LAB MANUAL

CH-405: Chemical Reaction Engineering Lab-III

(Undergraduate Level)

Chemical Engineering Department, IIT Roorkee

 CH-405: CHEMICAL ENGINEERING LABORATORY

CHEMICAL REACTION ENGINEERING (UNDERGRADUATE LEVEL)

Experiment No. 1
Title: Decomposition of Calcium Carbonate
1.Objective: To study the decomposition of calcium carbonate in a muffle furnace and to interpret
decomposition –time data in terms of a suitable reaction model.
2.Introduction: Fluid solid reactions are numerous and of great industrial importance. Most
common examples are roasting of ores, burning of carbon/coke, decomposition of calcium
carbonate etc. Treatment of above type of reactions requires the consideration of two factors in
addition to those normally come across in homogeneous reactions. The modification of kinetic
expressions resulting from the mass transfer and the heat transfer limitations between phases and
the contacting patterns of the reacting phases. Purpose of this experiment is the development of
rate expressions for the decomposition of calcium carbonate.
There are two types of idealized simple models for the non-catalytic reaction of particles of
unchanging size surrounded by fluid.

a. Progressive conversion model

Here we visualize that the reactant gas enters and reacts throughout the particle at all times,
most likely at uniform rate at different locations within the particles. Thus, solid reactant
is converted continuously and progressively throughout the particles.
b. Unreacted core model
Here we visualize that the reaction occurs first at the outer skin of the particles. The zone
of the reaction then moves into the solid and may leave behind completely converted
material and inert solid shell. We refer to these as ‘ash’ .Thus, at any time there exists an
unreacted core of material which shrinks in size during reaction.

Decomposition of CaCO3 is reasonably represented by unreacted core model. Unreacted

CaCO3 model for spherical particles of changing size visualizes five steps occurring in
succession during reaction.

A(fluid) + b.B (solid) Fluid and/or solid product

Step 1. Diffusion of gaseous reactant A through the film surrounding the particle to the surface
of the solid.

Step 2. Penetration and diffusion of A through the blanket of ash to the surface of the unreacted
core.

Step 3. Reaction of gaseous A with solid at this reaction surface.

Step 4. Diffusion of gaseous products through the ash back to the exterior surface of the solid.
Step 5. Diffusion of gaseous products through the gas film back into the main body of fluid.

It is not necessary that at a time all the steps may have controlling influence on the reaction.
Depending upon the type of reaction some of them may control the overall rate of conversion.

3. Experimental Section:
3.1. Apparatus:
1. Chemical balance with weight box.
2. Dessicators.
3. Muffle furnace with automatic temperature control.
4. Stainless steel trays.
5. Calcium carbonate particles.
6. Tongs.
7. Asbestos gloves.

3.2. Description of flow Diagram:

Sample
After Weighing Place the Remove Sample After 25
sample inside Muffle Furnace min and Place in After Cooling
at 8000C Desiccator For Cooling Weighing the sample

Input scientific Muffle Desiccator scientific Output

weighing Furnace at weighing
balance 8000C balance

3.3 Experimental Procedure:

1. Maintain the temperature in the muffle furnace at the desired value (8000C) by adjusting
the controls.
2. Weigh known amount (about 10g) of calcium carbonate in six stainless steel trays whose
masses are also known individually.
3. Put these trays in muffle furnace.
4. Remove one tray after every 25 min from muffle furnace.
5. Keep these trays in dessicators to avoid absorption of moisture by material during
cooling.
 6. Weigh these trays quickly when material cools down (give approx. 50 min for cooling).
7. Calculate conversion of solids by loss in weight of trays. Thus you are having conversion
vs time date. (100 % conversion corresponds to a 44 % loss in mass of sample).
8. Try to fit data to models discussed in theory.
9. Best fitted model will represent the decomposition of calcium carbonate at the
temperature of study.

3.4. Observations and Calculation:

Following are the conversion-time relations for the various models for solids of identical size:
Diffusion through gas film controls: t /   X B
Diffusion through ash film controls: t /   1  3(1  X B ) 2 / 3  2(1  X B )
Chemical reaction controls: t /   1  (1  X B )1/ 3
Where: t=time
XB= Fractional conversion of solids
τ = Time for complete conversion of solid.

3.5 Results and Discussion:

Table-1

S.No Mass of Mass of Mass of Time Mass after Mass of CaCO3 Fraction Decomposition (XB)
empty Caco3 tray with Taken For Decomposition in Decomposed in
Tray in sample CaCO3 Heating in gm (Mnew) gm(Mdec)
gm(M1) (Msam) in min(texp)
gm(M2)
M dec  M 2  M new X B  M dec /(0.44  M sam )
1
2
3
4
5

Table-2
S.No Model-1 Model-2 Model-3 Model-1 Model -2 Model-3
t / 1  X B t /  2  1  3(1  X B )2 / 3  2(1  X B ) t /  3  1  (1  X B )1 / 3
1.
2.
3.
4.
5.
Table-3
S.No. Theoretical Time (Min) % Deviation
Model-1 Model-2 Model-3 %D= ((texp  tth ) / tth )  100
tth,1  1  X B tth, 2   2  X B tth,3   3  X B Model-1 Model-2 Model-3
1.
2.
3.
4.
5.

4. Conclusions:
 Experiment No. 2
Title: Batch Reactor

1. Objective
Study of a homogeneous catalytic esterification reaction in a batch reactor and determine
the order of reaction, predict the forward & reverse rate constants kf and kr by differential
as well as integral methods and compare the two results explaining the reason for the
difference in the values of the rate constants.
2. Introduction
A Batch Reactor is a closed system with no input and output streams. A batch reactor can
operate under the following conditions:
 Isothermal (temperature of reaction mass remains constant)
 Perfectly mixed (composition of the reaction mixture is uniform throughout)
 Constant volume (volume of the reaction mixture within the reactor remains
constant; there is no appreciable change in the density of reaction mass)
In homogeneous reactions, all reacting species remain in a single phase. The rate of
reaction for such a reaction can be defined as the moles of a component appearing by
reaction per unit volume of the reaction mixture per unit time. Time rate is influenced by
variables like temperature, pressure and concentration.

Stirrer

0.
2
18
m
0.

Reaction
0.138m
vessel
Constant temperature bath
vessel 0.29
5m

Figure 1: Experimental setup

3. Theory
For isothermal operation of the constant volume batch reactor, rate of reaction is dependent
only on the composition so that a solution for conversion xA with respect to time is obtained
from the mass balance. At constant volume the fractional conversion x A and reactant
concentration CA are related by:
xA = (CAo − CA) / CAo
Where CAo is the initial reactant concentration and is equal to NAo/V ( NAo is the moles of
reactant A corresponding to zero conversion at time t= 0 and V is the reaction mixture
volume).
For a reversible second order reaction:
A+B↔C+D
the specific reaction rate (rate of formation of C or disappearance of A) is given by,
1 𝑑𝑁𝐴 𝑑𝐶𝐴
−rA = =− = (kfCACB − krCCCD) …………………(1)
𝑉 𝑑𝑡 𝑑𝑡
From stoichiometry, if CA =CAo (1− xA)
Then CB =CAo (α− xA), CC =CAo (β− xA), and CD =CAo (γ− xA), and expressing in terms of
fractional conversion, we obtain,
1 𝑋𝐴 𝑑𝑋𝐴
t= ∫ 1 ......…………… 2)
kf CAo 0 (1−𝑥𝐴)(𝛼−𝑥𝐴)−𝐾 (𝛽+𝑥𝐴)(𝛾+𝑥𝐴)

Where t is the time required for conversion xA, K is the reaction equilibrium constant, α =
CBo/ CAo, β = CCo/ CAo, γ = CDo/ CAo.
The experiment involves the study of the esterification of ethyl alcohol and acetic acid.
A B C D
CH3COOH + C2H5OH = CH3COOC2H5 + H2O ………………..(3)
In an isothermal batch reactor with stirrer using HCl as a catalyst.

4. Experiment section
4.1. Apparatus
Constant temperature bath with stirrer, Round bottom flask, Heating mantle, Stop watch,
Titration apparatus for the collection and analysis of samples.
4.2. Chemical required
Ethyle alcohol, Acetic acid, Conc. HCl, NaOH solution, Phenolphthalein.
4.3. Utilities required
Electricity, Water, Ice.
4.4. Experimental procedure
 Add a known quantity (400 ml) of aqueous solutions of ethyl alcohol of known
concentration to the given reactor.
 Start the stirrer and control the hot water at the desired reaction temperature
(approx. 40ᴼC).
 Heat a known quantity (400 ml) of aqueous solution of acetic acid of known
concentration to the desired reaction temperature separately.
 Add the aqueous solution of acetic acid quickly in the reactor and collect 10 ml
sample in a conical flask, containing ice and analyze for initial concentration.
 Add measured quantity (2 ml) of Conc. HCl (as catalyst) in to the reactor mixture
and start the stop watch.
 At regular intervals of 10 minutes, withdraw 10 ml samples from the reactor in a
flask containing ice.
 Analyze these samples for acetic acid content by titrating with standard NaOH
using phenolphthalein as indicator.
4.5. Observation and calculation
 Tabulate the concentration of acetic acid vs. time.
 Determine the order of reaction and predict the forward and reverse rate constants
kf and kr by differential as well as integral methods and compare the two results
explaining the reason for the difference in the values of the rate constants.
 Write the rate equation giving the units of various terms.
4.6. Sample of calculation
Std. NaOH vs oxalic acid
Ndil NaOH *Vdil NaOH =Noxalic acid* Voxalic acid
→ Ndil NaOH = (0.19*18.2)/100 = 0.03458
Diluted NaOH contained 2ml NaOH (std) for 100 ml dil. NaOH
Hence, Normality of std. NaOH =(0.03458*100)/2 = 1.729
and,
 Acetic acid vs std. NaOH
Nacetic acid* Vacetic acid = Ndil NaOH *Vdil NaOH
→ Nacetic acid = (1.729*44.5)/10 = 7.69
Now,
Finding CAo, CBo, CCo, CDo
Normality of acetic acid = 7.69
400 ml of this solution is present in 800 ml reaction mixture
Moles of acetic acid in 800 ml reaction mixture = 7.69* (400/1000) = 3.08
CAo = 3.08/(800/1000) = 3.84 moles/L

Conc. of acetic acid solution = normality of acetic acid solution

=7.69 moles of acetic acid/L solution
461.6 kg acetic acid/m3 solution [Mol. wt. of acetic acid= 60]
461.6 kg acetic acid / 1049.5 kg solution [density of solution =1049.5 kg/m 3]

Hence, weight of water in 1 m3 solution = 1049.5 – 461.64 = 587.85 kg

Water in 1L solution = 587.85 g
→587.85/18 [mol. wt. of water 18]
=32.65 moles
Moles of water fed with 400 ml acetic acid solution = 32.65 *(400/1000) = 13.06 moles

Ethanol solution is of 95.9 % purity.

1 mole of solution = .959 mole of ethanol + 0.041 mole of water
= (0.959*46 + 0.041*18) g [mol.wt. of ethanol=46, mol.wt. of water=18]
=44.8 g solution [density of ethanol solution = 778.8 kg/m3]
=.0575 L solution

1 L solution = 1/.0575 =17.36 moles of solution.

17.36* 0.041 moles of water =0.72 mole of water

Moles of water fed with 400 ml of ethanol sol. = 0.72*(400/1000) = 0.284

 Now, Total moles of water fed in 800 ml of reactor mixture = 13.06+0.28=13.34

CDo = 13.34/ (800/1000) = 16.68 moles/L

Moles of alcohol fed in 800ml reactor mixture = .284*(0.959/0.041) = 6.66

CBo = 6.66/(800/1000) = 8.325 moles/L

No ethyl acetate is present initially so CCo = 0

Now,
Conc. of acetic acid in reaction mixture (CA) = normality of sample withdraw
CA = Nstd NaOH *Vstd NaOH used /10 => 1.729*Vstd NaOH /10 => .1729 * Vstd NaOH

Table 1: The calculated value of CA at different times is shown in the table

S. No. Time,t (min) Vstd NaOH used (ml) CA(moles/L)
1 0
2 10
3 20
4 30
5 40
6 50
7 60
8 70
9 80
10 90

Now CA Vs t can be plotted and – dCA/ dt at various points can be obtained

Experimentally, we have ; K306 = 1.4114 , ∆Hᴼ298 = 13110 J
Using, ln {K316/K306} = − ∆Hᴼ298 /R {(1/316.15)− (1/306.15)}
K316 = ……..
This value of K will be used further in differential and integral analysis:
We have : f(CA) = aCA2+ bCA+ c
Where,
a= K−1 =………..
b= K(CBo−CAo) +2CAo+CDo = ………. moles/L
c= − CAoCDo−CAo2 = …………. moles/L
f(CA)= ……… CA2+ …………… CA+………….
both, –dCA/dt and f(CA) at various values of CA can be determined for differential method.

Differential method:
–dCA/dt as slope of (CA Vs t) curve and f(CA) were found for all values of CA and are listed in
given below:

Table 2: The calculated value of f(CA) and –dCA/dt as slope of (CA Vs t) curve at different times
is shown in the table
S. No. CA(moles/L) –dCA/dt (moles/Lmin) f(CA) (moles/L)2
1
2
3
4
5
6
7
∑–dCA/dt = ∑ f(CA) =

We have,
∑–dCA/dt =k2∑ f(CA)
k2 =………… L/min mole
k1=Kk2 =…………….. L/min mole
Integral method:
f(CA)= …………………… CA2+ …………….. CA+………..
Integrating,

F(CA) =CAo∫CA−dCA/f(CA) =

Table 3: CA Vs t is known , now F(CA) Vs t data can be generated

S. No. Time,t (min) CA (moles/L) F(CA) (L/moles)
1 10
2 20
3 30
4 40
5 50
6 60
∑t= ∑ F(CA)=

We have
∑ F(CA) =k2∑t
k2=…………. L/mole min
k1=Kk2 =……………… L/mole min

we had : Kexpel =………. at the reaction temperature( ….ᴼC)

Th data equation is − rA=k2f(CA)

4.7. Results and discussion

From differential method, k1= …………… L/min mole ; k2 =………….. L/min mole
Rate equation is:
−rA(moles/L min) =……….(L/moles min)*{CA (moles/L)}2 + ……………(min-1)*CA(moles/L)
+………..(moles/L min)
From integral method, k1= …………… L/min mole ; k2 =……………… L/min mole
Rate equation is:
−rA(moles/L min) =……………(L/moles min)*{CA (moles/L)}2 + …………….(min-
1
)*CA(moles/L) +…………(moles/L min)
4.8. Sources of error
 Variation in reaction temperature
 Titrations should be done carefully
 Stirring should be continuous

5. Conclusions

6. References
1. H. SCOTT FOGLER, Elements of chemical Reaction engineering, Forth Edition
2. OCTAVE LEVENSPIEL, Chemical Reaction Engineering, Third Edition
3. J.M. SMITH, H.C. VAN NESS and M.M. ABBOTT, Introduction to chemical engineering
thermodynamics, Fifth edition
 Experiment No. 3
Title: Semi batch reactor

Object: Study of non catalytic homogeneous saponification reaction in a semi batch reactor and
to interpret the kinetic data of the given reaction in the form of rate equation, that is to determine
the value of rate constant.

Apparatus:

 Semi batch Reactor assembly including agitation system

 One 1 – 15 dm3 capacity container for use as constant level overhead tank for reactant.
 Stop watch
 Titration apparatus for collection and analysis of sample
Chemicals required:

 Ethyl acetate
 NaOH solution
 HCl solution
 Phenolphthalein
Theory: A semi batch reactor can be considered as a continuous operated tank reactor where
incoming and outgoing flows are not equal to each other. Consequently the mass of reaction
mixture is not constant. The reactor can equally well be considered as a batchwise operated reactor
with a feed of a reactant stream or a discharge of a product stream.

A+B C+D

In a semi batch operation considered here, one reactant (NaOH; depicted as A) having
concentration CA0 in solution is added initially (volume added = Vo ). Then other reactant (ethyl
acetate; depicted as B)having concentration CBo in solution is added continuously at a constant
volumetric rate vB . The continuous feed of one of the reactant causes change in the composition
in addition to the changes due to the reaction itself. No stream is withdrawn from the reactor.

At any time t,

The total volume (V) of the reaction mixture is given by:

V = Vo + VBt

If n is number of moles of any component of the reaction mixture at time t , its concentration in
the mixture is given by:

C = N/V = N/( Vo + VBt)

N = CV
Initial number of moles of reactant A taken NA0 is given by :

NA0 = CA0V0

At any time t,

Number of moles of A in reaction mixture is

NA = CAV = CA(Vo + VBt)

Where CA is concentration of A in reaction mixture at time t. Therefore fractional conversion of

reactant A at time t is given as:

𝑁𝐴 𝐶𝐴 . 𝑉
𝑥𝐴 = 1 − = 1−
𝑁𝐴0 𝑁𝐴0

At any time t if concentration of say A is known i.e CA is known,

𝑁𝐴 𝐶𝐴 . 𝑉
𝑥𝐴 = 1 − = 1−
𝑁𝐴0 𝑁𝐴0

Then,

NB = CBovBt - NAoxA

CB = NB / V

NC = ND = NAoxA

CC = CD = NC (or ND)/V

If CA v/s t is known , CB , CC , CD can be determined . Fractional conversion of B at any time is

given by :

𝑁𝐴𝑜 𝑥𝐴
𝑥𝐵 = 1 −
𝐶𝐵𝑜 𝑣𝐵 𝑡

K , the equilibrium constant is independent of time or concentration and can be obtained as

K= CCeCDe/CAeCBe (experimental value)

Theoretically as shown below:

First we use,
∆𝐺 0
= −𝑙𝑛𝐾298 ……………………………………(C)
𝑅𝑇

At 298.15 K
i.e ΔG0298 is standard Gibbs energy change for the chemical reaction at 298.15 K.

R is universal gas constant.

T = 298.15 K is the temperature

Then we use :
0
𝐾 −∆𝐻298 1 1
ln 𝐾 = (𝑇 − 298.15) ……………………….(D)
298 𝑅

Where k is equilibrium constant at reaction temperature T.

ΔH0298 is standard enthalpy change of reaction at 298.15 K.

The above equation can be used only if the difference between T and 298.15 K is small so that
ΔH0 is almost independent of temperature.

In the present experiment the reaction is :

NaOH + CH3COOC2H5 CH3COONa + C2H5OH

(A) (B) (C) (D)

It occurs at atmospheric temperature in a semi batch reactor.

Reaction:

NaOH + CH3COOC2H5 CH3COONa + C2H5OH

Since volume of the reaction mixture is changing with time, concentration of A in the reactor is
𝑛𝑎
given by Ca= 𝑉

nA is the number of moles of A in the reaction mixture of volume=V

And
𝐹𝑡𝐶𝑏𝑜−(𝑛𝐴𝑜−𝑛𝐴)
CB = 𝑉

where, V=Vo+Ft

transient component balance(for component A) is:

𝑑𝑛𝐴
- 𝑑𝑡 = 𝑘𝑉𝐶𝑎𝐶𝑏

or,

𝑑𝑛𝐴 𝑛𝐴(𝐹𝑡𝐶𝑏𝑜 − (𝑉𝑜𝐶𝑎𝑜 − 𝑛𝐴))

− =𝑘
𝑑𝑡 𝑉𝑜 + 𝐹𝑡

𝑑𝑛𝐴 𝑛𝐴(𝐹𝑡𝐶𝑏𝑜−(𝑉𝑜𝐶𝑎𝑜−𝑛𝐴))
The plot of − vs will give straight line of slope equal to k.
𝑑𝑡 𝑉𝑜+𝐹𝑡

Procedure:

1. The overhead constant level container is fitted with aqueous solution of ethyl acetate of
known conc. (to be determined).
2. The peristaltic pump is switched on and certain flow rate was maintained.
3. In order to determine concentration of NaOH (both reactant and titrant), 10mL of NaOH
with 2-3 drops of phenolphthalein is titrated with known concentration of oxalic acid until
the colour changed is observed.
4. For determination of ethyl acetate concentration, 10mL of ethyl acetate is taken in a conical
flask containing 20mL of NaOH of known concentration. Excess NaOH is titrated after 2-
3 hours with known concentration of HCl.
5. To determine concentration of HCl, 10mL of HCl with 2-3 drops of phenolphthalein is
titrated with known concentration of NaOH.
6. At t=0, addition of ethyl acetate at fixed rpm along with stopwatch was started .
7. NaOH concentration at every 5 minutes was found by collecting 10mL of sample (using a
pipette) from the reactor in a conical flask containing 20mL of HCl of known
concentration(to be determined) and titrating the excess HCl using standard NaOH(titrant).
8. Equilibrium concentration is determined at certain temperature.
Calculations:

Normality of NaOH(titrant)=Na

Normality of NaOH(reactant)=Nb

Normality of HCl=Nc

Total final volume of reaction mixture withdrawn from the reactor=Vt

Volume withdrawn as samples=10×n

Total final volume should have been=Vt+(10×n)

Volume of NaOH(reactant) initially taken in the reactor =Vo.

Avg. flowrate of ethyl acetate that is been added=F

Total volume of ethyl acetate added=F×t

Finding normality of ethyl acetate solution

10mL of ethyl acetate solution and 20mL of NaOH is mixed and kept for 2 hours. After 2 hours,
the solution is titrated with HCl.

Calculating concentration of NaOH in reaction:

meq of NaOH(titrant) used=n2

meq of HCl fed=no

meq of HCl used=n2

meq of HCl left=no-n2

meq of NaOH left unreacted in 10mL sample=no-n2

concentration of NaOH=( no-n2)/10

Precautions:

1. Always use clean water and good quality chemicals and standard solution for titration.
2. Keep close all drain valves while filling reactant in feed tank
3. Titrations should be done with extreme care.
4. Flow rate of ethyl acetate should not be disturbed
5. There should be no leakage from reactor.
6. Handle the chemicals carefully.
Sources of error:

1. Errors in titration and other experimental errors

2. Change in flow rate of ethyl acetate
References:

1. Octave Levenspiel,"Chemical Reaction Enginn=eering vol-3"4th edition,Asian books Pvt

Lt.,1991,Page 5-6,61.
 Experiment No. 4
Title: Tubular Flow Reactor
1. Objectives

--- Study of non-catalytic homogeneous saponification reaction in a tubular flow reactor and to
interpret the kinetic data of the given reaction in the form of a rate equation.

2. Introduction

Tubular reactor consists of a cylindrical pipe and is normally operated at steady state. Tubular
reactors are used most often for gas-phase reactions. A schematic of a tubular reactor is shown in
Figure 1.

dV
CA0 CAf
FA0 FA + dFA FAf
FA
D
XA0 = 0 XAf = 0
v0 L vf

dXA

XA

Distance through reactor

Figure 1: Schematic diagram of a tubular flow reactor

Where,
L = Length of the reactor tube, m
D = Diameter of reactor tube, m

In the tubular reactor, the reactants are continually consumed as they flow down the length of the
reactor. In modeling the tubular reactor, we assume that the concentration varies continuously in
the axial direction through the reactor. Consequently, the reaction rate, which is a function of
concentration for all but zero-order reactions, will also vary axially. For the purposes of the
material presented here, we consider systems in which the flow field may be modeled by that of a
plug flow profile (e.g. uniform velocity as in turbulent flow) as shown in Figure 1. That is, there
is no radial variation in reaction rate and the reactor is referred to as a plug-flow reactor (PFR).
The assumptions that plug flow analysis are valid when flow is laminar. The following
saponification of ethyl acetate is considered for kinetic experiment.
B + A  C + D

CH3COOC2H5 NaOH CH3COONa C2H5OH

Reynolds Number
du
Re 
 (1)
where,
volumetric flow rate (mL/min)
u=
Cross sectional area of reactor(m2 )

πd2
Cross-sectional area of reactor = (2)
4

d = diameter of reactor, m
u = linear velocity of liquid through the reactor, m s-1
ρ = liquid density, kg m-3
μ = Liquid viscosity, kg m-1s-1

Space time, τ is defined as:

1
  = (time required to process one reactor vol. of feed measured at specified conditions)
s
= [time] (3)
where, s is space velocity:
1
s  = (no. of reactor volumes of feed at specified conditions which can be treated in unit time)

= [time-1] (4)

In terms of conditions of the stream entering the reactor,

(moles A entering)
1 CA V vol. of feed
(volume of reactor)
  0  moles A entering (5)
s FA0
time

V Reactor volume
 = volumetric flow rate (6)
v0
The material balance of reactant A across the differential volume element of dV (from Figure 1)
we can write as

Rate of flow of A Rate of flow of A Rate of disappearance of A

( )= ( ) + ( )
into the system out of the system by reaction

Rate of accumulation of A
+( ) (7)
within the system

Rate of flow of A into the system = FA, moles.time-1

Rate of flow of A out of the system = FA+ dFA, moles.time-1
Rate of disappearance of A by reaction = (-rA)dV, moles.time-1
Rate of accumulation of A within the system = 0, moles.time-1

From Eq. (7), we get

FA= (FA+ dFA) + (-rA)dV (8)
Noting that
dFA= d[FA0(1-XA)] = - FA0dXA (9)
we obtain on replacement
FA0dXA = (-rA)dV (10)
Integrating both sides,
V X Af
dV dX A
0 FA0  
0
(rA )
(11)


X Af
V dX A

FA0 CA0
 
0
(rA )
(12)

X Af
V VCA0 dX A

v0

FA0
 CA0 
0
(rA )
(13)

Now,
The specific reaction rate (-rA) for a reversible second order (in both directions and first order with
respect to each reactant) reaction,

AB  CD
is given by:

(-rA) = kfCACB - krCCCD (14)

Where kf and kr are the rate constants for forward and reverse reaction, respectively. For isothermal
operation, rate of reaction is dependent only on composition; so that a solution for change in
concentration with respect to reactor volume is obtainable from the mass balance over a differential
reactor volume,

-vdCA = (-rA)dV (15)

where v is the volumetric flow rate and V is the reactor volume. Neglecting the change in the
volume of reaction system due to fractional conversion can be related to limiting reactant
concentration,

CA =CA0(1-XA) (16)

CA
XA  1 
C A0 (17)
A + B  C + D
At t=0 CA0 CB0 CC0 CD0
At t = t CA0(1-XA) CB0-CA0XA CA0XA CA0XA
= CA =CB = CC = CD

At equilibrium,

(-rA) = kfCACB - krCCCD = 0 (18)

2
k f CC CD CCe CDe (CA0 X Ae )(CA0 X Ae ) CA0 X Ae
K    
k r CA CB CAe CBe CA0 (1  X Ae )(CB0  CA0 X Ae ) (1  X Ae )(C B0  C A0 X Ae ) (19)

where CAe, CBe, CCe and CDe are equilibrium concentrations and K is termed as equilibrium
constant.

Substituting in Eq. (14)

(-rA) = kf CA0(1-XA)(CB0-CA0XA) - krCA02XA2 (20)
= kr [(K-1)CA02XA2 - KCA0(CA0+CB0)XA + KCA0CB0]
= kr (aXA2 + bXA + c) (21)
Substituting in Eq. (13)
X Af
V VCA0 dX A
 
v0 kr 
0
aX  bX A  c
2
A
(22)
 X Af
C dX A
k r  A0
 
0
aX 2A  bX A  c
(23)

By using Gibbs free energy G at 298 K temperature,

G
  ln K 298 (24)
RT
where, R = Universal gas constant, kcal k-1mol-1
K298 = equilibrium constant at the reaction temperature T.
To find out KT,

KT H 0298  1 1 
ln  
R  T 298 
(25)
K 298
where, KT =K is equilibrium constant at the reaction temperature T.
and, H 0298 = Heat of reaction at 298 K, kcal mol-1

3. Experimental section

3.1 Apparatus

1. Plug flow reactor

2. Two 10-15 dm3 capacity containers for use as constant level, overhead tanks for reactants
3. Stop watch
4. Titration apparatus for collection and analysis of samples
 Pipette, burette, conical flasks, beakers, measuring cylinders, pH indicator.

3.2 Chemical Required

Ethyl acetate, NaOH solution, HCl solution, Phenolphthalein, Oxalic Acid.

3.3 Utilities required

Electric supply, de-ionised water.

3.4 Experimental procedure

1. Fill the overhead constant level containers with aqueous solution of ethyl acetate and NaOH
of know concentrations.
2. By manipulation of values adjust the volumetric flow rates of two reactants to desired value.
Ensure that CB0/CA0 value is close to unity.
3. Final the reactant concentrations at the reactor inlet by collecting (by momentarily operating
stop cock provided at reactor inlet) the sample and analyzing as below.
 For NaOH: Collect 10 ml of sample (reaction mixture) in a conical flask containing 20 ml
of HCL of know concentration and titrating the excess HCl using standard NaOH with
phenolphthalein as indicator.
For CH3COOC2H5 : 10 ml of sample in a conical flask containing 20 ml of NaOH of know
concentration and titrating the unreacted NaOH after allowing sufficient time (around 2.5 h,
for complete conversion of ethyl acetate to sodium acetate) using standard HCl with
phenolphthalein as indicator.

4. After allowing sufficient time for steady state to achieve keeping the flow rate at a constant
value, analyze for NaOH concentrations is reactor effluent at 10 min interval till two readings
are identical.
5. Repeat above steps at different volumetric flow rates of the feed stream entering the first
reactor.
6. Measure the volume of the tubular reactor.
7. Measure the ambient temperature.

3.5 Observations and calculations

1. Tabulate ethyl acetate and NaOH concentrations at reactor inlet, NaOH concentration in
reactor outlet volumetric flow rate of reaction mixture.
2. Find the flow regime, that is, laminar or turbulent flow, and indicate whether plug flow
analysis is valid?
3. Determine the order of reaction and calculate the rate constants kf and kr using each set of
data.
4. What are the values of equilibrium conversion , equilibrium constant and rate of reaction ?
5. Plot fractional conversion of ethyl acetate as a function of liquid hourly space velocity
defined as volumetric flow rate/ hr/volume of reactor keeping all other variables constant.
Note: Experiment can be repeated for different initial concentrations of reactants and at different
volumetric flow rates.

Table1
Thermodynamic data
Compounds H 0f (kcal mol-1) G 0f (kcal mol-1)
NaOH -112.193 -100.18
CH3COOC2H5 -110.72 -76.11
CH3COONa -175.45 -152.31
C2H5OH -66.35 -41.76

Length of tubular flow reactor, L = 140 cm

Diameter of tubular flow reactor, d = 2.5 cm
Reading when 10 mL std. NaOH is titrated with 0.19 N oxalic acid = ......... mL of oxalic acid
Reading when 10 mL reactant NaOH is titrated with 0.19 N oxalic acid = ....... mL of oxalic acid
Reading when 10 mL HCl is titrated with std. NaOH = ......... mL of NaOH
Normality of Normality of Ethyl Acetate:
10 mL (N1) Ethyl Acetate + 20 mL (N2) NaOH (Normality known)
Kept it for 2.5 hr,
Titrate with N3 (Known) HCl - say V1 mL
N3V1 = N2VNaOH
VNaOH = (N3V1)/N2 mL
(20- VNaOH) mL of N2 NaOH is consumed by 10 mL of N1 Ethyl Acetate
N1 × 10 = (20- VNaOH) × N2
N1 = ((20- VNaOH)×N2)/10
= Normality of Ethyl Acetate
Table 2
Observation Table
S. RPM Flow rate of NaOH Flow Rate of Time Volume of NaOH
No. (mL/min) Ethyl Acetate (min) (mL)
(mL/min)

3.6 Sample of Calculations

3.7 Results and discussion

Table 3
Results
Space Space XA XB Reaction Rate Reaction Rate Rate of
Time, τ Velocity, S (%) (%) Constant, kf Constant, kr reaction,
(min) (min-1) (L mol-1 min-1) (L mol-1 min-1) (mol L-1 min-1)

3.8 Sources of Error:

4.Conclusions

References

1. H. Scott Fogler, Elements of chemical reaction engineering, Second edition, 1955.

2. Octave Levenspiel, Chemical reaction engineering. Second edition, 1999.

3. J. M. Smith, H. C. Van Ness, M. M. Abbott, Introduction to chemical engineering

thermodynamics, Sixth edition, 2003.
 Experiment No. 5
Title: Packed bed reactor
Title
To study a non-catalytic reaction in a Packed Bed Reactor.
Objective
To determine the reaction rate constant for saponification of Ethyl acetate with Sodium
Hydroxide at ambient conditions.
1. Introduction
In a Packed bed reactor (PBR), material flows through the reactor as a plug so PBR's are also
called plug flow reactors (PFR). In an ideal plug flow reactor (PFTR) there is no mixing in the
direction of flow and complete mixing in direction perpendicular to flow. Concentration of
reactants 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
packed bed. It is expected that the yield of reaction should be high in case of a packed bed reactor
as compared to an equal volume plug flow reactor.
Theory: Schematic diagram of non catalytic packed bed reactor is given in Figure 1.

Product

Z= Packed height

NaOH (A)
Feed
Vo, CAo, CBo
Ethyl Acetate
(B)
Assuming plug flow conditions to exist in the reactor, then under steady state condition
performance equation for PFR:

X Af
VR dX A
FAo
 
0
 rA
(1)

For the saponification reaction in packed bed reactor

CH 3COOC 2 H 5  NaOH 
K
CH 3COONa  C2 H 5OH
B (A)
Rate of reaction is:
 rA  KC ACB (2)
For the condition: CAo = CBo
Equation (2) is reduced to:
 rA  KC A2 (3)
Concentration of reactant after time, t

C A  C Ao (1  X A ) (4)
By substituting Eq.(3) and (4) into Eq. (1)
X Af
VR 1 dX A
FAo

KC A2  0
(1  X A ) 2
(5)

Where FAo = Vo CAo

FAo = molar flow rate of NaOH

Vo = Volumetric flow rate of feed, LPM

VR = Volume of Reactor, L
Equation (5):
X Af
VR 1 dX A
Vo

KC Ao 
0
(1  X A ) 2
(6)

By integrating Eq. (6), space time for the reaction is:


1 X Af
=
1 C AO  C A  (7)
KC Ao (1  X Af ) K (C A  C AO )

When CAo and CBo are differ, then,

  C  

1
KC Ao CBo

ln  Bo   X Af 
C Ao   1  C Ao 
 CBo 
  
 1  X Af  (8)
  C Ao  
C Ao  C A
X Af 
C Ao

C A = Concentration of un-reacted NaOH at steady state

K = Reaction rate constant
2. Experimental Section
2.1 Description of experimental setup
The setup consists of a glass column packed with Raschig Rings and two feed tanks. Peristaltic
pumps are provided to measure the individual flow of both reactants. The flow rate can be adjusted
by operating the knob provided on the pumps. The concentration of feed and the product coming
out from the reactor are analyzed by chemical titration and check the effect in the performance of
the reactor.
2.2 Utilities required
Conical flask, Measuring Cylinder, Burette, Pipette, Beaker, Funnel
2.3 Chemical required
Sodium Hydroxide (NaOH), Ethyl Acetate ( CH 3COOC 2 H5 ), Hydrochloric Acid (HCl),
Indicator (Phenolphthalein)
2.4 Experimental procedure

1. Close the drain valves provided at the bottom of the feed tanks.
2. Fill the one of the feed tank with NaOH (R) and other with Ethyl acetate of unknown
normality.
3. Ensure the knob provided on the pumps is at zero position.
4. Set the rotation selection switch towards clockwise rotation arrow.
5. Set the other switch provided on the pump towards "Manual" option.
6. Switch ON the pumps and set at desired flow rates of reactants in to the reactor.
7. Measure the flow rate of the feed by switching on the one pump at a time and taking the
chemical from the outlet point at the bottom of the reactor.
8. Switch off the knob and start filling the chemicals into the reactor and wait for reactants
to come out from the outlet of the reactor.
 9. After about 10-15 min, collect the sample at the outlet in a graduated cylinder and transfer
10 ml of sample into the titration tank immediately that already contains 20 ml of standard
HCL.
10. Using phenolphthalein as indicator, titrate the solution (i.e., excess HCl) with NaOH (T)
and note down the volume of NaOH (VNaOH) used.
11. Collect the sample at 10 min interval until reaction reaches to steady state.
12. Repeat all steps for 4-5 different flow rates of feed by changing the RPM of the both pumps.
13.
2.5 Observation
Data:
Volume of the reactor (VR) = -------------ml
Volumetric flow rate (V0) = ------------- ml/min
Initial concentration of NaOH (CAO) = ------------- g mole/L
Volume of HCl used (VHCl) = ------------- ml
Volume of sample (Vsample) = ------------- ml
Normality of NaOH (NNaOH) = ------------- g mole/L
Normality of HCl (NHCl) = ------------- g mole/L
Normality of Ethyl Acetate (NEA) = ------------- g mole/L

Table 1 Observation table for the experiment.

Time (min) Volume of NaOH (T) used (ml)
0
10
20
30
40
50
Sample calculation
Formulae used
VHCl N HCl
HCl O  , g mole
1000
VNaOH N NaOH
HCl R  HCl O  , g mole
1000
HCl R
CA   1000 , g mole/L
Vsample

C Ao  C A
XA 
C Ao

VR  60
 , min
Vo

Eq. (7) can be written as:

1  1 1 
   
K  C A C AO 

 1 1 
Plot  vs.    on a simple graph and find the slope (1/K); from slope find K and report K
 C A C AO 
at the reaction temp.
For N= 12 RPM
VR= 1400 ml
Vo = 37.5 ml/min
CAo= 0.125 g mole/L
VHCL= 20 ml, VSAMP = 10 ml
NHCl =0.23 g mole/L
VNaOH (T)=27.9 ml
τ = VR/Vo =37.33 min
HClO=VHCl*NHCl/1000 =0.0046 gmole/ L
HClR=HClO-(VNaOH*NNaOH/1000)=0.000136 gmole/L
CA=HClR/VSAMP*1000=0.0136 gmole/L
1/CA-1/CAo= 65.529 L/mol
Calculation Table:
RPM Vo(ml/min) τ (min) VNaOH (T) HCLR CA [1/CA-1/CAo]
12 37.5 37.33 27.9 0.000136 0.0136 65.52941176
15 45.5 30.769 27.3 0.000232 0.0232 35.10344828
17 48.5 28.8659 27 0.00028 0.028 27.71428571
19 54 25.925 26.7 0.000328 0.0328 22.48780488

K =1/slope
=1/0.722 = 1.385 L/g mol*min.
3. Results and discussions
The reaction rate constant from the calculations was found to be around 1.385 L/g mol/min.

4. Conclusions

5. Precautions & Sources of error:

1. Always use clean water and good quality chemicals and standard solution for titration.
2. Close all the drain valves while filling the reactant in feed tanks.
3. Flow should not be disturbed during the experiments.
4. Handle the chemicals carefully.
6. References
Octave Levenspiel, "Chemical reaction engineering", 3rd Edition.
Coulson J M and Richardson JF, "Chemical engineering", Sixth edition.

Nomenclature:
CA= Concentration of un-reacted NaOH in the reactor, gmole/L
CA0= Initial Concentration of NaOH in the feed mixture, gmole/L
HClO= Amount of HCL taken for quench, gmole/ml
HClR= Amount of HCL reacted with NaOH, gmole/ml
K = Rate constant, L/g mol min
N = RPM of the pumps
NHCl = Number of moles of HCl used, g mole/L
NNaOH = Number of moles of NaOH used, g mole/L
VR = Reactor volume, L
Vo = Volumetric feed rate, (ml/min)
VHCl = Volume of N/10 HCl taken for quench, ml
VSAMP = Volume of sample taken, ml
VNaOH = Volume of NaOH used for neutralizing, ml
XA = Degree of conversion
τ = Residence time, min
 Experiment No. 6
Title: Residence time distribution studies in a packed bed reactor.

1. Objectives

1. RTD studies in a packed bed reactor.

2. To plot RTD curves for a packed bed reactor by using pulse input.
3. To determine dispersion number.
2. Introduction

2.1 Concept of RTD

The idealized plug flow and batch reactor are the only two classes of reactor in which all the atoms
in the reactor have the same residence time. In all other reactor types the various atoms in the feed
spend different times inside the reactor; that is; there is a distribution of residence times of the
material within the reactor. In any reactor the distribution of residence times can significantly
affect its performance. This distribution of time for the stream of fluid leaving the reactor is called
the exit age distribution E, or the residence time distribution (RTD) of fluid. E has the units of
time-1.

The RTD of a rector is a characteristic of the mixing that occurs in the chemical reactor. There is
no axial mixing in a plug flow reactor and this omission is reflected in the RTD.

Packed bed reactor

In a pulse input, an amount of tracer No (kg or moles) is suddenly injected in one shot into the feed
stream entering the reactor (𝑣 m3/s) in as short a time as possible. The out let concentration is then measured
as a function of time. The effluent concentration time curve is referred to as the C curve in RTD analysis.
From the material balance for the vessel we find

∞ 𝑁𝑜 𝐾𝑔.𝑠
Area under the Ci curve A = ∫0 𝐶𝑑𝑡 = ∑𝑖 𝐶𝑖 ∆𝑡𝑖 =
𝑣
[ 𝑚3 ]……………..1

∞
∫0 𝑡 𝐶𝑑𝑡 ∑𝑖 ∆𝑡𝑖 𝐶𝑖 𝑡𝑖 𝑉
Mean of the Ci curve 𝑡̅ = ∞ = ∑𝑖 ∆𝑡𝑖 𝐶𝑖
= 𝑣 [s]………………...2
∫0 𝐶𝑑𝑡
To find the E curve from the Ci curve simply change the concentration scale such that the area under the
curve is unity. Thus simply divide the concentration readings by No/𝑣.

𝐶𝑖
E= ∞ ……………………………3
∫0 𝐶𝑑𝑡

An alternative way of interpreting the residence time function is in its integral form: Fraction of material
𝑡
leavening the reactor that has resided in the reactor for times between t1and t2 =∫𝑡 2 𝐸 𝑑𝑡, and it is clear that
1

the fraction of all the material that has resided for time t in the reactor between t=0 and t=∞, is 1; therefore,
∞
∫0 𝐸𝑑𝑡=1.
The another RTD function commonly used is normalized RTD 𝐸𝜃 , here time is measured in terms of mean
𝑡
residence time 𝜃 =𝑡̅, thus

𝐸𝜃 = E 𝑡̅………………………….….4
Student should always remember one restriction on the E curve –that is the fluid only enters and only leaves
the vessel one time. This means that there should be no flow or diffusion or upflow eddies at the entrance
or at the vessel exit , this known as the closed boundary condition therefore relationship between Ci and
the E curve only holds exactly for vessels with closed boundary conditions.
It is very common to compare RTDs by their moments instead of trying to compare their distributions, two
moments are commonly used; the first moments is residence and second one is variance or square of the
standard deviation , it is defined by
∞
𝜎 2=∫0 (𝑡 − 𝑡̅)2 E dt ………………..….5
Equation 5, can be written as
∑ 𝑡𝑖2 𝐶𝑖
σ2 = ( ∑ 𝐶𝑖
)- τ 2 ………………….6

 Large σ2 means higher spreading

 Small σ2 means low spreading
The normalized variance (𝜎𝜃 ) can be calculated by dividing the variance by square of mean
residence time (𝑡̅).
2.2 Concept of Dispersion
RTD is sufficient to characterize a reactor if the reaction is first order or if the fluid flows in a state
of complete segregation or maximum mixedness. For non first order reactions in a fluid with good
micromixing, to predict conversions and product distribution for such systems, a model of reactor
flow pattern is necessary. The dispersion model is useful for flow systems which has small
deviation from plug flow. When an ideal pluse tracer is introduced into the fluid entering a vessel
the pluse spreads as it passes through the vessel. To characterize the spreading diffusion like
process is superimposed on plug flow which is termed dispersion. The dispersion coefficient
D(m2/s)represents this spreading.
 Large d means rapid spreading of the tracer curve
 Small D means slow spreading
 D=0 means no spreading, hence plug flow
Also D/𝜇𝐿 is the dimensionless group known as dispersion number characterizes the spread in
the whole vessel. The dispersion number is calculated form following equation

−1+√1+8σ2𝜃
D/µL= ………………………….7
8

3. Experimental section

3.1 Apparatus

Experimental set up consists of a glass column packed with rasching rings and one feed tank. A
peristaltic pump is provided to control the flow of feed. The flow can be adjusted by operating a
knob provided on the pump. To understand the RTD characteristics, a special arrangement is
provided to inject the tracer at the lower end of the reactor by using a syringe. Sample can be taken
periodically from the out let connected at the top of the reactor.

3.2Experimental set up

Schematic diagram of the experimental set up is shown in Figure 1.

Dimensions of various part of the reactor set up are as follows:

Column height = 74 cm, Inner diameter of reactor = 4.68 cm, Outer diameter of the reactor =5.08 cm,
Porosity of bed= 0.70

feed tank capacity = 20 L

Pore volume of the reactor =1.0 L

Type of packing: Rasching ring, length of rasching ring =8 mm, Inner dia. Of rasching ring =4mm, Outer
dia. of rasching ring =6 mm
Out let

1. Feed tank
2. Peristaltic pump
3. Packed bed reactor
4. Inject point

1
4 2 RPM

OO
OO

Figure 1 Schematic diagram of the reactor set up.

3.3 Utilities required

Electricity Supply single phase, 220 V AC, 50Hz, 5-15 amps combined socked with earth
connection

Table 1. Glassware and chemicals required.

S No. Item Quantity

1 Conical flask, 250ml 5

2 Measuring cylinder 100ml 2

3 Burette 50ml 1

4 Syringe 1

5 Concentrated NaOH (N/8) 100 ml

6 HCL (N/33) 500 ml

7 Phenolphthalein indicator 10 ml
3.4 Experiment procedure

1. Close the drain valve provided at the bottom of the feed tank and column.
2. Fill the tank with water.
3. Take the sample (20ml NaOH) in the syringe and fit it to the injection point.
4. Ensure the nob provided on the pump is at zero position.
5. Open the column in let valve.
6. Connect electric supply to the pump.
7. Switch on the pump and set the pump RPM at required number say 40 and wait for steady
state to come.
8. After flow stabilization inject quickly the pulse tracer from the syringe.
9. Start the stop watch simultaneously. Collect 10ml of exit stream sample from the top at 1
min interval.
10. Take the sample and titrate with N/33 HCL solution using phenolphthalein indicator.
11. Repeat the experiment for different flow rate.

3.5 Observations and calculation

Data given

Length of column, L=1.0m

Volume of the sample, V2=10ml

Strength of acid, N1=N/33 gmoles/l

Pore volume of the reactor, VR=1.0 L

3.5.1 Observation

Table 2. Volume of titrant consumed and corresponding sample concentration

S.No. t, min Volume of titrant V1, ml N(RPM)

3.5.2 Calculation

It is very common to compare the RTDs by their moments instead of trying to compare their
distributions. For this purpose three moments are normally used. The first is the mean residence
time. The second moments commonly used is taken about the mean and is called the variance or
square of the standard deviation. Magnitude of this moments is an indication of the spread of the
distribution; the greater the value of this moment, the greatr a distribution’s spread or greater
deviation from ideality.

Calculate the volumetric flow rate, LPH

Vo= (0.1476*N-0.08), LPH =……………..LPH, where N is the RPM of the pump

Calculate sample concentration, mole /L

𝑉1𝑁1
Ci= x40 gm/L, =…………….min,
𝑉2

Where V1, ml is the volume of the HCL used,

N1 is the strength of HCL used for titration

V2 volume of the sample (10ml)

Calculate mean residence time from eq. 2 = ……………min,

Calculate theoretical mean residence time, min

𝑉𝑅
τ t= x60,min =……………min
𝑉𝑜

Where VR is the volume of the column in liter and Vo is the volumetric flow rate

Calculate the variance of distribution from eq.6 =………………

Calculate generalized variance =……………….

Calculate the dispersion number from eq.7 =……………….

Calculate the RTD function from eq. 3 =……………….

Calculate generalized RTD function from eq. 4 =……………….

Calculate residence time distribution theoretically

𝑉𝑅
τ= *60, min
𝑉𝑜

Plot E curve
3.6 Results and Discussion

Mean residence time, variance and dispersion number of the system are found to be ……, ……
and …….. respectively

Student shall discuss the spreading of the curve and deviation of reactor from plug flow based on
these parameters.

4. Conclusions

RTD experiment was carried out and concentration vs time data was developed from this data,
reactor was characterized by calculating mean residence time, variance and dispersion number. C
and E curve was plotted.

References

1. Octave Levenspiel, “Chemical reaction engineering, 3rd ed.”, John Wiley & Sons, NY,
2001, Page 260-265, 294-296.
2. H.Scott Fogler, “Elements of chemical reaction engineering, 3rd ed.” PHI Pvt Ltd New
Delhi, page 809-826.
3. Coulson &Richardson, “Chemical Engineering Vol.- 3” 4th ed . Asian Books Pvt.Ltd,
ND,1991, Page 87-92.