1

Expt No: Date:

BATCH REACTOR – EQUIMOLAR CONSTANT VOLUME SYSTEM

AIM:

To verify the order and determine the rate constant for the reaction between
equimolar concentration of Sodium Hydroxide and Ethyl acetate in a constant volume batch
reactor.

APPARATUS:

Conical flasks, Burette, Pipette and Stop Watch

CHEMICALS:

Sodium Hydroxide (Na OH)

Ethyl Acetate (CH3 COO C2H5)
Acetic Acid (CH3 COOH)
Phenolphthalein Indicator

THEORY:

In the batch reactor the reactants are charged in to a container, well mixed and left to
react for a certain period. The resultant mixture is then discharged. This is an unsteady state
operation where in the concentration inside the reactor varies with time but uniform at any
instant of time.

Writing the material balance

Input = output + disappearance + accumulation

For a batch reactor, first two terms vanish

Rate of loss of reactant A within the reactor due to chemical reaction = - rate of accumulation
of reactant A within the reactor
(-rA)V = -dNA/dt = NA0 dxA/dt
xa
therefore, t = NA0 dxA/(-rAV)
0
For a constant volume batch reactor,
Xa
t = CA0 dxA/(-rA)
0
 2

Determination of order of reaction by the differential method of analysis

Let the rate equation be represented as -rA = k CAn where k is the reaction rate constant
and n is the order of reaction

Taking logarithms on both sides

ln(-rA) = ln k + n ln CA

Draw tangents at different values of CA to the curve of plot of CA vs t. The slopes

of the tangents will be the values of -rA for the corresponding values of CA.

The slope of the approximate linear plot of ln (-rA) vs ln CA gives the order of the
reaction n, the y-intercept gives ln k from which rate constant k can be calculated.

This is only an exercise for verification of order, though it is well known that the
order is 2 since this is an elementary reaction

Verification of order by integral method of analysis

-rA = -dCA/dt = k CAn

dCA/CAn = -k dt
on integration, we get
CA1-n – CA01-n = (n-1)kt

Substituting the value of n as two, k values are calculated for different values of CA.
The steady constant value of k proves that the order of reaction is verified and found to be
two

REACTION :.

In the present experiment the following saponification reaction between Sodium

Hydroxide(NaOH) and ethyl Acetate (CH3 COO C2H5 ) is studied.

NaOH + CH3 COO C2 H5 CH3 COO Na + C2H5OH

PROCEDURE:

Take 250ml of NaOH and 250ml of CH3 COO C2 H5 of known concentrations CA0
and CBO (CA0 = CBO = 0.05N) in a conical flask and start mixing. The conical flask serves as
the batch reactor. Then 10ml of the reaction mixture is taken separately in each of eight
different conical flasks labeled 1 to 8. A reaction time of 5, 10, 15, 20, 25, 30, 40 and 50
minutes is given for each sample respectively. After the reaction time, the reaction is arrested
by adding excess Acetic acid solution of known concentration and volume (0.05N, 20 ml).
 3

The excess Acetic acid is estimated by titration against Sodium Hydroxide solution of known
concentration (0.05N) to determine the moles of unconverted Sodium Hydroxide in the
reaction mixture at the time of arresting the reaction. From this we can find out the
conversion XA at that instant.

OBSERVATION TABLE:

Batch No Time (min) Initial Volume of Volume of NaOH

Acetic acid Added Run down
Vo ml V1ml
1 5
2 10
3 15
4 20
5 25
6 30
7 40
8 50

CALCULATIONS:

Batch Volume of Volume of Moles of Con of

No Acetic acid Acetic acid NaOH NaOH XA XA/(1-XA)
not used used unreacted CA mol/ lit
V1 ml (Vo - V1)ml
1
2
3
4
5
6
7
8

Volume of acetic acid not used (V1 ml) = Volume of NaOH used in the back
Titration
 4

Volume of acetic acid taken (Vo ml) = 20 ml

Volume of acetic acid used for arresting = (Vo – V1) ml
Moles of acetic acid used = (Vo – V1) * 0.05 * 10-3
= Moles of NaOH unused in the reaction
mixture at the time of arresting the
reaction

Concentration of NaOH in the reaction mixture at the time of arresting the reaction

(CA) = Moles of NaOH unused / Volume of reaction mixture.

= [((Vo – V1) * 0.05 * 10-3 / 10*10-3] mol/lit

Initial concentration of NaOH in the reaction mixture = CAO = 0.05/2 = 0.025 mol/lit

Conversion = XA = (CAO – CA)/CAO

The rate constant can also be determined from the linear plot of XA/(1-XA) Vs time t the
slope of which equal to KCAO from which we can determine the rate constant K by the
integral method of analysis with n equal to 2

RESULT:

For the saponification of ethyl acetate by Sodium hydroxide, the order of the reaction
is determined by the differential method of analysis and verified by the integral method of
analysis and found to be 2 and also the rate constant has been determined .

ANALYSIS REPORT:
 5

Expt No: Date:

BATCH REACTOR - NON-EQUIMOLAR CONSTANT VOLUME SYSTEM

AIM:

To determine the rate constant for the reaction between non-equimolar concentrations
of Sodium Hydroxide and Ethyl acetate in a constant volume batch reactor.

APPARATUS:

Conical flasks, Burette, Pipette and Stop Watch

CHEMICALS:

Sodium Hydroxide (Na OH)

Ethyl Acetate (CH3 COO C2H5)
Acetic Acid (CH3 COOH)
Phenolphthalein Indicator

THEORY:

In the batch reactor the reactants are charged in to a container, are well mixed and are
left to react for a certain period. The resultant mixture is then discharged. This is an unsteady
state operation where in the concentration inside the reactor varies with time but uniform at
any instant of time.

Writing the material balance

Input = output + disappearance + accumulation

For a batch reactor, first two terms vanish
Rate of loss of reactant A within the reactor due to chemical reaction = - rate of accumulation
of reactant A within the reactor
(-rA)V = -dNA/dt = NA0 dxA/dt
xA
therefore, t = NA0 dxA/(-rAV)
0
For a constant volume batch reactor,

xA
t = CA0 dxA/(-rA)
0
THE ORDER OF THE REACTION HAS ALREADY BEEN VERIFIED IN EXPERIMENT
I AND VERIFIED TO BE 2
 6

We use the integral method of analysis of data of reactants. For the second order reaction of
non-equimolar concentrations of A and B, A+B….> products,

-rA = -dCA/dt = K CACB M=CB0 / CA0

We get the expression KCA0(M-1)* t = In [(M-XA)/M(1-XA)]

The plot of in [(M-XA)/M(1-XA)] Vs time t gives a straight line of slope equal to

KCA0 (M-1) from which we can determine the rate constant K.

REACTION :.

In the present experiment the following saponification reaction between Sodium

Hydroxide(NaOH) and ethyl Acetate (CH3 COO C2 H5 ) is studied.

NaOH+ CH3 COO C2 H5 ……> CH3 COO Na + C2H5OH

PROCEDURE:

250ml of NaOH and 500ml of CH3 COO C2 H5 of known concentrations CA0 and CBO
(CA0 = CBO = 0.05N) are taken in to a conical flask and start mixing thoroughly. The conical
flask serves as the batch reactor. Then 10ml of he reaction mixture are taken separately in
each of the eight different conical flasks labeled 1 to 8. A reaction time of 5,10,15,20,25,30,
40 and 50 minutes is given for each sample respectively. After the reaction time, the reaction
is arrested by adding excess Acetic acid solution of known concentration and volume (0.05N,
20 ml). The excess Acetic acid is estimated by titration against Sodium Hydroxide solution
of known concentration (0.05N) to determine the moles of unconverted Sodium Hydroxide in
the reaction mixture at the time of arresting the reaction. From this we can find out the
conversion XA at that instant.

OBSERVATION TABLE:

Batch No Time (min) Initial Volume of Volume of NaOH

Acetic acid Added Run down
Vo ml V1ml
1 5
2 10
3 15
4 20
5 25
6 30
7 40
8 50
 7

CALCULATIONS:

Batch Volume of Volume of Moles of Concentration

No Acetic acid Acetic acid NaOH NaOH XA M-XA/M(1-
not used used unreacted CA XA)
V1 ml (Vo - V1)ml Mole/liters
1
2
3
4
5
6
7
8

Volume of acetic acid not used (V1 ml) = Volume of NaOH used in the back titration
Volume of acetic acid taken (Vo ml) = 20 ml
Volume of acetic acid used for arresting = (Vo – V1) ml
Moles of acetic acid used = (Vo – V1) * 0.05 * 10-3
= Moles of NaOH unused in the reaction
mixture at the time of arresting

Concentration of NaOH in the reaction mixture at the time of arresting the reaction (CA) =
Moles of NaOH unused / Volume of reaction mixture.
= [((Vo – V1) * 0.05 * 10-3 / 10*10-3] mol/lit
Initial concentration of NaOH in the reaction mixture = CAO = 0.05/3 = Mol/lit
Conversion = XA = (CAO – CA)/CAO
M= CB0/CA0 =2

GRAPH:

The plot of [(M-XA)/M(1-XA)] Vs time t gives a straight line of slope equal to KC AO (M-
1) from which we can determine the rate constant K.

Related Exercise: (i) Derive rate equation for non Equimolar system for elementary second
order reaction, (ii) analysis the result by doing the experiments with one reactant as excess.

RESULT:

For the saponification of ethyl acetate by Sodium hydroxide, the rate constant has
been determined and found to be
 8

Expt No: Date:

SEMI BATCH REACTOR

AIM:

To study the performance of semi batch reactor for the second order reaction of
saponification of ethyl acetate by sodium hydroxide

APPARATUS:

Conical flasks
Burette
Pipette
Stop watch

CHEMICALS:

Ethyl acetate
Sodium hydroxide
Acetic acid
Phenolphthalein indicator

THEORY:

There are two basic types of Semi batch reactors. In the first type, one of the
reactants is slowly fed to a rector containing the other reactant, which has already been
charged to the reactor. This type of reactor is used when unwanted side reactions occur at
high concentrations of A or the reaction is highly exothermic. In the second type, both the
reactants are fed to a reactor at constant flow rates. In the present case, we are studying the
performance of semi batch reactor of first type.

The performance equation of the semi batch reactor is same as that of constant
volume batch reactor with time t being replaced by t.

K CAo (M-1). t =In [(M-XA )/M(1-XA)]

Over the total reaction time of t minutes, the semi batch reactor is treated as a series
of N (=t/t) constant volume batch reactors.

PROCEDURE:

Take 50ml of NaOH solution of known concentration (0.05N) in the container (a

conical flask of capacity of 250 ml which serves as the reactor) and add ethyl acetate solution
 9

of known concentration (0.05N) at a constant known flow rate for a known reaction or
operation time of t minutes (say 30 minutes, the total volume of the reaction mixture must
increase to about 100ml). Take a sample of 20ml of reaction mixture into another conical
flask and arrest the reaction by adding excess acetic acid of known concentration and volume
(0.05N, 20ml). The quantity of acetic acid in excess is determined by titration against
standard NaOH solution. This gives the quantity of unreacted NaOH left in the reactor at the
time of arresting the reaction (at the reaction time t ) from which we can determine the
conversion of NaOH in the semi batch reactor. We can also determine the conversion
theoretically from the batch reactor performance equation by approximating the semi batch
reactor as a series of N batch reactors. Refer any chemical reaction engineering book for
derivation.
Xa =

OBSERVATIONS:

Volume of NaOH initially taken in the reactor = 50 ml

Normality of NaOH = 0.05 N
Volumetric flow rate of ethyl acetate solution = QB ml/min
Total reaction or operating time of the semi batch reactor = t minutes
Volume of sample of reaction mixture taken for analysis = 20 ml
Volume of acetic acid added to the sample = 20 ml
Normality of acetic acid used = 0.05 N
Volume of NaOH consumed in back titration = X ml
Normality of NaOH used for back titration = 0.05 N

MODEL CALCULATIONS:

Moles of acetic acid left in the analysis sample after arresting the reaction
= Moles of NaOH consumed in the back titration
= X * 10-3*0.05
Moles of acetic acid used to neutralize NaOH to completely arrest the reaction
= 20*10-3*0.05 – X* 10-3*0.05
Moles of Na OH left at the end of reaction time in 20ml analysis sample
= 0.05* (20-X) * 10-3
Volume of reaction mixture in the reactor = (50 + QB * t) ml
Therefore, moles of Na OH left in the reactor at the end of reaction time
= [(50 + QB *t) / 20] * 0.05 * (20-X) * 10-3
Moles of Na OH initially taken in the reactor = 50 * 0.05 * 10-3 = NAO
Experimental value of conversion = XA exp = (NAO-NA)/NAO

THEORETICAL CALCULATIONS:

Total time of semi batch operation = t min

 10

For equimolar concentrations, for a second order reaction by the integral method of
analysis
XA/(1-xA) = kCA0 t k can be calculated by substituting the values of x A, CA0,
t(=30min)

Time for each interval = t/N = t mins

N=1
Volume of ethyl acetate added = t * QB ml
Total volume of reaction mixture = V1 = (50 + t * QB)ml
Moles of Na OH added = NAO1 = 50 * 10-3 * 0.05
Moles of ethyl acetate added = NBO1 = t * QB * 10-3 * 0.05
CB01 = NB01 / V1
CAo1 = NAo1 / V1
M1 = CBo1 / CAo1
k CA o 1 (M1-1) * t = In [(M1 - XA1)/M1 (1-XA1)]
the same k value can be substituted from which xA1 can be calculated

CA1 =CA01 ( 1-XA1)

CBI =CB01 ( 1-XA1/M)
NA1 =NA01 ( 1-XA1)
NB1 =NB01 (1-XA1/M)

N= 2
NB02 =NB1+ Ethyl acetate added in the second interval
=(NB1 + t * QB * 10-3 * 0.05) moles
NA02 = NA1 moles
Volume of the reaction mixture = V2 =(50+2 * t * QB ) ml
CB02 =Nbo2/V2
CA02 =NA02/V2
M2 = CB02/ CA02
K CA 02 (M2-1) * t = In [ ( M2 – XA2 )/M2 (1-XA2)]
the same k value can be substituted from which xA2 can be calculated

The calculations are repeated as above up to N =6

The theoretical value of conversion is XA,th = (NA01-NA6)/NA01= i=I i=6 XAi
 11

Expt No: Date:

ADIABATIC BATCH REACTOR

AIM:

To study the reaction rate under adiabatic condition for hydrogen peroxide and sodium
thiosulfate reaction.

APPARATUS:

Thermoflask, thermometer, stop watch and conical flasks.

THEORY :

The effect on the temperature of the reaction mixture consisting of H2O2 and Na2S2O3
when the reaction is carried out adiabatically can be observed and correlated with the rate of
the reaction. As the reaction is exothermic, temperature increases as the reaction proceeds
and becomes constant when reaction is completed. The rate of the reaction and temperature
for the reaction is correlated to various parameters as
1/(TF – T)2 dT/dt = KOCAO e-E / RT / (TF – TO)

where,

T0 – initial temperature – (K)

TF – Final temperature – (K)
T - Temperature at any instant of time – (K)
K0 – Frequency factor (lit/mol- min)
CA0- Initial concentration of H2O2-(mol/lit)
E -Activation energy – (J/k mol)

EXPERIMENTAL SETUP :

The apparatus consists of an insulated Dewar vessel (Thermo flask ) fitted with a two
holed rubber cork carrying a long mercury thermometer (0-10000C) through one hole and a
glass funnel with a valve in the other. A stopwatch is used to record the time at various
intervals and the temperature is noted.

PROCEDURE :

Prepare solutions of Na2S2O3 and H2O2 each of 0.10(or) 0.05N concentration. Transfer
exactly 200ml of Na2S2O3 solution into the reactor and note its temperature. Transfer exactly
200ml of H2O2 solution. Mix the contents well and after attaining the maximum steady
temperature and record the temperature at regular intervals of time until the maximum
temperature is reached.
 12

OBSERVATIONS and CALCULATIONS

Time T DT/dt 1/[TF-T] ln[(1/(TF-T)2)/ 1/T

(dT/dt)]
Sec
30
60
90
120
150
180
210
240
270
300
330
360
390
420
450
480
510
540
570
600
630
660
690
720
750
 13

GRAPH :

A plot of T vs t is made . various dT/dt values are calculated. Then plot a graph between
1/T Vs In [1/(TF-T)2 dT/dt]. From the Slope and intercept, we can calculate the activation
energy (E) and frequency factor (K0)

RESULT :

Activation energy E = J/k mol.

Frequency factor Ko = lit/mol- min
 14

Expt No: Date:

TEMPERATURE DEPENDENCY OF REACTION RATE

AIM :

To establish the nature of temperature dependency of the reaction rate constant for the
saponification reaction of ethyl acetate with Na OH solution.

APPARATUS ;

Conical flask ( one 1000 ml size and 12 of 250 ml )

Burette
Pipette
Stop Watch

CHEMICALS:

Ethyl acetate
Sodium hydroxide
Acetic acid
Phenolphthalein indicator

THEORY:

The influence of temperature on the rate constant is expressed in terms of an

empirical equation known as Arrhenius equation:

K = ko exp (-E/RT)

Where ko is called frequency factor and E is called the activation energy of the reaction. This
expression fits experiment well over wide temperature ranges and is strongly suggested from
various stand points as being a very good approximation to the true temperature dependency.

As in batch reactor experiment, we determine the value of the rate constant K at a

particular temperature assuming a second order reaction kinetics (i.e. concentration
dependent term f2 (composition) , CA CB . From the values of rate constants at a various
temperatures, we can determine the frequency factor and activation energy (i.e. temperature
dependency) follows:

K1 = K0 exp (-E/RT1) at temp T1

K2 =K0 exp (-E/RT2) at temp T2
In (K1 /K2) =E/R{1/T2 – 1/T1]
E = RT1T2 / (T1 – T2)  (K1/K2)
K0 =K1 /exp(-E/RT1)
 15

REACTION:

The saponification reaction studied is given by

NaOH + CH3COOC2H5 CH3cCOONa + C2H5OH

PROCEDURE:

Place 400ml 0.05N NaOH solution in a 1000ml conical flask which as a reactor.
Transfer 20ml of Acetic acid solution into each of Eight 250ml conical flasks which are
serially labeled. Place the reactor on a hot plate cum magnetic stirrer and start heating by
stirring the contents uniformly till the desired temperature is obtained. Carefully transfer
200ml of 0.05N ethyl acetate into the reactor & start the stopwatch simultaneously. At the
time intervals of 10 minutes, pepett out 20 ml of the reaction mixture, into each of the conical
flask. The Acetic Acid already present in the analysis flask neutralizes the alkali in the
sample reaction mixture and arrests the saponification reaction. Back Titrate these reaction
sample mixtures with aqueous NaOH solution using phenolphthalein as indicator. Note down
the room temperature and conduct the experiment at various temperatures (minimum two
temperatures.)

OBSERVATION

Vol. Of NaOH Vol. Of NaOH Vol. Of NaOH

S.No Time used in Back used in Back used in Back
Min. titration ml. at titration ml. at titration ml. at
temp, T1 temp, T2 temp, T3
1
2
3
4
5
6
7
8
9
10
 16

MODEL CALCULATIONS: ( For temp T1)

CA0 = Initial concentration of Na OH taken in the reactor, mols/litre

CB0 = Initial concentration of ethyl acetate, mols/litre

M= CB0/ CA0

At the time, t = 1 minute

(V1)= ml of HCL excess
= (Volume of Na OH used in back titration)*(Normality of Na OH/Normality of HCL
= Volume of Na OH used in back titration
vol. of HCL added to the sample =20 ml
moles of Na OH left in the reaction mixture = (20 – V1 )*(Normality of HCL)* 10-3

CA = moles of Na OH left in the reaction mixture / (20* 10-3

XA =(CA0 -CA) / CA

Repeat the above calculations for t = 2,…….12mins

The plot of In [(M-XA ) / M(1-XA )] vs t is observed to be a straight line

With slope equal to K CA0 (M-1) from which the rate constant k can be calculated

Repeat the above procedure at the other two temperatures also and the corresponding
k values are noted against the corresponding temperatures.

The plot of In k vs T observed to be a straight line with a slop equal to (-E/R),

y-intercept equal to In ko from which the activation energy E and the frequency factor k0 can
be calculated

TABULATION

T1 T2 T3
t (mins) XA In [(M-XA)/M(1- XA In [(M-XA)/M(1- XA In [(M-XA)/M(1-
XA)] XA XA)]

1
2
3
4
5
6
7
 17

8
9
10

S.No T 1/T K In K
1 T1 K1
2 T2 K2
3 T3 K3

GRAPH:

Plot a graph of ln k vs 1/T, rate constant k and frequency factor k0 can be calculated
from slope and y-intercept respectively

RESULT:

1. Activation energy is determined and found to be

2. Temperature effect on Rate constant
 18

Expt No: Date:

PLUG FLOW REACTOR

AIM:

To study the performance of a plug flow reactor for the second order reaction of
Saponification of Ethyl acetate by Sodium hydroxide.

Theory:

Plug flow reactor is characterized by the fact that the flow of fluid through the reactor
is orderly with no element of fluid overtaking.(or) mixing any other element ahead (or)
behind. Actually there may be lateral mixing of fluid in PFR however there must be no
mixing or diffusion along the flow path.

The necessary and sufficient condition for the plug flow is for the residence time in
the reactor to be the same for all elements of fluid.

For equimolar concentration of NaOH and ethyl acetate, the performance equation is

Xa

 = CAO  dxA/ -rA xA

= CAO  dxA/kCA2
o o
xA
= CAO  dxA/kcA02 (1-xA)2
o

 kCAO  = xA/1-xA

Plot a graph of xA/1-xA (Vs) , the slope of the approximated straight line is k CA0 , from
which the rate constant k can be determined experimentally.

REACTION :

NaOH + CH3 COO C2H5  CH3 COO Na + C2H5 OH

 19

EXPERIMENTAL SET UP :
The set up consists of a transparent glass tube of 8mm diameter and 1.5 length, 15 in
number, connected together. The reactants are allowed to enter at a constant flow rate by
means of Rotameters

PROCEDURE:

Sodium hydroxide and Ethyl acetate solutions of known concentration (CA0 = CB0
= 0.05N) are allowed to enter at constant flow rates in to the plug flow reactor. Sufficient
time is given for system to attain steady –state conditions. Now, product is collected and
reaction is arrested by adding excess acetic acid (20ml, 0.05N). The titration with standard
NaOH is done taking 10ml of mixture.

OBSERVATIONS :

Volume of reactor =V= litres

Volumetric flow rate =v= lits/min
Residence time =  = V/v = min
Normality of acetic acid =0.05 N
Volume of acetic acid for arresting the reaction = 20ml
Normality of NaOH = 0.05 N
Volume of sample = 10ml
Titrate value of NaOH = Xml

CALCULATIONS :

Moles of acetic acid used for arresting =(20-X) * 0.05 * 10-3

Moles of unreacted NaOH = (20-X) * 0.05 * 10-3
CA = Concentration of NaOH at any time = (20-X) * 0.05 * 10-3 /10*10-3
CAO = initial concentration of NaOH = 0.05 /2 =0.025
XA,expt = Conversion of NaOH = (CA0-CA) * 100/CA0

S.NO Flow rate Volume  Reactor

V of (min) mixture CA xA XA,the
(ml/min) Reactor volume
V m3 X ml
1
2
3
4
5
6
7
8
 20

GRAPH :

A plot of 1/ (-rA) vs XA is made and the conversion is calculated by using the area under
the curve, which is equal to  / CA0 or V/FA0 . These are compared with those of the
experimental values.

RESULT :

For the given reaction, the conversion is calculated experimentally and compared
with theoretical values as well as with graphical technique. The rate constant is also
determined experimentally.
 21

Expt No: Date:

MIXED FLOW REACTOR

AIM :

To study the performance of a Mixed Flow Reactor for carrying out a second order
reaction of saponification of ethyl acetate by NaOH

CHEMICALS :

Acetic acid , Sodium hydroxide , Ethyl acetate , phenolphthalein indicator.

THEORY :
In mixed flow reactor, properties of the reaction mixture are uniform
throughout the volume. With equimolar concentration of reactants at inlet for this second
order reaction, the outlet concentration of reactants also remain equimolar.

i.e., CAO = CBO i.e., CA = CB

From the design equation of the CSTR,

/CA0 = V/FA0 = XA/ (-rA),

where –rA = k CA2

A straight line plot is approximated from the plot of xA/(1-xA)2 vs t , the slope of which gives
k CA0 from which the rate constant k can be calculated

REACTION

NaOH + CH3 COO C2H5  CH3 COO Na + C2H5 OH

A B C D

-rA = kCACB = kCA2 as CA = CB at any time

EXPERIMENTAL SETUP

Its consists of a cylindrical container with flow connections for inlet and outlet
sections. The constant inflow of reactants can be maintained by rotameters.
 22

PROCEDURE

Sodium hydroxide and ethyl acetate solutions of known concentrations (CAO = CBO
= 0.05 N ) are allowed to enter at constant flow rates in the mixed flow reactor. Sufficient
time is given for system to attain steady state conditions.. Now product is collected and the
reaction is arrested by adding excess acetic acid(20ml, 0.05N). After mixing thoroughly,
ttitration with standard NaOH is done taking 10ml of mixture.

OBSERVATIONS:

Volume of reactor = V = liters

Volumetric flow rate = v = lits/min
Residence time =  = V/v = min
Normality of the acetic acid = 0.05 N
Volume of acetic acid for arresting the reaction = 20 ml
Normality of NaOH = 0.05 N
Volume of sample = 10 ml
Titrate value of NaOH = X ml
Moles of acetic acid used of arresting = (20-X)* 0.05*10-3
Moles of unreacted NaOH = (20-X)* 0.05*10-3
CA = Concentration of NaOH at any time = (20-X)* 0.05*10-3 /
10*10-3
CAO = Initial concentration of NaOH =0.05 / 2 = 0.025
XA = Conversion of NaOH =(CAO- CA)*100 / CAO

Flow rate Volume of Reaction

v the reactor  mixture CA XA
(ml./min.) V (min.) volume
m3 X ml.

GRAPH :

 A plot of 1/ (-rA) vs XA is made and the conversion is calculated by using the

area under the curve, which is equal to  / CA0 or V/FA0 .
 Plot a graph of xA/(1-xA)2 vs t
 23

These are compared with those of the experimental values.

RESULT :

For the given reaction, the conversion is calculated experimentally and compared
with theoretical values as well as with graphical technique.

The rate constant is also determined experimentally.

 24

Expt No: Date:

COMBINED REACTOR PFR FOLLOWED BY CSTR (MFR)

AIM:

To study the performance of combined reactor in series (PFR - CSTR) for the
saponification of the Ethyl acetate.

CHEMICALS

Ethyl Acetate (0.05N), NaOH(0.05N), Acetic Acid(0.1N).

APPARATUS REQUIRED

Conical flasks, measuring jar(100ml), burette, pipette.

THEORY

For getting maximum conversions for orders greater than 0 (for the types whose rate
concentration curve rises monotonically), the reactors should be connected in series. They
should be connected in such than one the ordering of the units should be plug small mixed.
The reverse ordering should be followed if the ordering should be followed if the order is less
than one.

For reactions where the rate of concentrations curve passes through a maximum or
minimum arrangement of units on the actual shape of the curve, the conversion level desired
and the units available. No simple rules can be suggested.

For present system of the sodium hydroxide and ethyl acetate the rate curve is a
concave.

If the reactors of different types are connected in series such as a PFR followed by
CSTR, we may write for the two reactors.

XA1
V1 / FAO = /CAO =  d XA/ (-rA)
XA0
Where XAO = 0 And

V2 / FAO = (XA2 – XA1) / (-rA)

 25

For the performance equation is

XA1
V1 / FAO = 1 /CAO =  dxA / kCAO 2 (1-xA)2
O
XA1
 k1 CAO = [1/(1-xA)] = [1/(1-xA1)] - 1
o

= xA1/1-xA1 (1)

For the CSTR the performance equation is,

V2 / FAO = 2 / CAO = (XA2 – XA1) / (-rA)

= (XA2 – XA1) / kCAO2 (1-xA2)2

 k 2 CAO = (XA2 – XA1) / (1-xA2)2 (2)

xA2 is find conversion which is determined experimentally = 1-CA/CAO

xA1 is intermediate concentration (2) / (1) given,

2 /1 = {(XA2 – XA1) / (1-xA2)2} x {(1-xA1) / xA1} = V2 / V1

Volume of the CSTR / volume of the plug flow reactor = Constant.

 From, the above the intermediate conversion can be calculated.

EXPERIMENTAL SETUP

The set up consists of a transparent glass tube of 8mm diameter, 1.5m length and 14
number of tubes are connected together serves as the PFR. The out let of the CSTR is
connected to PFR. The reactants are allowed to enter at a constant flow rate by means of
Rotameters.

PROCEDURE

NaOH, CH3COOC2H5 of known concentrations of 0.05N are allowed to enter at a

constant flow rates. Sufficient time is given for the system to attain the steady state. Sample
is collected at the end of the plug flow reactor outlet and 10 ml of this sample is arrested by
adding acetic acid of known concentrations and the volume (0.05N, 20ml)and it is titrated
against NaOH (0.05N) for finding out the conversion using phenolphthalein indicator.
 26

OBSERVATIONS

Volumetric flow rate of ethyl acetate = VA = lit. / min.

Volumetric flow rate of sodium Hydroxide = VB = lit. / min.

Total volumetric flow rate = VA + VB = lit. / min.

Initial concentrations of ethyl acetate = CAO = 0.05/2=0.025

Initial concentrations of sodium hydroxide = CBO = 0.05/2=0.025

-rA = k CACB = kCAO2 (1-XA)2

CALCULATIONS

Moles of acetic acid used for arresting = (20 – X)*0.05*10-3

Moles of unreacted NaOH = (20 – X)*0.05*10-3

CA = Concentrations of NaOH at any time = (20 – X)*0.05*10-3 / 10*10-3

CAO = initial concentrations of NaOH = 0.05/2 = 0.025

XAexpt. = Conversion of NaOH = (CAO – CA) * 100/CAO

-A = KCA CB= KCAO2 (1-XA)2

XA1
XA1 can be calculated from V1/FAO =  / CAO =  dXA / (-rA)
XA0
Where
XAO = 0
And
XA2 can be calculated from
V2 / FAO = (XA2 – XA1) / (-rA)

Final Conversion = XA2 =

 27

S.No Flow Rate Volume Reaction CA XA 2.

V of the  mixture
(ml/min) reactor (min) volume
Xml
1
2
3
4
5
6
7
8

When rate constant is known the intermediate conversion, intermediate concentration can be predicted using
(i) Analytical method and (2) Graphical method.

RESULT
 The rate constant k is determined by experimentally.
 Experimental values for Intermediate and final conversions are compared with
values obtained by analytical and graphical methods.
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Expt No: Date:

PACKED BED REACTOR

AIM:

To determine the reaction rate constant , K for the saponification of ethyl acetate with sodium hydroxide at
ambient conditions.

INTRODUCTION:
In an ideal plug flow reactor (PFR) there is no mixing in the direction of flow and complete mixing
perpendicular to the direction of flow. Concentration of the reactant varies along the length of the reactor but
not in the radial direction. In case of a non-catalytic packed bed reactor (PBR), an additional contact surface is
provided for the reaction by the packed bed. It is expected that the yield of the reaction should be high in case of
a packed bed reactor as compared to an equal volume plug flow reactor.
THEORY:
REACTION :
NaOH + CH3COOC2H5 CH3COONa + C2H5OH
(A) (B) (C) (D)
The above reaction is second order reaction (n=2)
For second order reaction
-rA = - dCA /dt
-rA = K(CA)2
Where –rA is the rate of disappearance of A , CA is the concentration of A at anytime t , K is the rate constant .
Assuming plug flow condition to exist in the reactor, then under steady state condition:
The performance equation for the packed bed reactor is:
Ʈ = VR/VO
In terms of concentration , we can write,
Ʈ = - 1/K ʃCA CAO dCA/CA2
On solving the bove equation we get,
Ʈ = 1/K [1/CA]CA CAO
Ʈ = 1/K [(CAO-CA)/CACAO]
Rate constant, K= (CAO – CA)/ Ʈ CAO CA
Degree of Conversion , XA = (CAO – CA)/CAO
Also, a plot of Ƭ Vs. XA/(1-XA) shall yield a straight line for an assumed second order reaction with slope =
1/(KCAO). From this slope rate constant, K can be calculated.
DESCRIPTION:
The set-up consists of a glass column packed with raschig rings and two feed tanks . Reactants are fed to the
reactor through distributor , fixed at the bottom of the column . Rotameters are provided to measure the
individual flow rate of chemicals . The flow rate can be adjusted by operating the needle valve provided on
respective rotameter. The compressed air is used for circulation of feed. Pressure gauge , pressure regulator ,
and safety valve are fitted in the air compressed line. The concentration of feed and the product coming out
from the reactor are analysed by chemical titration .
EXPERIMENTAL PROCEDURES:
STARTING PROCEDURE:
1.)Prepare 20L of N/10 NaOH solution by dissolving 80gm of sodium hydroxide in 20L of distilled water.
2.) Prepare 20L of N/10 ethyl acetate solution by mixing 176 gm (or 196 ml) of ethyl acetate in 20 L of distilled
water.
3.) Take 20ml of N/10 hydrochloric acid in measuring cylinder
4.) Fil the burette by N/10 sodium hydroxide (Standard Solution).
5.) Close all the valves V1-V10 .
6.) Open valve V4 ams V6 , fill sodium hydroxide solution in feed tank A.
7.)Close valve V4 and V6.
 29

8.) Open valve V5 and V7, fill ethyl acetate solution in feed tank B.
9.)Close V5 and V7.
10.) Connect compressed air supply to set-up valve V1.
11.) Connect electric supply to the set-up.
12.) Open valve V1 and set air pressure 0.5 to 1kg/cm2 by pressure regulator and pressure gauge .
13.) Pass sodium hydroxide and ethyl acetate into the reactor by allowing equal flow rate controlled by valve
V2-V3.
14.)After about 10 min or time equal to the residence time of the reactor (which ever is greater ) collect exact 10
ml of sample from the outletin measuring cylinder that already contain 20 ml of hydrochloric acid.
15.) Transfer the sample solution in conical flask .
16.) Titrate the solution , using phenolphthalein as an indicator against N/10 sodium hydroxide (add NaOH
from the burette).
17.) Repeat the experiment for different flow rates of feed .

CLOSING PROCEDURE:
1.)When experiment is over , stop the flow of feed by closing the valve V 2-V3.
2.)Reduce air pressure to 0 kg/cm2 by pressure regulator and pressure gauge.
3.) Close the valve V1.
4.) Drain the feed tanks and reactor by opening the valve V 8-V10.

OBSERVATION AND CALCULATION :

DATA
Working volume of reactor VR = ______ Lit
Volume of HCl VHCl = 20 ml
Volume of sample VSAMP = 10ml
Normality of NaOH in feed solution N NaOH = 0.1 g eq/L
Normality of NaOH used for titration N1 = 0.1 g eq/L
Normality of HCl NHCl = 0.1 g eq/L

OBSERVATION TABLE:
S.NO VA(LPH) VB(LPH) V1(ml)

CALCULATIONS:
CAO=NNaOH/2 (mol/L)
HClO = (VHCl NHCl)/1000 (mole)
HClR=HClO –(V1N1)/1000(mole)
CA = HClR/VSAMP × 1000 (mole/L)
XA = (CAO-CA)/CAO
Ʈ= (VR ×60)/(VA+VB) (min)
K= (CAO- CA)/(Ʈ CAO CA)(L/mole min)
Expt No: Date:

RTD STUDIES IN PACKED BED COLUMN

AIM

To determine the behavior of the packed bed reactor through RTD studies and to
determine the dispersion number.

APPARATUS

Stop clock, Syringe and titration setup.

CHEMICALS

Oxalic acid, NaOH and phenolthalien indicator.

PROCEDURE

Plug flow reactor and mixed flow reactor are the two main types of flow that
represent the extreme behavior of any flow reactor. A mixed flow reactor offers a complete
mixing while plug flow reactor is assumed to have no mixing at all. This assumption is
theoretical, in actual no reactor meet either of the flow reactor real reactors deviate from the
ideal plug flow or mixed flow reactors because of channeling of fluid, by recycling of fluid
or by creation of stagnant regions in the reactor. In all types of reactors this type of flow
should be avoided to achieve a good performance of the unit.

The non-ideal behavior can be studied by the Residence time distribution approach.
Many types of models can be used to characteristic non-ideal flow with in the vessels. Some
draw the analogy between mixing in actual flow and a diffusional process. These are
dispersion models. Others build a chain or network of ideal mixers, while still others
visualize various flow regions connected in series or parallel. Such models are useful in
accounting for the deviation of real systems, such tubular vessels or packed beds, from plug
flow; others describe the deviation of real stirred tanks from the ideal or mixed flow; and still
others account for fluidization represent tubular vessels or packed beds.

D / uL called the vessel dispersion number is the parameter which measures the
extent of axial dispersion. Thus D/uL> 0 for the plug flow and  for the mixed flow.

Under the conditions of small extents of dispersion the symmetrical C curve is given by
C = 0.5* ( D / uL)-1/2 * exp. [-(1-)2 / (4D / uL)] from which we can calculate the
dispersion number by trial and error and it has to be tested for better matching with the
experimental curve.
 31

The dispersion number can also be calculated using the maximum value of C() from the
graph by C()max = 0.5 * (* D / uL)-1/2
The dispersion number can also be calculated using statistics.

PROCEDURE

Experimental setup consists of a packed bed column. Water is allowed to enter the
column at constant flow rate. The flow rate is maintained for about 5 min. to come to the
steady state. The stopwatch, Glacial acetic acid are kept ready. 20 ml. Of NaOH (0.05N) is
taken in a syringe and injected directly into the tube and simultaneously stopwatch should be
started. The samples of the liquid coming out of the reactor are collected at a regular intervals
of the time (up to the residence time) and the sample is around 15 ml. These samples using
phenolthalien indicator are titrated against standard oxalic acid solution of 0.5 N taken in the
burette for finding out he normality of the NaOH in the Sample
.
OBSERVATIONS

Length of the reactor = cm.

Diameter of the reactor = cm.
Volume of the reactor,VR = cc
Actual Volume available for flow, V = VR* . Where  = Void Fraction
Flow rate, VO = cc / min.
Residence time, = min.

Time Normality of NaOH

Min. mol. / lit.

CALCULATIONS

Calculations using statistics

t =  Ci ti / Ci
()2 = ( Ci ti2 / CI) – (t)2
2 = 2 / (t)2
where 2 = variance
we can calculate the dispersion number from
2 = 2(D/uL)

D = dispersion coefficient and D/uL is Dispersion number.

 32

Calculation using graph

1. The dispersion number can be calculated using the maximum value of C()from the
graph by C()max = 0.5 * (* D/uL)-1/2
2. Under the conditions of small extents of dispersion, number by trial and error and it has
to be better matching with the experimental curve.
C = 0.5*(D / uL)-1/2*exp[ –(1-)2 / (4D /uL)]

Time Volume of Normality Concentra Ci ti Ci  = ti

ti acid of the acid tion of ti 2 / t- C=E=Ci/((Ci)
min. consumed taken NaOH Ci t) C =
ml. mol / lit. Mol. / lit. t` C

GRAPH

Plot a Graph of C() Vs 

RESULT

The RTD studies in a packed bed Column is made and the dispersion number is calculated.