ocw.mit.edu/courses/chemical-engineering/10-
37-chemical-and-biological-reaction-engineering-spring-2007/lecture-notes/lec09_03072007_w.pdf

Conclusion
The unit operations laboratory is employed to reinforce to senior chemical engineering for us and the
basic chemical engineering principles associated with various pieces of equipment. The unit operations

17
laboratory is also used to familiarize ours us with the safety concerns regarding each piece of
equipment and about operational issues. The result of manipulation is to confirm or not the theory
value. The knowledge and skills give us to acquire in our unit operations laboratory are the
understanding and the ability to operate the unit operations of gas absorption, heat transfer,
evaporation, fluid mechanic and distillation, ability to conduct a Hazard and Operability Analysis
ability to scale pilot data to industrial levels. in addition to these specific
chemical engineering skills, we require competence in criteria.

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