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CH2401 Chemical Reaction Engineering-II Dept.
of Chemical Engineering 2015-2016

St. JOSEPH’S COLLEGE OF ENGINEERING
DEPARTMENT OF CHEMICAL ENGINEERING
UNIT-I (NON-IDEAL REACTORS)
PART-A (Questions & Answers)
1. What are the factors responsible for deviations from ideal plug flow in a tubular reactor?
The factors responsible for deviations from ideal plug flow in a tubular reactor are (i) Mixing in
longitudinal direction (formation of vortices and eddies, cause this effect) and (ii) Incomplete mixing in
radial direction (formation of parabolic velocity profile, may cause this effect).
2. What are the reasons for non-ideality in real reactors? (NOV/DEC 2013)
The reasons for non-ideality in real reactors are
 Presence of stagnant regions (or dead zones), bypassing or short-circuiting – CSTR
 Mixing in longitudinal direction, incomplete mixing in radial direction and Channeling - PFR
Note: Deviations from ideal performance divide into two classifications;
(i) The first is a flow arrangement in which elements do not mix, but follow separate paths through the
reactor (segregated flow). These elements are retained in the reactor for different times, that is, they have
different residence times.
(ii) The second is a flow arrangement whereby elements of fluid partially mix (micro mixing).
3. Explain the term Channeling.

Channeling occurs in fixed-bed fluid-solid catalytic reactor. The non-uniform packing arrangement results
in a higher velocity near the tube wall where the porosity is greatest. Hence, the time for reaction (residence
time) near the wall will be less than that at the centre of the tube. This means that the composition of the
fluid will vary radially, so that the requirement of complete radial mixing is not satisfied.
4. Explain the term short-circuiting.

Short-circuiting of fluid oftenly occurs in stirred-tank reactors. Here a part of the fluid entering the tank
follows a shortened path to the exit and maintains its identity (does not mix) while doing so.
5. What data do you need in predicting the behavior of a real reactor?

To predict the behavior of a real reactor, we need the following data’s;
 RTD (Residence Time Distribution) of material, which is flowing through the vessel.
 State of aggregation of the flowing material, its tendency to clump and for a group of molecules to
move about together.
 Earliness and Lateness of mixing, of material in the vessel.
6. What is method of inquiry in stimulus response experiment?

Method of inquiry in stimulus (It is a tracer input into the fluid entering the vessel) response experiment is
the method of determining the ‘E’ curve or RTD by introducing pulse or step tracer into the vessel.
7. What is ‘E’ function? Explain.

It is evident that the elements of fluid taking different routes through the reactor may take different lengths
of time to pass through the vessel. The distribution of these times for the stream of fluid leaving the vessel
is called the exit age distribution ‘E’ or the residence time distribution ‘RTD’ of fluid (or it is the
distribution needed to account for non-ideal flow). ‘E’ has the units of time-1.
Note: To find ‘E’ curve from the CPulse curve (a plot of CPulse vs. time‘t’) simply change the concentration
scale such that the area under the curve is unity. Thus, E = CPulse/(M/v) or ∫E(t).dt = 1
Where ‘M’ is the amount of pulse tracer added (kg or moles) and ‘v’ is the volumetric flow rate fluid
entering the vessel.
Note: (M/v) is equivalent to the area under the CPulse curve. The relationship between CPulse and ‘E’ curves
only holds exactly for vessels with ‘closed‘boundary conditions (that is, there should be no flow or
diffusion or upflow eddies at the vessel entrance at the vessel exit).
St. Joseph’s College of Engineering 1 ISO9001:2008

CH2401 Chemical Reaction Engineering-II Dept. of Chemical Engineering 2015-2016
8. Explain ‘F’ function.

The dimensionless form of CStep curve (a plot between CStep vs. time‘t’) is called ‘F’ curve. It is found by
having the tracer concentration rise from zero to unity. Thus, F = CStep/CMax = CStep/(m/v)
Where ‘m’ is the mass or molal flow rate of tracer introduce, continuously and ‘v’ is the volumetric flow
rate fluid entering the vessel.
9. Give the relationship between E(t) and F(t).

The relationship between ‘E’ and ‘F’ curves for the fraction of the exit stream that has resided in the
reactor for a period of time shorter than a given value ‘t’ is given by
t
∫ E(t) dt = [Frac. of effluent which has been in reactor for less than time ‘t’] = F(t)
0
(or) dF/dt = E(t)
Note: The above relationships only hold for closed vessels.
10. What is the requirement of tracer material used for the conduct of stimulus response experiment?
[Dec-2012]
The requirement of tracer material is;
 It should be non-reactive or inert.
 It should be soluble or miscible in the reacting fluid.
 Properties (density) should be similar to reacting fluid.
 It should be easily detectable.
 It should not adhere on the walls of the reactor.
11. What is the difference between ‘E’ and ‘C’ curve?

‘C’ curve is a plot between CPulse and time ‘t’ and area under the ‘C’ curve has the dimensions of Kg-s/m3 or
Kmol-s/m3.‘E’ curve is a plot between {CPulse/(M/v)} and time ‘t’ and area under the ‘E’ curve is always
unity.
Note: (M/v) is equivalent to the area under the CPulse curve. .
12. Sketch E (θ) for (i) ideal PFR (ii) ideal CSTR. (NOV/DEC 2014)
Ideal PFR Ideal CSTR
13. State the relationship between E and F function. [Dec-2012]

The relationship between „E‟ and „F‟ curves for the fraction of the exit stream that has resided in the
t
reactor for a period of time shorter than a given value „t‟ is given by ∫ E(t) dt = [Fraction of effluent which
0
has been in reactor for less than time „t‟] = F(t) (Or) dF/dt = E(t) Note: These relationships only hold for
closed vessels.
14. What are mean residence time, standard deviation and skewness of a RTD function?
Mean residence time (tm): It is the mean time of passage, or when the curve passes by the exit or it is the
time corresponding to the peak value of either CPulse curve or ‘E’ curve. (First moment of probability
distribution of a real valued random variable)

Standard deviation (or variance) (σ2): It is a measure of the spread of the tracer curve. (Second moment of
probability distribution of a real valued random variable)

 2   t - t m 2 E t dt
0
Skewness (s3): It is a measure of the extent that a distribution is skewed to one direction or another in
reference to the mean. (Third moment of probability distribution of a real valued random variable)
1 
s3  3 
0
(t  tm )3 E (t )dt
 2
15. Define Intensity of dispersion.

It is a dimensionless number signifies the characterizing of spreading of the tracer in a packed bed of pipes
or tubes. It is represented by (D/Ud). Where‘d’ is a characteristic length (dtube or dp)
16. What is Dispersion number?

It is a dimensionless number characterizing the spreading of the tracer in the whole vessel, which is defined
as the ratio of movement of longitudinal dispersion to movement by bulk flow. It is represented as (D/UL).
Where ‘D’ is the dispersion coefficient or coefficient of molecular diffusion (in m2/s), ‘U’ is the velocity of
fluid flow (in m/s) and ‘L’ is the length of the non-ideal tubular reactor (in ‘m’).
17. Define Peclet number. What are the values of Peclet number for (i) ideal CSTR (ii) ideal PFR?
The reactor Peclet number (NPe) is defined as the ratio of the rate of transport by convection to that of the
rate of transport by diffusion or dispersion. It is given by NPe = (U L)/D.
Where ‘D’ is the dispersion coefficient or coefficient of molecular diffusion (in m2/s), ‘U’ is the velocity of
fluid flow (in m/s) and ‘L’ is the length of the non-ideal tubular reactor (in ‘m’).
For ideal CSTR, NPe = 0 and for ideal PFR, NPe = ∞.
18. What is Tank’s-in-series model? State its limitations.

 It is the model useful for representing flow in real vessels, for scale-up, and for diagnosing poor flow.
 It is simple, can be used with any kinetics, and it can be extended without too much difficulty to any
arrangement if tanks, with or without recycle.
 This model is applicable only for not very viscous fluids, flowing in a pipe or tube.
19. Define Sherwood number and Schmidt number.

The Schmidt number (NSc) is defined as the ratio of the molecular momentum transfer to that of the
molecular mass transfer.
It is given by NSc = μ/( d).
Where‘d’ is the characteristic dimension of the reactor, ‘’ is the density of the reacting fluid, and ‘μ’
is the viscosity of the reacting fluid.
The Sherwood number (NSh) is defined as the ratio of the total mass transfer to that of the molecular mass
transfer.
It is given by NSh = (kg d)/D.
Where‘d’ is the characteristic dimension of the reactor, ‘kg‘ is the mass transfer coefficient, and ‘D’ is the
diffusivity of the reactant.
20. Differentiate between the segregated flow model and mixing models.
 Complete segregation model or Segregated flow model
All molecules of same age group remain together as they travel through the reactor and are not mixed
till the exit point. This is called as complete segregation model.
 Maximum mixed ness model or mixing model
Molecules of different age group are completely mixed at the molecular level as soon as they enter the
reactor. This is called as ‘complete micro mixing‘ or maximum mixed ness model.
Note: Both the models are said to be Zero parameter models.

PART-B (Questions & Answers)
1. (i) Explain the effects of Non-ideal flow with examples.

(ii) Derive relationship between E and F curves.
Ans: (i) The factors responsible for deviations from ideal plug flow in a tubular reactor are (i)
Mixing in longitudinal direction (formation of vortices and eddies, cause this effect) and (ii)
Incomplete mixing in radial direction (formation of parabolic velocity profile, may cause this
effect). The reasons for non-ideality in real reactors are
 Presence of stagnant regions (or dead zones), bypassing or short-circuiting – CSTR
 Mixing in longitudinal direction, Incomplete mixing in radial direction and Channeling -
PFR
Note: Deviations from ideal performance divide into two classifications;
 The first is a flow arrangement in which elements do not mix, but follow separate paths
through the reactor (segregated flow). These elements are retained in the reactor for
different times, that is, they have different residence times.
 The second is a flow arrangement whereby elements of fluid partially mix (micro mixing).
(ii)
2. (i) Explain the method of conducting Stimulus response experiments.

(ii) Derive the equation to find out conversion by direct use of tracer curve.
Ans: (i)
 On the above Pulse and Step are easier to interpret, Periodic and Random are harder.
There are two experimental methods for finding E- curve;
I. Pulse (non-continuous input) experiment
 C-curve (Cpulse vs. t)
 E = Cpulse/Area under C-curve
II. Step (continuous input) experiment

 F-curve (CStep vs. t)
 E = dF/dt or F = ∫ E dt

(ii) To evaluate reactor behavior in general we have to know four factors:

1. The kinetics of the reaction
2. The RTD of fluid in the reactor
3. The earliness or lateness of fluid mixing in the reactor
4. Whether the fluid is a micro or macro fluid
For macrofluids, imagine little clumps of fluid staying for different lengths of time in the reactor
(given by the E function). Each clump reacts away as a little batch reactor, thus fluid elements will
have different compositions. So the mean composition in the exit stream will have to account for
these two factors, the kinetics and the RTD. In words, then

3. A sample of tracer was injected as a pulse to a reactor and the effluent concentration (C) measured
as a function of time, resulting in the following data;
t, min 0 1 2 3 4 5 6 7 8 9 10 12 14
3
C, g/m 0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
(i) Plot C(t) and E(t).
(ii) Determine the fraction of material leaving the reactor that has spent time between 3 and 6
minutes in the reactor and the fraction of material leaving that has spent 7.75 and 8.25 minutes in
the reactor.
Ans: (i) Plot the given C vs. t and get area under the C-curve [Σ(c. ∆t) = 49.9 g-min/m3]
Then, E(t) = C(t) / Area under the c-curve[Σ(c. ∆t)] and
Plot E vs. t, which is E-curve.
(ii) Using the above E-curve,
Find the area under the curve between 3 and 6 minutes, which gives the fraction material
leaving, ≈ 0.5 and
The area between 7.75 and 8.25 minutes ≈ 0.03
4. A first order reaction is carried out in a Non-ideal tubular reactor. Assuming that the Axial
dispersion model is valid, derive an expression for conversion in the reactor.
Ans: By material balance on the tubular reactor, we get
D (∂2CA/∂x2) – U (∂CA/∂x) – k CAn = 0
 On normalizing the above expression for entire length of reactor, we get

[D/(U. L)] (∂2CA/∂z2) – (∂CA/∂z) – k τ CAn = 0
 In terms of conversion, we have

[D/(U. L)] (∂2XA/∂z2) – (∂XA/∂z) + k τ CAon-1(1 – XA)n = 0
 On solving the above second order differential equation for first order (n = 1) reaction, we
get
1 – XA = 4 a exp{(1/2) [(U. L)/D]} / {(1+a)2 exp{(a/2) [(U. L)/D]} -
(1+a)2 exp{(-a/2) [(U. L)/D]}}
Where a = SQRT{1 + 4 k τ [D/(U. L)]}
5. The concentration reading in the table represents a continuous response to a pulse input;
t, min 0 5 10 15 20 25 30 35
C, gm/lit 0 3 5 5 4 2 1 0
This vessel is used as a reactor for a liquid decomposing with rate -rA = k CA & k = 0.307 min-1.
Find the conversion expected in the reactor and compare it with the PFR by
(i) Direct use of Tracer curve.
(ii) Using Dispersion model.
Ans: (i) Since ∆t = 5 min, constant
 Σ(C. ∆t) = ∆t. Σ(c) = 5 * 20 = 100 g-min/lit.
 E = c/[∆t. Σ(c)] or c/area under the c-curve.
 Using this E-value, find the [∆t. Σ(E. e-kt)] = 1 – XA ≈ 0.106
or XA ≈ 0.894
(ii) Since ∆t = 5 min, constant
 Σ(c. ∆t) = ∆t. Σ(c) = 5 * 20 = 100 g-min/lit.
Σ(t. c. ∆t) = ∆t. Σ(t. c) = 5 * 300 = 1500 g-min2/lit.

Σ(t2. c. ∆t) = ∆t. Σ(t2 . c) = 5 * 5450 = 27250 g-min3/lit.
 Mean residence time, t = Σ(t. c. ∆t)/Σ(c. ∆t) = 1500/100 = 15 min
 Variance, σ2 = {Σ(t2. c. ∆t)/Σ(c. ∆t)} – t2

= (27250/100) – (15)2 = 47.5 min2
 Assuming small extent or deviation from plug flow, we know
σθ2 = σ2/t2 = 2[D/UL] = 47.5/(15)2 = 0.2111

or [D/UL]= 0.1056 or [UL/D] ≈ 9.47
 We know,
Substituting the given ‘k’ and determined t & (D/UL) into the above, we get
a = 1.5057 and 1 – XA ≈ 0. 0875 or XA ≈ 0.9125
6. For a Non-ideal reactor described by N-Tank’s in series model, derive an expression for E().
Ans:
 Tank-1: By material balance, we get C1 = C0 e-t/ ti and Eθ1 = ti E1 = e-θi
 Tank-2: By material balance, we get C2 = C0 (t/ti) e-t/ ti and Eθ2 = ti E2 = (θ2) e-θ2
 Tank-3: By material balance, we get C3 = C0/2! (t/ti)2 e-t/ ti and

Eθ3 = ti E3 = (1/2!) (θ3)2 e-θ3
 Tank-4: By material balance, we get C4 = C0/3! (t/ti)3 e-t/ti and

Eθ4 = ti E4 = (1/3!) (θ4)3 e-θ4
 Similarly, for Nth tank, we get CN = C0/(N-1)! (t/ti)N-1 e-t/ti and

EθN = ti EN = 1/(N-1)! (θN)N-1 e-θN
 In the dimensionless form of time, θ = t/toverall and θi = N. θ, and using the above ‘EθN’, we
get
Eθ = N. Eθi = [NN/(N-1)!] θN-1e-Nθ
7. The tracer concentration in the effluent stream of a reactor as a function of time is tabulated as
follows;
t (s) 0 100 200 300 460 500 670 735 840 960
C (g/m3) 0 2.9 8.7 12.4 10 6.5 3.0 1.5 0.5 0

Calculate the conversion as per the Tank’s-in-series model, if a first order irreversible liquid phase
reaction takes place in the reactor. The rate constant is k = 0.0056 s-1.
Ans:
 Σ(c. ∆t) = 4920 g-sec/m3 Σ(t. c. ∆t) = 1898462.5 g-sec2/m3
Σ(t2. c. ∆t) = 871514937.5 g-sec3/m3
 Mean residence time, t = Σ(t. c. ∆t)/Σ(c. ∆t) =1898462.5/4920 = 385.8664 secs
 Variance, σ2 = {Σ(t2. c. ∆t)/Σ(c. ∆t)} – t2

= (871514937.5/4920) – (385.8664)2 = 28244.3038 secs2
 By Tanks-in-series model, we know that

N = 1/σθ2 = t2/σ2 = (385.8664)2 / 28244.3038 = 5.2716 ≈ 6
 Therefore, 1 – XA = 1/{1 + [(k. t)/N]}N

= 1/{1 + [(0.0056 * 385.8664)/6}6 ≈ 0.158
(or) XA = 0.842 or 84.2%
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UNIT-II (HETEROGENEOUS REACTIONS & SOLID CATALYSIS)
1. Define Catalysis.
“Catalysis” is a term refers to a process in which the rate of reaction is influenced by a substance (catalyst)
that remains chemically unaffected.
2. List the general characteristics of catalysis.

The general characteristics of catalysis are;
 A catalyst accelerates reaction by providing alternate paths of products, the activation energy of each
catalytic step being less than that for the homogeneous (non-catalytic) reaction.
 In the reaction cycle, active centers of catalysis first combine with at least one reactant and then are
reproduced with the appearance of product. The freed center then combines with reactant to produce
another cycle.
 Comparatively small quantities of catalytic centers are required to produce large amounts of product.
 Equilibrium conversion is not altered by catalysis. A catalyst which accelerates the forward reaction in
an equilibrium system is a catalyst for the reverse reaction.
 The catalyst can radically alter selectivity.
3. What do you mean by rate controlling step in heterogeneous reactions?

The slowest possible step in the sequence of steps involved in heterogeneous processes is said to be rate
controlling step.
Note: The sequence of steps involved in heterogeneous processes is;
 Transport of reactants from the bulk fluid to the fluid-solid interface.
 Intraparticle transport of reactants into the catalyst particle (if it is porous).
 Adsorption of reactants at interior sites of the catalyst.
 Chemical reaction of adsorbed reactants to adsorbed products (surface reaction - the intrinsic
chemical step.
 Desorption of adsorbed products.
 Transport of products from the interior sites to the outer surface of the catalyst particle.
 Transport of products from the fluid-solid interface into the bulk-fluid stream. (Mostly the reaction
step is the rate controlling one)

4. What is homogeneous catalysis? Give one example.
Homogeneous catalysis is one in which the reactants, the catalyst and the products are in same or single .
The basis for the any catalytic theory is that first the catalyst and one or more of the reactants form an
intermediate complex, a loosely bound compound – which is unstable. This complex then takes part in
subsequent reactions which results in the final products and the regenerated catalyst.
The kinetics of the hydrolysis of ethyl acetate catalyzed by hydrochloric acid can be explained by the
following mechanism.
CH3COOC2H5 + H+  CH3C00C2H5 [H+]
CH3C00C2H5 [H+] + H2O  C2H5OH + CH3C00H + H+
5. Does a catalyst alter equilibrium conversion of a chemical reaction? Explain.

No. With a reversible reaction, a catalyst which increases the rate will increase the rate of both the forward
and the backward reaction. This is useful because the catalyst will, cause the reaction mixture to reach its
equilibrium composition more quickly. So, the catalyst will not change the equilibrium composition of the
substance and hence the conversion.
6. Is the selectivity of multiple reactions affected by catalysts? Explain.

Yes, the selectivity of multiple reactions is affected by catalysts. It means that the selectivity changes only
the rate of desired and undesired materials in the multiple reactions. Thus, in the presence of appropriate
catalyst, products containing predominantly the materials desired can be obtained from a given feed.
7. Define adsorption and adsorbent. (NOV/DEC 2013)

It is a surface phenomenon, in which accumulation of any substance (Adsorbate) on the surface
of another substance (Adsorbent) takes place.
Two types of adsorption may occur;
 Physical adsorption: It is non-specific and somewhat similar to the process of condensation. The
forces attracting the fluid molecules to the solid surface are relatively weak.
 Chemisorption: It is specific and involves forces much stronger than in physical adsorption.
8. What is Chemisorption?
 It is specific and involves forces much stronger than in physical adsorption.
 The process is often irreversible.
 The energy of activation is low for non-activated adsorption and high for activated adsorption.
9. Explain two characteristics of physical adsorption. [Dec 2012]

Some of the important characteristics of physisorption are as follows;
(i) Deficient of specificity: since the van der Waal forces are universal, a given surface of adsorbent
does not show any preference for any specific gas. It can adsorb all the gases but to a different
extent.
(ii) (ii) Reversible nature: physical adsorption of a gas by the solid is reversible and thus equilibrium
is reached rapidly Solid + Gas gas/solid + Heat Thus, according to Le-chatelier's principle, -
Increase of pressure pushes the equilibrium in forward direction leading to more adsorption of gas
and decrease of pressure cause desorption to occur. - Since process is exothermic, therefore,
lowering of temperature favors more adsorption and increase of temperature leads to desorption.
10. State the assumptions of Langmuir adsorption isotherm.

The assumptions made over Langmuir treatment of adsorption are;
 All the surface of the catalyst has the same activity for adsorption.
 There is no interaction between adsorbed molecules (or) the amount adsorbed has no effect on the
rate of adsorption per site.
 All the adsorption occurs by the same mechanism, and each adsorbed complex has the same
structure.
 The extent of adsorption is less than on complete monomolecular layer on the surface.
11. Derive the Langmuir isotherm for the adsorption of a single species.

Since the adsorption is limited to complete coverage by a monomolecular layer, the surface may be divide
into two parts; the fraction ‘θ’ covered by the adsorbed molecule and the fraction (1 – θ), which is bare.
Since only those molecules striking the uncovered part of the surface can be adsorbed, the rate of adsorption
per unit of total surface will be proportional to (1 – θ); that is
rad = k p (1 – θ)
The rate of Desorption will be proportional to the fraction of covered surface. That is
rde = kI θ
At equilibrium, rad = rde or k p (1 – θ) = kI θ
Solving for ‘θ’, we get θ = k p/(kI + k p) = K p/(1 + K p) = v/vm
The above equation is called ‘Langmuir isotherm’. Where K = k/kI is the adsorption equilibrium constant,
expressed in units of (pressure)-1.
12. Write the B E T equation for multilayer adsorption.

The Brunauer-Emmett-Teller (B E T) equation is
P / [v (po – p)] = [1 / (vm c)] + {[(c – 1) p] / (c vm po)}
Where p - partial pressure of adsorbed gaseous molecule
p0 - saturation or vapor pressure
v - volume of gas adsorbed
vm - volume adsorbed when all the active sites are covered
c - a constant for the particular temperature and gas-solid system
13. A non-porous catalyst particle is of size 2 microns and density is 2 g/cm3. Calculate the external
surface area per gram of the particle.
The external surface area per gram of the particle, Sg
= 6 / [(Size of the particle, dp) (Density of the particle, ρp)]
= 6 / {[2 x 10-4 (cm)] [2 (g/cm3)]}
Or Sg = 1.5 x 104 cm2/g
14. Explain the principle of mercury-penetration method for the determination of pore-size distribution
in a catalyst particle.
The mercury-penetration method for the determination of pore size distribution in a catalyst particle
depends on the fact that mercury has a significant surface tension and does not wet most catalytic surfaces.
This means that the pressure required to force mercury into the pores depends on the pore radius.
15. List the advantages of the Langmuir-Hinshelwood method in developing rate equations.
The advantages of the Langmuir-Hinshelwood method are;
 The resultant rate equation may be extrapolated more accurately to concentrations beyond the range
of experimental measurements used.
 The method does take into account adsorption and surface reactions (which must occur) in a
consistent manner.
16. Give the classification of catalyst.

There are two broad classes of catalyst;
 Biochemical catalysts, called Enzymes, are found everywhere in the biochemical world and in
living creatures and operate at close to ambient temperature.
 Man-made catalysts, mostly solids, usually aim to cause the high-temperature rupture or synthesis
of materials.
17. What is Catalyst promoter? (NOV/DEC 2014)

Catalyst promoters are substances which do not act as catalyst but enhance the efficiency or activity or
selectivity or stability of catalyst and prolong catalyst life. For example, the catalytic activity of V 2O5 in
oxidation of SO2 is enhanced appreciably when sulphates of alkali metals are added in small amounts.
18. What is catalyst inhibition? (NOV/DEC 2014)

Catalyst inhibitors are substances which decrease the rate of reaction, or activity or selectivity or stability of
the catalyst. For example in the oxidation of ethylene, ethylene oxide is the desirable product. At the

same conditions CO2 and H2O are also formed by complete oxidation, but this reaction is undesirable and
needs to be suppressed. In this process silver supported alumina is a good catalyst but if halogen compound
is added, CO2 and H2O formation is reduced.
19. State the types of catalyst poisoning.

The decrease in the activity of catalyst due to poisons, which will be defined as substances (either in the
reactants stream or produced by reaction) which lower the activity of catalyst.
The types of catalyst poisoning are;
 Deposited poisons
 Chemisorbed poisons
 Selectivity poisons
 Stability poisons
 Diffusion poisons
20. Difference between physical adsorption and chemisorptions.(NOV/DEC 2013)
1. (i) Explain the steps involved in catalytic chemical reactions.

(ii) Discuss the nature of catalytic reaction with suitable examples.
Ans: (i) The sequence of steps involved in heterogeneous processes is;
 Transport of reactants from the bulk fluid to the fluid-solid interface.
 Intraparticle transport of reactants into the catalyst particle (if it is porous).
 Adsorption of reactants at interior sites of the catalyst.
 Chemical reaction of adsorbed reactants to adsorbed products (surface reaction - the
intrinsic chemical step.
 Transport of products from the interior sites to the outer surface of the catalyst particle.
 Transport of products from the fluid-solid interface into the bulk-fluid stream.
(ii) A catalyst is effective in increasing the rate of reaction because it makes possible an alternative
mechanism, each step of which has a lower free energy of activation than that for an uncatalyzed
process.
 The combination of reactant and the catalyst is a widely accepted basis for explaining the
catalysis.
 A relatively small amount of catalyst can cause conversion of a large amount of reactant.
 The position of equilibrium in a reversible reaction is not changed by the presence of the
catalyst.
Note: Choose any simple example and match with above points.

2. Explain the various theories of adsorption and derive the related equation.
Physical adsorption
 It is nonspecific (similar to the process of condensation) and forces attracting the fluid
molecules to the solid surface are relatively weak.
 Equilibrium between the solid and the gas molecules is usually rapidly attained and easily
reversible.
 The energy of activation is usually low (no more than 1 kcal/mol).
The various adsorption isotherms are;
 Langmuir isotherm {Cg/C = (I/Cm) Cg + [1/(Kc. Cm)]}
 Freundlich isotherm {ln(C) = (1/n) ln(P) + ln(c. Cm)}
 Temkin isotherm {C = (k1Cm) ln(P) + (k1Cm)ln(k2)}
The above isotherms importance and significance to be explained with necessary plots.
3. Consider a solid catalyzed reaction A  R + S. Assuming Langmuir-Hinshelwood model, derive

the kinetic Rate equation. Assume Surface reaction to be rate controlling.
Ans: The reaction mechanism is
A + X  A.X (Adsorption)
A.X + X  R.X + S.X (Surface reaction)
R.X  R + X
S.X  S + X (Desorption)
Given, Surface reaction is rate limiting.
 The concentration of reaction components at equilibrium are

CA = K A C A C v CR = KR CR Cv and CS = KS CS Cv ------ 1
 For the surface reaction, we get r|sur = [ksur CA Cv – ksur| CR CS]

Substituting equation 1 into the above, we get
r|sur =ks (Cv2 ) [KA CA – (KR KS/Ksur) CR CS] ------ 2
 By equilibrium concepts for surface reaction, we know

K = (Ksur KA)/(KR KS) or (KR KS/Ksur)= KA,/K ------ 3
 We know, Cm = CA + CR + CS + Cv
Substituting equation 1 into the above and simplifying, we get
Cv = Cm /[(KA CA) + (KR CR) + (KS CS) + 1] ------ 4

 Finally Substituting equations 3 and 4 into equation 2, we get
r|sur =ks KA (Cm2 ) [CA – (1/K) CR CS]/[(KA CA) + (KR CR) + (KS CS) + 1]2
4. Tertiary butyl alcohol (TBA) is produced by the liquid phase hydration (W) of isobutene (I) over
an amberlyst-15 catalyst. The liquid is normally a multi-phase mixture of Isobutene, water and the
solid catalyst. The reaction can be represented as I + W  TBA. If all the species set adsorbed on
to the catalyst surface and if the adsorption of Isobutene is rate limiting, derive the Rate equation
for the reaction.

Ans: Let A – Isobutene (I), B – Water (W) and R – Tertiary Butyl Alcohol (TBA). Thus the
given reaction becomes A+BR
A + X  A.X (Adsorption)
B + X  B.X
A.X + B.X  R.X + X (Surface reaction)
R.X  R + X (Desorption)
 Given, Adsorption of ‘A’ is rate limiting.
 The concentration of reaction components (leaving ‘A’) at equilibrium are

CB = KB CB Cv and CR = KR CR Cv ------ 1
 From the surface reaction, we get KS = [CR Cv]/[CA CB]
Or CA = [CR Cv]/[KS CB]

Using equation 1 and the overall equilibrium constant {K = [KA KB KS]/KR} into the
above, we get CA = (KA/K) (CR Cv/CB) ------ 2
 We know, Cm = CA + CB + CC + Cv
Substituting equations 1 and 2 into the above and simplifying, we get
Cv = Cm /[(KA/K)(CR/CB) + (KB CB) + (KR CR) + 1] ------ 3
 We know, the rate of adsorption of ‘A’ is
rA| = kA [ CA Cv – (1/KA) CA]

Substituting equation 2 into the above, we get
rA| = kA Cv [CA – (1/K) (CR/CB)]
Finally, Sub. equation 3 into the above, we get
rA| = (kA Cm) [CA – (1/K) (CR/CB)] / [(KA/K)(CR/CB) + (KB CB) + (KR CR) + 1]
5. Describe in detail the Nitrogen adsorption method for the determination of Surface area of a
catalyst.
Ans: By the application of Langmuir adsorption isotherm for mono-molecular layer of adsorption,
Brunauer-Emmett-Teller (BET) extended the Langmuir isotherm to apply it for the multilayer
adsorption. As a result, the BET equation is
{P/[v (po – p)]} = [1 / (vm c)] + [(c – 1)/(c vm)] (p/po)
Where p - partial pressure of adsorbed gaseous molecule
p0 - saturation or vapor pressure
v - volume of gas adsorbed
vm - volume adsorbed when all the active sites are covered
c - Constant for the particular temperature and gas-solid system
 The above equation will give a linear plot with vm = 1/[Slope + Y-int)
 For the N2 adsorption at -195.5 C, the surface area Sg = 4.3653 vm (m2/g-cat)
o
6. Explain briefly about determination of Pore-volume distribution by Mercury penetration method.

7. Explain in detail about the Preparation of Catalyst.

Ans: There are four methods of catalyst preparation;
 Precipitation
 Gel formation
 Simple mixing of components
 Impregnation
Note: You can explain any two methods of catalyst preparation.

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UNIT-III (GAS-SOLID CATALYTIC REACTORS)
1. Explain Knudsen diffusion.(NOV/DEC 2013)

If the pore size of a solid catalyst is small and as the gas is less dense, then in such cases, molecules collide
more frequently with the catalyst pore walls as compared to collisions among each other. This type of
diffusion phenomena is called Knudsen diffusion.
2. Distinguish between Knudsen diffusion and Bulk diffusion.

Bulk diffusion occurs when the pores of a solid catalyst are considerably large and the gas is relatively
dense or if the pores are filled with liquid.
If the pore size of a solid catalyst is small and as the gas is less dense, then in such cases, molecules collide
more frequently with the catalyst pore walls as compared to collisions among each other. This type of
diffusion phenomena is called Knudsen diffusion. When the reaction mixture in the pore is liquid, Knudsen
diffusion does not occur.
3. Write short notes on surface diffusion.

The transport by movement of adsorbed molecules over the catalyst surface is called Surface Diffusion. The
direction of diffusion is that of the increasing surface concentration. Surface diffusion contributes little to
overall transport through a porous mass unless appreciable adsorption occurs.
4. Define Effective diffusivity. (NOV/DEC 2014)

In a porous catalyst, the pores in a catalyst are not straight and they follow tortuous (zig-zag),
interconnecting paths having varying cross sectional area. To account this variation, effective diffusivity is
considered.
Effective diffusion coefficient accounts for the average diffusion taking place at any position in the catalyst
pellet and it is the function of both bulk diffusivity and Knudsen diffusivity. It is denoted by ‘De’. Effective
diffusivities in porous catalysts are usually measured under conditions where the pressure is maintained
constant by external means.
5. What is a Parallel pore model?

This is a geometric model of the pore system, used to convert ‘D’ to ‘De’ for the porous pellet. It is the
model based on the properties (s, Vg, p), to represent the mono-disperse pore-size distribution in a catalyst
pellet. By this model, the effective diffusivity is De =  D/.
Where ‘’ is the tortuosity factor, ‘’ is the porosity of the pellet and ‘D’ is the diffusivity (in the absence of
surface diffusion).
6. What is Random pore model?

This model was originally developed for pellets containing a bi-disperse pore system (considering both
Macro and Micro pores) to convert ‘D’ to ‘De’. By this model, the effective diffusivity is De = [M2] DM +
[μ2 (1 + 3M)/ (1 - M)] Dμ
Where DM & Dμ are the diffusivities for macro and micro pore regimes and M & M are the porosities for
the macro and micro pore regimes.
7. What are the resistances in porous catalyst?

The resistances in porous catalyst are;
 Resistance offered by the diffusion of reactants (gas or liquid) into the pores of the solid catalyst
(Pore diffusion resistance or diffusional mass transfer resistance)
 Resistance offered by the resultant rate equation for the surface phenomena (Reaction resistance)
8. Define Thiele modulus. Give its significance. (May/June 2014)

It is a dimensionless number (denoted by ‘MT or Ф’), defined as the ratio of the intrinsic chemical reaction
rate in the absence of mass transfer limitation to the rate of diffusion through the particle. Thiele Modulus is
useful in predicting the reactor behavior from known kinetic information.

9. Define Effectiveness factor. (NOV/DEC 2014)
The effectiveness factor (denoted by ‘η’) is defined as the ratio of actual rate for the whole pellet to the rate
evaluated at outer surface conditions. OR It is the ratio of reaction rate with diffusion to the rate without
diffusion resistance.
10. Explain the significance of effectiveness factor.

For diffusion in single cylindrical pore, follows a first order kinetics, the effectiveness factor is η = tanh
(ФL) / ФL Where ‘ФL’ is the Thiele modulus and is given by ФL = L / (k p / De)1/2
‘L’ is the thickness of cylindrical pore.
For small ФL (ФL < 0.4), η ≈ 1, the concentration of reactant does not drop appreciably within the pore; thus
pore diffusion offers negligible resistance.
For large ФL (ФL > 4), η = 1/ФL, the reactant concentration drops rapidly to zero on moving into the pore,
hence diffusion strongly influences the rate of reaction.
11. Define Effectiveness factor. [Dec 2012]

The effectiveness factor (denoted by „η‟) is defined as the ratio of actual rate for the whole pellet to the rate
evaluated at outer surface conditions. OR It is the ratio of reaction rate with diffusion to the rate without
diffusion resistance.
12. What is the effect of catalyst pellet size on the effectiveness factor?
In the regime of strong diffusion resistance, the rate (thus the effectiveness factor) varies inversely
proportional to the catalyst pellet size. So, Increase in pellet size will decrease the value of effectiveness
factor and vice-versa.
13. Can effectiveness factor of a catalyst be greater than one? Explain.

Yes. For exothermic reactions (only), where pore resistance just begins to intrude, the effectiveness factor
can become greater than unity; because heat is released and catalyst particles are hotter than the surrounding
fluid. (Hence, non-isothermal rate is always greater than the isothermal rate as measured by the bulk fluid
stream conditions).
14. ‘In a catalyst pellet, if the rate of diffusion through the pores is much higher than the rate of reaction,
then the value of Thiele modulus will approach unity’. Justify this statement.
By the definition, we know that the Thiele modulus is the ratio of the intrinsic chemical reaction rate in the
absence of mass transfer limitation to the rate of diffusion through the particle.
If the rate of diffusion through the pores (denominator term) is much higher than the rate of reaction
(numerator term), then the value of Thiele modulus will approach unity.
15. Write short notes on ‘Non-isothermal effectiveness factor’.

For an exothermic reaction, the temperature rises going into the pellet, the increase in rate of reaction
accompanying the temperature rise can more than offset the decease in ate due to drop in reactant
concentration. Then ‘η’ values are greater than unity. While η > 1 increase the rate per pellet, and therefore
the production per unit mass of catalyst, there may also be some disadvantages. With larger ‘η’ there will be
a large increase in temperature toward the center of the pellet, resulting in sintering and catalyst
deactivation. The desired product may be subject to further reaction of unwanted product or undesirable
side reactions may occur. If these reactions have higher activation energies than the desired reaction, the
rise in temperature would reduce selectivity.
For an endothermic reaction, there is a decrease in temperature and rate into the pellet. Hence ‘η’ is always
less than unity. Since the rate decreases with drop in temperature, the effect of heat-transfer resistance is
diminished.
16. Explain ‘Wagner Modulus’.

It is the modulus which accounts the pore resistance effects on the solid catalyzed reaction, which is given
by MW = MT2 η = L2 (-rA||| / CA)obs / De
Where ‘MT’ is the Thiele modulus, ‘η’ is the effectiveness factor, ‘L’ is the characteristic size of the
catalyst, (-rA|||) is the reaction rate based on the volume of the catalyst pellet, ‘C A’ is the fluid concentration
at absolute conditions and ‘De’ is the effective diffusivity.

17. When is it said that a reaction follows ideal mechanism in gas-solid catalytic reactions
If η → 1 (‘MT or Ф’ is large enough) then it is said that the gas solid catalytic reaction follows ideal
mechanism. That is, this condition means that diffusion into the pellet is relatively slow, so that reaction
occurs before the reactant has diffused far into the pellet.
18. Define Effective thermal conductivity. (NOV/DEC 2013)

The effective thermal conductivity (ke) is the energy transferred per unit of total area of pellet
(perpendicular to the direction of heat transfer).
19. Compare fixed and fluidized - bed reactors for gas-solid catalytic operation.
 It is not possible to use fine size catalyst particles in fixed bed reactor. This results in plugging and
high pressure drop. High pressure increases the operating cost.
It is possible to use fine size catalyst particles in fluidized bed reactor. Fine size particles provide
large interfacial / contact area.
 Catalyst regeneration can be a problem in fixed bed reactor. If the regeneration needs to be
frequently done, this problem will be bottleneck in operation.
Catalyst particle regeneration is quite easy in fluidized bed reactors. If the regeneration needs to be
done frequently, the catalyst particles can be entrained with the product stream, separated in
cyclone separator and then sent to the regenerator.
20. List some of the problems that would be encountered in the operation of a fluidized catalytic reactor.
In operation of a fluidized catalytic reactor, some difficulties can occur. They are;
 Slugging: When the gas passes up through the catalyst bed in the form of large gas bubbles, it is
called as Slugging of fluidized bed.
 Channeling: When the gas is not evenly distributed in the catalyst bed cross section and is
concentrated in channels through the catalyst bed, the phenomena is called as Channeling of
fluidized bed.
1. Explain the methods of determining the effective diffusivity.

2. Show that the Effectiveness factor (η) for a first order reaction in an isothermal spherical catalyst
pellet is given by
Where ‘Φ’ is the Thiele modulus.

Ans: By material balance, at steady state, we have
d2CA/dx2 + (2/r) dCA/dx – (k’ ρp/De) CA = 0
 On solving with boundary conditions, we get

CA/CAs = (rs/r) Sinh [3Ф(r/rs] / Sinh (3Ф)
Where ‘Ф’, Thiele modulus = (rs/3) SQRT (k| ρp/De)
 By definition, effectiveness factor (η) = rA, with diffusion / rA, without diffusion
= [dCA/dx]x = L / CAs
 Using the above equations, on solving, finally we get

η = (1/Ф) [(1/ tanh (3Ф)) - (1/3Ф)]
or
3. A first order irreversible reaction takes place in a solid catalyst. Considering a single straight pore
(cylindrical or slab shaped) in the catalyst particle, develop an expression for concentration profile
of the reactant in the pore and derive the expression for effectiveness factor for the same. State all
assumptions made.
Ans: By material balance, at steady state, we have
d2CA/dx2 – (2 k’’/De r) CA = 0
 On solving with boundary conditions, we get

CA/CAs = Cosh [m (L – x)] / Cosh (m L)
This is the concentration profile of the reactant.
Where m = SQRT [2 k|/De r] and (m L) is the Thiele modulus.
 By definition, effectiveness factor (η) = rA, with diffusion / rA, without diffusion
= CA,avg / CAs =[dCA/dx]x = L / CAs
 Using the above equations, on solving, finally we get

η = tanh (m L) / (m L)
4. Explain briefly;
(i) Effectiveness factor under Non-isothermal conditions.
(ii) Effective Thermal conductivity and the effect of Pore volume on it.
Ans: (i) When reaction is so fast that the heat released (or absorbed) in the pellet cannot be
removed rapidly enough to keep the pellet close to the temperature of the fluid, then non-
isothermal effects intrude.
For exothermic reactions only, where the pore resistance just begins to intrude, the
effectiveness factor can become greater than unity; because of a temperature gradient within the
particle or by the gas film surrounding the particle.

(ii) Ans: The effective thermal conductivity (ke) is the energy transferred per unit of total area of
pellet (perpendicular to the direction of heat transfer).
 Effective thermal conductivity is low for porous solid particles because of more void
regions or fractions.
 So, Effective thermal conductivity is inversely proportional to the Pore volume.
5. A first order heterogeneous irreversible reaction A  R is taking place within a spherical catalyst
pellet which is plated throughout the pellet. The reactant concentration midway between the
external surface and the center of the pellet is equal to 1/10 of the concentration at the external
surface. The concentration of the reactant at the external surface is 0.001 gmol/lit. The pellet
diameter is 2 x 10-3 cm and the diffusion coefficient is 0.1 cm2/s.
(i) What is the concentration of the reactant at a distance of 3 x 10-4 cm from the external pellet
surface?
(ii) To what diameter should the pellet be reduced, if the effectiveness factor is to be 0.8?
Ans: (i) We know, the concentration profile for the diffusion through porous spherical catalyst is
CA/CAs = (rs/r) [sinh(m r)/sinh(m rs)]
 Substituting the given CAs = 1x10-3 mol/lit, CA = (1/10) CAs = 1x10-4 mol/lit, rs = ds/2 =
1x10-3 cm and at r = rs/2 (mid-way) = 5x10-4 cm into the above , we get (by trial and error
method) m ≈ 6000
 Now substituting rs - r = 3x10-4 cm or r = 7x10-4 cm, determined ‘m’ and the other given
data’s into the above equation, we get CA ≈ 2.364x10-4 mol/lit
(ii) We know, for spherical catalyst,

ηs = [3/(m rs)] {[1/tanh(m rs)] – [1/(m rs)]}
 For the given rs = ds/2 = 1x10-3 cm and m ≈ 6000, the above equation yields
ηs ≈ 0.417
 Also, we know ηs α (1/rs) or ηs1/ηs2 = rs2/rs1
 Substituting the given ηs = 0.8 along with the determined values into the above, we get
rs2 ≈ 0.0005 cm

Says that the pellet is approximately reduced to half of its original value.
6. (i) Derive a mathematical equation for the design of a fixed bed (packed bed) catalytic reactor in
which a first order gas phase reaction A  R is carried out
(ii) Compare the packed bed reactor and fluidized bed reactor for a catalytic chemical reaction.
Ans: The basic assumption is the heterogeneous region is isothermal.
 Writing material balance for the differential portion of the packed bed reactor, we get,
FAo dXA = (-rA|) dW
 Which on integrated over the whole reactor gives

XA
W/FAo = ∫ dXA/(-rA|)
0
 For first order catalytic reactions, the above equation (on simplification) becomes
K| Τ| = - (1 + εA) ln(1 – XA) - εA XA Where Τ| = W CAo/FAo
(ii) Ans: Packed Bed Reactor (PBR)

 Primarily employed in the manufacture of Industrial chemicals
 Most widely used reactors for immobilized enzymes and immobilized microbial cells
Advantages:
 High conversion per unit mass of catalyst
 Low operating cost
 Stabilization of operating conditions
Disadvantages:
 Poor temperature control
 Undesired thermal gradients may exist
 Channeling may occur
 Unit may be difficult to service and clean
Fluidized Bed Reactor (FBR)

 Primarily employed in petroleum refineries in the cracking of crude oil.
 In this type of reactor, a fluid (gas or liquid) is passed through a granular solid material
(usually a catalyst possibly shaped as tiny spheres) at high enough velocities to suspend the
solid and cause it to behave as though it were a fluid
Advantages:
 Good mixing
 Good uniformity of temperature
 Catalyst can be continuously regenerated with the use of an auxiliary loop
Disadvantages:
 Bed-fluid mechanics not well known
 Severe agitation can result in catalyst destruction and dust formation
 Uncertain scale-up
 Entrainment loss
7. A first order catalytic reaction A  R is carried out in a packed bed reactor. The molal feed rate of
the reactant is 12.5 kmol/hr. The following data is available;
W (kg cat) 0.625 1.87 3.125 4.375 6.25 7.5 8.75

XA 0.058 0.139 0.213 0.288 0.381 0.440 0.493
Calculate the weight of the catalyst for 40% conversion in a packed bed reactor, if the molal feed
rate is increased to 125 kmol/hr.
 Ans : We know
That is, a plot of XA vs. W/FAo will give slope as –rAI.
 From the given data, FAo = 12.5 kmol/hr, we have

W/FAo (X) 0.05 0.15 0.25 0.35 0.5 0.6 0.7
XA (Y) 0.058 0.139 0.213 0.288 0.381 0.440 0.493
 From the plot between XA vs. W/FAo, at XA = 0.4, We get

W/FAo ≈ 0.53
 Now, for the given new FAo = 125 kmol/hr, we get

W = 0.53 * 125 ≈ 66.25 Kg
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UNIT-IV (GAS-SOLID NON-CATALYTIC REACTORS)
1. Give the industrial importance of Gas-Solid non-catalytic reactions.

Gas-Solid non-catalytic reactions are employed in;
(Solids does not appreciably change in size during the reaction)
 Roasting of ores.
 The preparation of metals from their oxides in reducing atmospheres.
 The platting of metals.
 Reactions of carbonaceous materials.
(Reactions in which solids change in size)
 Manufacture of carbon disulfide [CS2 (gas)]
 Manufacture of sodium cyanide [NaCN (liquid)]
 Manufacture of sodium thio sulfate [Na2S2O3 (solution)]
 Dissolution reactions
 Attack of metal chips by acids
 Rusting of iron
2. Give two examples of an fluid-solid reaction in which the particles do not change their size on
reaction.
 Iron is prepared form crushed and sized magnetic ore in continuous-countercurrent, three stage,
fluidized bed reactors according to the reaction
Fe3O4 (s) + 4 H2 (g) → 3 Fe (s) + 4 H2O (g)
 With steam, water gas is obtained by the reactions
C (s) + H2O (g) → CO (g) + H2 (g)
C (s) + 2 H2O (g) → CO2 (g) +2 H2 (g)
3. Name the models used in gas-solid non-catalytic reactions. (NOV/DEC 2013)

For the Gas-Solid non-catalytic reactions, two idealized models are available;

(i) Progressive-conversion model [PCM]
(ii) Shrinking-core model [SCM]
4. Briefly explain the Progressive Conversion Model for the gas-solid non-catalytic reactions.
 Solid reactant is converted continuously and progressively throughout the particle.
 The reaction rates are different at different locations within the particle.
 This model does not match with the real situations.
5. Explain Progressive Conversion Model. [Dec 2012]
 Solid reactant is converted continuously and progressively throughout the particle.
 The reaction rates are different at different locations within the particle.
 This model does not match with the real situations.
6. In the ‘Shrinking Core Model’ for gas-solid non-catalytic reactions, explain the term ‘Shrinking
Core’.
Shrinking Core means, at any time, there exists an unreacted core of material which shrinks in size during
reaction.
7. Explain the mechanism of Shrinking Core Model.

 At any time there exists an unreacted core of material which shrinks in size during reaction.
 The reaction rate depends on the movement of unreacted core and the resistances involved in it.
 Most of the practical situations (burning of coal, wood, briquettes, etc.) show that this model
approximately matches with reality.
8. What are the limitations of Shrinking Core Model? (NOV/DEC 2014) (May June 2014)
It is the best simple representation for the majority of reacting gas-solid systems. However, there are two
broad exceptions to this statement;
 First, Slow reaction of a gas with a very porous solid will not fit to the reality.
 Second, when solid is converted by the action of heat and without needing contact with gas – Such
as baking bread, roasting chickens are mouth watering examples of such reactions.
9. What are the advantages of FBR? (NOV/DEC 2013)

Uniform Particle Mixing: Due to the intrinsic fluid-like behavior of the solid material, fluidized beds do
not experience poor mixing as in packed beds. This complete mixing allows for a uniform product that can
often be hard to achieve in other reactor designs. The elimination of radial and axial concentration gradients
also allows for better fluid-solid contact, which is essential for reaction efficiency and quality.
Uniform Temperature Gradients: Many chemical reactions require the addition or removal of heat. Local
hot or cold spots within the reaction bed, often a problem in packed beds, are avoided in a fluidized
situation such as an FBR. In other reactor types, these local temperature differences, especially hotspots,
can result in product degradation. Thus FBRs are well suited to exothermic reactions. Researchers have also
learned that the bed-to-surface heat transfer coefficients for FBRs are high.
Ability to Operate Reactor in Continuous State: The fluidized bed nature of these reactors allows for the
ability to continuously withdraw product and introduce new reactants into the reaction vessel. Operating at
a continuous process state allows manufacturers to produce their various products more efficiently due to
the removal of startup conditions in batch processes.
10. Bring out the differences between ‘Progressive Conversion Model’ and ‘Shrinking Core Model’ used
in gas-solid non-catalytic reactions.
Progressive-conversion model:
Shrinking-core model:
 The reaction rate depends on the movement of unreacted core and the resistances involved in it.
 Most of the practical situations (burning of coal, wood, briquettes, etc.) show that this model

approximately matches with reality.
11. Explain the characteristics of Fluidized bed reactor. [Dec 2012]

A fluidized bed reactor (FBR) is a type of reactor device that can be used to carry out a variety of
multiphase chemical reactions. In this type of reactor, a fluid (gas or liquid) is passed through a granular
solid material (usually a catalyst possibly shaped as tiny spheres) at high enough velocities to suspend the
solid and cause it to behave as though it were a fluid. This process, known as fluidization, imparts many
important advantages to the FBR. As a result, the fluidized bed reactor is now used in many industrial
applications.
Today fluidized bed reactors are still used to produce gasoline and other fuels, along with many other
chemicals. Many industrially produced polymers are made using FBR technology, such as rubber, vinyl
chloride, polyethylene, styrenes, and polypropylene. Various utilities also use FBR's for coal gasification,
nuclear power plants, and water and waste treatment settings. Used in these applications, fluidized bed
reactors allow for a cleaner, more efficient process than previous standard reactor technologies.
12. What are the three rate controlling steps assumed in the Shrinking Core Model for gas-solid non-
catalytic reactions?
The three rate controlling steps assumed in the Shrinking Core Model for gas-solid non-catalytic reactions
are;
 Diffusion of gaseous reactant A through the film surrounding the particle to the surface of the solid.
 Penetration and diffusion of A through the blanket of ash to the surface of the unreacted core.
 Reaction of gaseous A with solid at this reaction surface.
13. State all the assumptions made in the Shrinking Core Model used for gas-solid non-catalytic
reactions.
The assumptions made in the Shrinking Core Model used for gas-solid non-catalytic reactions are;
 The pellet retains its shape during reaction.
 There is no gaseous region between the pellet and the product layer.
 The temperature is uniform throughout the heterogeneous region.
 The densities of the porous product and the reactant (solid) are the same, so that the total radius of
the pellet does not change with time.
14. Explain the resistances that would encountered during the burning of coal.
The resistance that would be encountered during the burning of coal are;
 Diffusion resistance offered by the gas film surrounding the surface of the solid (coal) particle.
 Diffusion resistance offered by the blanket of ash surrounding the unreacted core of the (coal)
particle.
 Reaction resistance on the surface of the unreacted core (coal).
15. Explain how the rate determining step is calculated in gas-solid non-catalytic reactions.
The kinetic runs with different sizes of particles can distinguish between reactions in the chemical and
physical steps control (for gas-solid non-catalytic reactions) as,
t  R1.5 to 2.0 for film diffusion controlling
tR 2
for ash layer diffusion controlling
tR for
chemical reaction controlling.
16. Sketch the

concentration profile for the gas-
solid non-catalytic reaction in
which the resistance through
the ash layer is rate
controlling.

17. In a gas-solid non-catalytic reaction, a 4mm solid is 7/8th converted. What is the diameter of the
shrinking core?
Solution: Given D = 4 mm and XB = 7/8 or 0.875.
We know, the fraction unconverted is 1 – xB = (dc/D)3
Where ‘dc’ & ‘D’ are the diameters of the unreacted (shrinking) core and the original diameter of the solid
particle.
Substituting the given data into the above equation, we get
1 – 0.875 = (dc/4)3
On solving the above, we get dc = 2 mm
18. Find the rate controlling mechanism, form the following data
dP, cm XB t, hr
1 0.3 2
1 0.75 5
Solution: Since ‘dp’ is same for the two given data’s, we try to find the rate controlling mechanism by
considering the time‘t’ and conversion ‘XB’.
By assuming G-film surrounding the particles is rate controlling, we have
t/T = XB Where ‘T’ is the time for complete conversion.
Sub. the given first data into the above, we get T1 = 2/0.3 = 6.6667 hr
Sub. the given second data into the above, we get T2 = 5/0.75 = 6.6667 hr
Since T1 = T2, our assumption is correct.
That is, G-film surrounding the particles controls this reaction.
19. A gas-solid non-catalytic reaction taking place in a constant environment. It was found that the time
for complete conversion of 2mm particle is four times the time for complete conversion of 1mm
particle. What resistance is rate controlling?
Solution: Given D1 = 1mm, D2 = 2 mm and T2 = 4 T1.
From the given data, it was observed that
(T2 / T1) = (D2 / D1)2 or (R2 / R1)2
Or T α R2.
Thus, Diffusion through ash layer controls this reaction.
20. State how to reduce the gas film resistance for non-catalytic chemical reaction.
By increasing the mass transfer coefficient (kg), the gas film resistance (1/kg) can be reduced for non-
catalytic chemical reaction.
1. (i) Discuss the models used for studying the kinetics of non-catalytic reactions.
(ii) Derive the conversion vs. time relationship when gas film controls the reaction for spherical
particles of unchanging size according to unreacted core model.
Ans: (i) For the Gas-Solid non-catalytic reactions, the two idealized models are;

Progressive-conversion model:
Shrinking-core model:
 The reaction rate depends on the movement of unreacted core and the resistances involved
in it.
 Most of the practical situations (burning of coal, wood, briquettes, etc.) show that this
model approximately matches with reality.
(ii) The general stoichiometry is A (g) + b B (s)  Products. By this, we have

(-rA||) = (-rB||) / b
 On solving the above equations, with fundamentals, we get
-(dNB/dt) = 4π R2 b kg CAg
 Using dNB = 4π ρB rc2 drc into the above equation and on solving the integral, we get
t = (ρB R)/(3 b kg CAg) [1 – (rc/R)3]
 For rc =0 (complete conversion), we get

Τ = (ρB R)/(3 b kg CAg)
Or t/Τ = [1 – (rc/R)3]
 We know, 1 – XB = (rc/R)3 or 1 – (rc/R)3 = XB

Thus, we get t/Τ = XB
2. Derive the relationship between Time and Conversion when Diffusion through Ash layer controls
a Fluid-Solid reaction as per the Shrinking core model. Also, show that the time ‘τ’ required for
complete burning of the solid particle is proportional to the square of the radius ‘R’
Ans: By stoichiometry and material balance, with fundamentals, we get
-(dNB/dt) [(1/rc) – (1/R)] = 4π b De CAg
t = (ρB R2)/(6 b De CAg) [1 – 3 (rc/R)2 + 2(rc/R)3]

Τ = (ρB R2)/(6 b De CAg) Or Τ α R2
 From the above, we get

t/T = [1 – 3 (rc/R)2 + 2(rc/R)3]
 We know, 1 – XB = (rc/R)3 or rc/R = (1 – XB)1/3

Thus, we get
t/Τ = [1 - 3(1 – XB)2/3 + 2(1 – XB)]
3. Obtain an expression for the global rate of reaction and Conversion vs. Time for the reaction
A (g) + b B (s)  E (g) + F (s) considering a spherical pellet and Shrinking core model, when
Chemical reaction controlling this Gas-Solid non-catalytic reaction.
Ans: By stoichiometry, we have

(-rA||) = (-rB||) / b
Or –(1/4π rc2) dNB/dt = b k|| CAg
t = (ρB R)/(b k|| CAg) [1 – (rc/R)]

Τ = (ρB R)/(b k|| CAg)
Or t/Τ = [1 – (rc/R)]
 We know, 1 – XB = (rc/R)3 or rc/R = (1 – XB)1/3

Thus, we get t/Τ = [1 - (1 – XB)1/3]
4. (i) Explain in detail the determination of rate controlling step for non-catalytic reaction.
(ii) A batch of solids of uniform size is treated by gas in a uniform environment. Solid is converted
to give a non-flaking product according to the shrinking core model. Conversion is about 7/8 for a
reaction time of 1 hour and conversion is complete in two hours. What mechanism is rate
controlling?
Ans: (i) The kinetic runs with different sizes of particles can distinguish between reactions in the
chemical and physical steps control as,
t  R1.5 to 2.0 for film diffusion controlling
t  R2 for ash diffusion controlling
tR for chemical reaction controlling
(ii) Given, at t = 1 hr, XB = 7/8 and at Τ = 2 hr, XB = 1

 Assuming that chemical reaction controls the process, we know
t/Τ = [1 - (1 – XB)1/3]
 Substituting the given values into the above equation, we get LHS = RHS.
So, chemical reaction controls the process.
 Also, assuming that ash layer diffusion controls the process, we know
t/Τ = [1 - 3(1 – XB)2/3 + 2(1 – XB)]
Substituting the given values into the above equation, we get LHS = RHS.
Also, ash layer diffusion controls the process.
Hence, the process is combined resistance controlled one.
5. Two small samples of solids are introduced into a constant environment oven and kept there for
one hour. Under these conditions, 4mm particles are 58% converted and 2mm particles are 87.5%
converted.
(i) Find the rate controlling mechanism for the conversion of solids.
(ii) Find the time needed for complete conversion of 1mm particles.
Ans: (i) Let D1 = 4mm or R1 = 2mm and D2 = 2mm or R2 = 1mm.
So, XB1 = 0.58 and XB2 = 0.875
 Assuming that chemical reaction controls the process, we know

t/Τ = [1 - (1 – XB)1/3]
Given, t = 1 hr.
 For 4mm particles, (1/Τ1)= [1 - (1 – 0.58)1/3] or Τ1 ≈ 4 hr
 For 2mm particles, (1/Τ2)= [1 - (1 – 0.875)1/3] or Τ2 = 2 hr
This implies that Τ α R. Therefore, Chemical reaction controls the process.
(ii) Since Τ α R, the time needed for complete conversion of 1mm particle is 1 hour.
6. A feed consisting of 30% of 50µm, 40% of 100µm, and 30% of 200µm particles is to be fed
continuously in a thin layer onto a moving grate cross-current to a flow of reactant gas. For the
planned operating conditions the time required for complete conversion is 5, 10, and 20 minutes
for the three sizes of particles. Find the conversion of solids for a mean residence time of 8 minutes
in the reactor.
Ans: Given, the solids are in plug flow (moving grate) with tp = 8 min.
 Considering the gas at uniform composition, we know
Rm
1 – X B = ∑[1 – XB(Ri)] F(Ri)/F
R(tp=Τ)
 From the given time for complete conversion, we observe that Τ α R. Therefore, the
chemical reaction controls the operation. Thus, we have
1 – XB(Ri) = {1 – [tp/T(Ri)]}3
 Given T(50) = 5 min, T(100) = 10 min, T(200) = 20 min and F(50)/F = 0.3, F(100)/F = 0.4
and F(200)/F = 0.3
Substituting the given values into the above equations, we obtain
1 – X B = 0 + [1 – (8/10)]3 (0.4) + [1 – (8/20)]3 (0.3) = 0.068
0r X B = 0.932 (or) 93.2%
7. A fluidized bed reactor is operating at steady state with a solid feed of varying size distribution as
mentioned below;
50µm – 20%, 80µm – 20%, 100µm – 25%, 150µm – 15% and 200µm – 20%.
The fluidizing gas phase reactant has uniform composition. The time for complete conversion is 4,
8, 12, 16 and 19 minutes respectively of the above mentioned particles. The feed rate is 1.3 kg/min
and the reactor contains 15 kg of solids. Assuming the solids are hard and remain unchanged in
size & weight and also that chemical reaction is rate controlling, calculate the average fractional
conversion of the solid particles.
Ans: We know, for mixture of particles under mixed flow (fluidized bed) and chemical reaction
controls
 Given (50) = 4 min, (80) = 8 min, (100) = 12 min, (150) = 15 min, (200) = 18
min and F(50)/F = 0.20, F(80)/F = 0.20, F(100)/F = 0.25, F(150)/F = 0.15 F(200)/F =
0.20; Also, W = 15 Kg and F = 1.3 Kg/min.

 Substituting the given data along with = W/F = 15/1.3 = 11.5385 min into the above
equation, we get
≈ 0.204 or ≈ 0.796
--------------------------------------------------------------------------------------------------------------------------------------------
UNIT-V (GAS-LIQUID REACTIONS)
1. When the heterogeneous fluid-fluid reactions take place?

Heterogeneous fluid-fluid reactions are made to take place for one of the three reasons;
 The product of reaction may be a desired material.
 To facilitate the removal of an unwanted component from a fluid.
 To obtain a vastly improved product distribution.
2. Give the importance of equilibrium solubility in gas-liquid operations.

The solubility of the reacting components will limit their movement from one phase to other. This factor
will certainly influence the form of the rate equation since it will determine whether the reaction takes place
in one or both phases.
3. Define Enhancement factor. (NOV/DEC 2014)

The liquid enhancement factor (E) is defined as the ratio of rate of take up of gaseous ‘A’ when reaction
occurs to the rate of take up of gaseous ‘A’ for straight mass transfer, at same CAi, CA, CBi, CB in the two
cases. Or Enhancement factor E is defined as the ratio between the Sherwood number with chemical
reaction and that without reaction.
4. ‘Enhancement factor is always greater than or equal to one’. Justify this statement.
Since the rate of take up of ‘A’ when reaction occurs is greater than or equal to the rate of take up of ‘A’ for
straight mass transfer, the enhancement factor is always greater than or equal to one.
5. Define Hatta number. (NOV/DEC 2013)

Hatta number (MH) is defined as the square root of the ratio of maximum possible conversion in the liquid
film to maximum diffusional transport through the liquid film.
6. Explain the significance of Hatta number.

The significance of Hatta number (MH) is;
 If MH>2, reaction occurs in the liquid film and are fast enough.
 If 0.02 < MH < 2, reaction is influenced by all the resistances.
 If MH < 0.02, reactions are infinitely slow.
7. Does the enhancement factor decrease or increase with Hatta number? Explain.
Yes, Enhancement factor (E) decrease or increases with Hatta number (M H). Because the evaluation of ‘E’
depends on two quantities;
 The enhancement factor for an infinitely fast reaction (Ei)
 Maximum possible conversion in the film compared with maximum transport through the film
(MH2).
8. How do you classify the kinetic regimes in gas-liquid reactions?

The classification of kinetic regimes in a Gas-Liquid reaction based on the relative rates of reaction and
mass transfer. According to two-film theory, the reaction may occur in liquid film or in both liquid film and
main body of liquid or in main body of liquid.

Based on the above three factors of reactions, we have eight special cases from infinitely fast to slow
reaction as;
 Instantaneous reaction - with low Cliquid & high Cliquid
 Fast reaction - with low Cliquid & high Cliquid
 Intermediate rate with reaction in the film and in the main body of the liquid.
 Slow reaction - with & without mass transfer resistance.
9. What do you mean by instantaneous reactions in the gas-liquid operations?

In instantaneous reactions, the absorbing component of the gas and the liquid phase reactant can not co-
exist in the same region. In such reactions, the concentration of the liquid phase reactant at the gas-liquid
interface is zero.
10. Give examples for absorption with chemical reaction. (NOV/DEC 2013) (NOV/DEC 2014)
11. What do you mean by slow reactions in the gas-liquid operations?

In slow reactions, occurs in the main body of the liquid, mass transfer resistance is negligible and the
composition of liquid phase and gas phase reactants are uniform. Thus, the rate is determined by chemical
kinetics alone.
12. In a gas-liquid reaction, it was observed that the reaction occurs on a plane with in the liquid film. Is
the reaction slow, fast or instantaneous? Explain.
The reaction is either instantaneous of fast, with low concentration of liquid.
 For instantaneous reaction, the reaction plane exists where the two reactants interact in the liquid
film.
 For fast reactions, the reaction zone exists where the two reactants completely reacted in the liquid
film
13. What are the advantages of surface renewal theory?

The biggest advantage arises from the square root dependence on the diffusion coefficient. This allows one
to better predict the behavior of various solutes with different diffusion coefficients based on measured
behavior of one particular solute. The square root dependence gives more accurate prediction than the linear
dependence found with the two-film model. Recognize however that surface renewal is really most accurate
when surface renewal rates are high.
14. Brief the mechanism of Surface renewal theory. [Dec 2012]

This approach tries to apply the mathematics of the penetration theory to be more plausible physical picture.
The liquid is pictured as two regions, a large well mixed bulk and an interfacial region that is renewed so
fast that it behaves as a thick film. The surface renewal theory is caused by liquid flow.
15. What are the various resistances involved in developing rate equations for gas-liquid reactions?
The various resistances involved in developing rate equations for gas-liquid reactions are;
 Mass transfer resistances, to bring the reactants together.
 The resistance of the chemical reaction step.
16. Sketch the concentration profile for an instantaneous gas-liquid non-catalytic reaction.
Refer: “Chemical Reaction Engineering” by O. Levenspiel, Chapter no: 23, Page no: 531.
17. Write short notes on slurry reactors.

 A slurry reactor is a multiphase flow reactor in which reactant gas is bubbled through a solution
containing solid catalyst particles. The solution may be either a reactant or a product or an inert.
 Slurry reactors may be operated in a batch or continuous mode. One of the main advantages of
slurry reactors is that temperature control and heat recovery are easily achieved. In addition,
constant overall catalytic activity can be maintained by the addition of small amounts of catalyst
with each reuse during batch operation or with constant feeding during continuous operation.
 These reactors are widely used in hydrogenation of fatty acids over a supported nickel catalyst,
hydro-formation of CO with high-molecular-weight olefins on either a cobalt or ruthenium complex
bound to polymers, etc.
17. Explain Film penetration theory. [Dec 2012] (May/June 2014)

The penetration theory for mass transfer. Here the interfacial region is imagined to be very thick
continuously generated by flow. Mass transfer now involves diffusion in to this film. In this and other
theories the interfacial concentration in the liquid is assumed to be in equilibrium with that in the gas
18. What are the advantages of slurry reactors over fixed beds?
The advantages of slurry reactors over fixed beds are
a. It usually has a higher rate
b. It holds good for fast reactions on porous catalyst
Note: Slurry reactors can use very fine particles, and this lead to problems of separating catalyst from
liquid. (Only disadvantage of slurry reactor)
19. Write short notes on trickle bed reactors.

c. A trickle bed reactor is a three-phase version in which gas and liquid reactants are brought into
contact with solid catalyst particles.
d. In this gas and liquid flow counter-currently downward over a fixed-bed of catalyst particles
contained in a tubular reactor.
e. These reactors are widely used for hydro-desulphurization of liquid petroleum fractions and hydro-
treating of lubricating oils.
20. List the types of flow regime that are possible in trickle bed reactors.
In trickle bed reactor, four types of flow regimes are possible;
 Trickle flow regime: In this regime, gas flow is continuous.
 Dispersed bubble regime: In this regime, liquid phase is continuous and the gas moves into the
bubbles.
 Spray regime: In this regime, gas flow rate is high while liquid rate is low. Liquid falls in droplets
through the gas phase.
 Pulsed flow regime: In this regime, flow rates of both gas and liquid are high
1. Consider the Gas-Liquid Non-catalytic reaction A (g) + b B (l)  Products. Derive the global rate
equation assuming the reaction to be instantaneous and for the reaction taking place on
(i) Gas-Liquid interface.
(ii) A plane located in the Liquid film.
Ans: (i) Reaction occurs on a plane in the liquid film - With low CB
 The rate of transfer of ‘A’ from gas to liquid is given by the rate expressions;
For the gas film, -rA|||| = (kAg a) (PA – PAi)
On rearranging and dividing by ‘HA’, we get
(-rA||||)/[(kAg a) HA] = (PA/HA) – (PAi/HA)
For the liquid film, -rA|||| = (kAl a) (CAi – 0) (xo/x) = (kBl a) (CB – 0) (xo/(xo - x))
On rearranging, we get
xo/x = [(kBl/b kAl) CB + CAi]/CAi

 Substituting the above into the rate equation for liquid film, we get
[-rA||||/(kAl a)] = (kBl/b kAl) CB + CAi
= (kBl/b kAl) CB + (pAi/pA), by Henry’s law.
 Adding the above equation with the rate of gas film, we get
-rA|||| = {[(kBl/kAl) (CB/b)] + (pA/HA)}/[1/(kAg a) + (HA/kAl a)]
 By two film theory, we know that (kBl/kAl) α (DBl/DAl). Thus, finally we get
-rA|||| = {[( DBl/DAl) (CB/b)] + (pA/HA)}/[1/(kAg a) + (HA/kAl a)]
(ii) Reaction occurs on the G-L interface - With high CB

 If the concentration of ‘B’ is raised, only the resistance of the gas-phase controls the
reaction and the rate is not affected by increase in CB.
 Thus, the above final equation becomes
-rA|||| = (kAg a) pA, which is a first order rate with respect to ‘A’.
2. Derive the rate equation for fluid-fluid reaction for the following cases;
(i) Fast reaction in Liquid film with Low CB
(ii) Fast reaction in Liquid film with High CB
Sketch the concentration profiles of the reactants for these reactions.
Ans: (i) Fast reaction with low CB
 With low CB – Reaction occurs in a zone in the liquid film
 The rate of transfer of ‘A’ from gas to liquid is given by the rate expressions;
For the gas film, -rA|||| = (kAg a) (PA – PAi)
On rearranging and dividing by ‘HA’, we get
(-rA||||)/[(kAg a) HA] = (PA/HA) – (PAi/HA)
For the liquid film, -rA’’’’ = (kAl a) CAi E
On rearranging, we get
(-rA||||)/[(kAl a) E] = CAi = PAi/HA
On combing or adding the above equations, we get
-rA|||| = {1/[1/(kAg a) + HA/(kAl a E)]} PA
(ii) With high CB – Reaction occurs in a zone nearer to the G-L interface
 The derivation is same as the case-1, but with E = MH = SQRT(DAl k CB)/ kAl
Thus, the final rate expression is
-rA|||| = {1/[1/(kAg a) + HA/(a SQRT(DAl k CB))]} PA
3. Derive the rate equation for fluid-fluid reaction for the following cases;
(i) Intermediate reaction in the film and in the main body of the liquid.
(ii) Slow reaction in the main body of liquid with film resistance.
Ans: (i)

(ii)

4. Discuss in detail the Design procedure (PBR) for the reaction A (g) + b B (l)  Products with
Moderately to Infinitely fast rate in which the phases are being Counter-current Plug flow.
Ans: By differential material balance, we have G dYA = - L dXB (since b =1)
 For reaction between ‘A’ and ‘B’ on the differential volume, we have
Rate expression = (-rA||||) dVr
 By principles, G dYA = - L dXB = (-rA||||) dVr

On rearranging, we get dVr = G dYA/(-rA||||) = - L dXB/(-rA||||)
 We know, dYA = dpA/π and dXB = dCB/CT

Where ‘π’ and ‘CT’ are the total pressure of gas ‘A’ and total concentration
of liquid ‘B’.
Then, the above equation becomes
dVr = [(G/π) dpA/(-rA||||)] = - [(L/CT) dCB/(-rA||||)]
On integrating with dCB = dCA (since b =1), we get
pA2 CA1
Vr = (G/π) ∫[dpA/(-rA||||)] = (L/CT) ∫[dCA/(-rA||||)]
pA1 CA2
 For instantaneous reactions (first order), we have
-rA|||| = (KAg a) (pA – pA*) = (KAl a) (CA* - CA)
Substituting the above into the equation for volume of reactor (Vr), finally we get
pA2 CA1
Vr = [G/π(KAg a)] ∫ [dpA/(pA – pA*)] = [L/CT(KAl a)] ∫ [dCA/(CA* - CA)]
pA1 CA2
This is the design equation for packed bed reactor for G/L reaction based on the assumption that
the flow is countercurrent and plug flow of both streams.
5. Discuss the various design equation available for the absorber, for various type reaction with
various contacting pattern.

Ans: (i) For plug flow of both gas (G) and liquid(L) – countercurrent flow in the tower, we know
pA2 CA1
Vr = [G/π(KAg a)] ∫[dpA/(pA – pA*)] = [L/CT(KAl a)] ∫[dCA/(CA* - CA)]
pA1 CA2
Where Vr – Volume of reactor and Vr = h Acs
Acs – Cross sectional area of tower
G – Superficial mass gas velocity
L – Liquid mass flow rate
π – Total pressure of the gas entering the tower
CT – Total concentration of liquid in the tower
KAg a – Overall gas mass transfer coefficient
KAl a – Overall liquid mass transfer coefficient
(ii) For plug flow of both gas (G) and liquid(L) – co-current flow in the tower, we know
pA2 CA1
Vr = - [G/π(KAg a)] ∫[dpA/(pA – pA*)] = - [L/CT(KAl a)] ∫[dCA/(CA* - CA)]
pA1 CA2
The simple change in the above equation is a negative sign is used for up-flow and down-
flow of both streams when compared to countercurrent equation.
(iii) For Mixed flow of both gas (G) and liquid(L) – Mass transfer + reaction in an agitated
tank contactor, we know
(G/π) (pA,in - pA,out) = [L/(b CT)] (CB,in – CB,out) = (-rA||||)exit Vr
Where (-rA||||)exit is the rate to be evaluated at exit conditions.
(iv) Plug flow of gas (G) and mixed flow of liquid (L) – Mass transfer + reaction in
bubble tank contactors, we know
pA2
Vr = (G/π) ∫dpA/(-rA||||) with (G/π) (pA,in - pA,out) = [L/(b CT)] (CB,in – CB,out)
pA1
(v) Mixed flow of gas (G) and batch uniform liquid (L), we know
(G/π) (pA,in - pA,out) = - (Vl/b) dCB/dt = (-rA||||) Vr
Where ‘Vl’ is the volume of batch of liquid in the reactor.
6. (i) What are the various equipments used in Fluid-Fluid contacting with reaction?
(ii) Discuss in detail about Slurry reaction kinetics.
Ans: (i)

(ii)

7. The concentration of an undesirable impurity ‘A’ in air is to be reduced from 0.10% to 0.02% by
absorption in pure water. Find the height of tower required for counter current operations. Data:
For consistency, units are given in moles, meters, and hours;
 For the packing used,
 kA(g) a = 32,000 mol/hr-m3-atm
 kA(l) a = 0.1 hr-1
 The solubility of A in water, HA = 125 x 10-6 atm-m3/mol
 Liquid mass flow rate, L = 7 X 1015 mol/hr-m2
 Gas flow rate, G = 1 X 1015 mol/hr-m2 at  = 1 atm
 Molar density of liquid, CT = 56,000 mol/m3
Ans:
 From the given data’s of individual mass transfer coefficient and the solubility of water, we
find the overall mass transfer coefficient as
1/(KAg a) = 1/ (kAg a) + (HA/ kAl a) = 128.125 x 10-5 m3-atm-hr/mol
 By material balance on the absorption tower and with given data, we get
CA = 8000 pA – 1.6
 Then, pA – pA* = pA – HA CA = pA – 125x10-6 (8000 pA – 1.6) = 2 x 10-4 atm.
 Thus, we know the height of tower required for counter current operations is
pA2
h = [G/π(KAg a)] ∫[dpA/(pA – pA*)]
pA1
0.001
= [(1x105) (128.125 x 10-5)/(1)] ∫[dpA/(2 x 10-4)
0.0002
Or h ≈ 512 m
-------------------------------------------------- ALL THE BEST ------------------------------------------

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CH2401 Chemical Reaction Engineering-II Dept.

of Chemical Engineering 2015-2016

UNIT-I (NON-IDEAL REACTORS)

PART-A (Questions & Answers)

3. Explain the term Channeling.

4. Explain the term short-circuiting.

5. What data do you need in predicting the behavior of a real reactor?

6. What is method of inquiry in stimulus response experiment?

7. What is ‘E’ function? Explain.

St. Joseph’s College of Engineering 1 ISO9001:2008

8. Explain ‘F’ function.

9. Give the relationship between E(t) and F(t).

11. What is the difference between ‘E’ and ‘C’ curve?

Ideal PFR Ideal CSTR

13. State the relationship between E and F function. [Dec-2012]

St. Joseph’s College of Engineering 2 ISO9001:2008

15. Define Intensity of dispersion.

16. What is Dispersion number?

18. What is Tank’s-in-series model? State its limitations.

19. Define Sherwood number and Schmidt number.

St. Joseph’s College of Engineering 3 ISO9001:2008

PART-B (Questions & Answers)

1. (i) Explain the effects of Non-ideal flow with examples.

2. (i) Explain the method of conducting Stimulus response experiments.

II. Step (continuous input) experiment

St. Joseph’s College of Engineering 4 ISO9001:2008

(ii) To evaluate reactor behavior in general we have to know four factors:

St. Joseph’s College of Engineering 5 ISO9001:2008

 On normalizing the above expression for entire length of reactor, we get

 In terms of conversion, we have

Where a = SQRT{1 + 4 k τ [D/(U. L)]}

St. Joseph’s College of Engineering 6 ISO9001:2008

 Mean residence time, t = Σ(t. c. ∆t)/Σ(c. ∆t) = 1500/100 = 15 min

 Variance, σ2 = {Σ(t2. c. ∆t)/Σ(c. ∆t)} – t2

 Assuming small extent or deviation from plug flow, we know

σθ2 = σ2/t2 = 2[D/UL] = 47.5/(15)2 = 0.2111

 Tank-3: By material balance, we get C3 = C0/2! (t/ti)2 e-t/ ti and

 Tank-4: By material balance, we get C4 = C0/3! (t/ti)3 e-t/ti and

 Similarly, for Nth tank, we get CN = C0/(N-1)! (t/ti)N-1 e-t/ti and

St. Joseph’s College of Engineering 7 ISO9001:2008

 Mean residence time, t = Σ(t. c. ∆t)/Σ(c. ∆t) =1898462.5/4920 = 385.8664 secs

 Variance, σ2 = {Σ(t2. c. ∆t)/Σ(c. ∆t)} – t2

 By Tanks-in-series model, we know that

 Therefore, 1 – XA = 1/{1 + [(k. t)/N]}N

UNIT-II (HETEROGENEOUS REACTIONS & SOLID CATALYSIS)

PART-A (Questions & Answers)

2. List the general characteristics of catalysis.

3. What do you mean by rate controlling step in heterogeneous reactions?

St. Joseph’s College of Engineering 8 ISO9001:2008

5. Does a catalyst alter equilibrium conversion of a chemical reaction? Explain.

6. Is the selectivity of multiple reactions affected by catalysts? Explain.

7. Define adsorption and adsorbent. (NOV/DEC 2013)

9. Explain two characteristics of physical adsorption. [Dec 2012]

10. State the assumptions of Langmuir adsorption isotherm.

St. Joseph’s College of Engineering 9 ISO9001:2008

12. Write the B E T equation for multilayer adsorption.

16. Give the classification of catalyst.

17. What is Catalyst promoter? (NOV/DEC 2014)

18. What is catalyst inhibition? (NOV/DEC 2014)