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UNIT-I (CATALYTS)
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.
Effectiveness factor = actual mean reaction rate within pore /rate if not slowed by pore diffusion.
1. Bulk catalysts.
2. Supported catalyst.
Pore size distribution can be represented both in differential and cumulative ways.
18. What are the carrier or support used and why they are used with catalyst?
A catalyst support is the material, usually a solid with a high surface area, to which a catalyst is affixed. The
reactivity of heterogeneous catalysts and nanomaterial-based catalysts occurs at the surface atoms.Catalyst
support results in highly porous nature - increase of available surface area improve stability improves the
heat transfer characteristics. Some of Alumina, Asbestos, Carborundum, Iron oxide, Manganese, Activated
carbon, Zinc oxide.
The sol-gel process is a wet-chemical technique (Chemical Solution Deposition) for the fabrication of
materials starting from a chemical solution that reacts to produce colloidal particles (sol). Typical precursors
are metal alkoxides and metal chlorides, which undergo hydrolysis and polycondensation reactions to form
a colloid, a system composed of solid particles (size ranging from 1 nm to 1 μm) dispersed in a solvent. The
sol evolves then towards the formation of an inorganic network containing a liquid phase (gel). Formation
of a metal oxide involves connecting the metal centers with oxo (M-O-M) or hydroxo (M-OH-M) bridges,
therefore generating metal-oxo or metal-hydroxo polymers in solution. The drying process serves to remove
the liquid phase from the gel thus forming a porous material, then a thermal treatment (firing) may be
performed in order to favor further polycondensation and enhance mechanical properties.
Catalyst based on more than one component can be prepared by coprecipitation. According to IUPAC
nomenclature this term is used for the simultaneous precipitation of normal soluble component with macro
component from the same solution by the formation of mixed crystal by adsorption, occlusion or by
mechanical entrapment. Co-precipitation is very suitable for the generation of homogeneous distribution of
catalyst or for the creation of precursor of definite stoichiometry which can be easily converted into active
catalyst.
Incipient wetness impregnation is a commonly used technique for the synthesis of heterogeneous catalysts.
Typically, the active metal precursor is dissolved in an aqueous or organic solution. Then the metal-
containing solution is added to a catalyst support containing the same pore volume as the volume of
solution that was added. Capillary action draws the solution into the pores. The catalyst can then be dried
and calcined to drive off the volatile components within the solution, depositing the metal on the catalyst
surface
23. What are the main interactions that can occur between metals and support materials?
Electronic interactions; reduced support species on the metal surface; phase formation at interfacial
surfaces.
Part B
3. What is Chemisorption?
a. It is specific and involves forces much stronger than in physical adsorption.
b. The process is often irreversible.
10. A non-porous catalyst particle is of size 2 microns and density is 2 g/cm 3. Calculate the external
surface area per gram of the particle.
The external surface area per gram of the particle, S g
11. 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.
12. 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.
13. What do you mean by desorption?
Desorption is a phenomenon whereby a substance is released from or through a surface. The process is the
opposite of sorption (that is, either adsorption or absorption). This occurs in a system being in the state of
sorption equilibrium between bulk phase (fluid, i.e. gas or liquid solution) and an adsorbing surface (solid
or boundary separating two fluids).
14. Difference between physical adsorption and chemical adsorption (May 2015) & (Nov. 2013)
Where x is the mass of the gas adsorbed on mass m of the adsorbent at pressure p and k, n are constants
whose values depend upon adsorbent and gas at particular temperature. Though Freundlich Isotherm
correctly established the relationship of adsorption with pressure at lower values, it failed to predict value of
adsorption at higher pressure.
Where θ the number of sites of the surface which are covered with gaseous molecule, P represents pressure
and K is the equilibrium constant for distribution of adsorbate between the surface and the gas phase.
Langmuir-Hinshelwood mechanism. The two molecules A and B both adsorb to the surface. While adsorbed
to the surface, the A and B "meet," bond, and then the new molecule A-B desorbs.
First the reactants adsorb onto the surface. Through a series of bonds being formed and being broken,
adsorbed intermediates are produced and destroyed. Then the final product(s) is produced and it desorbs
from the solid.
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.
1. Derive the equation for effectiveness factor in a spherical pellet when the reaction is first order.
(May 2016)
2. An 0.86 g sample of Glaucosil is studied with N2 adsorption at – 195.8 oC. The following data are obtained:
Pressure (mm Hg) 6 25 140 230 285 320 430 505
3 o
Volume adsorbed, cm at 0 C and 1 atm: 61 127 170 197 215 280 277 335
The vapor pressure of N2 at -195.8 deg C is 1 atm; estimate the surface area (m 2/g) of the sample. The
density of N2 at -195.8 0C is 0.808 gm/cm3. (May 2015).
3. For a bimolecular reaction A → B → C → D when all the species are adsorbed onto the catalytic surface
and if surface reaction is rate controlling derive the rate expression for the formation of the product ‘C’.
(May, 2016); (Dec. 2014)
4. i) Derive the rate equation for heterogeneous reaction involving gas and solid. (May, 2012)
ii) Discuss in detail the different adsorption theories. (May, 2012)
7. Consider a solid catalyzed reaction A R + S. Assuming Langmuir-Hinshelwood model, derive the kinetic
8. 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.
9. Describe in detail the Nitrogen adsorption method for the determination of Surface area of a catalyst.
10. Obtain rate expression for finding out effectiveness factor for spherical catalyst particle.
11. Rate data for the pyrolysis of normal octane at 450 Deg C give an apparent, first order, irreversible rate
constant, Ko of 0.25 cm3/s.g. Thin apparent rate constant is defined
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11. 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. ‘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.
16. 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.
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.
PART-B (Questions & Answers)
1. Discuss the effect of mass and heat transfer on the performance of industrial catalytic reactors. (May, 2016)
2. Explain the methods of determining the effective diffusivity.
3. Show that the Effectiveness factor (η) for a first order reaction in an isothermal spherical catalyst pellet is
given by
8. 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
9. Compare the packed bed reactor and fluidized bed reactor for a catalytic chemical reaction.
10. 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 Calculate the
weight of the XA 0.058 0.139 0.213 0.288 0.381 0.440 0.493 catalyst for
40% conversion in a
packed bed reactor, if the molal feed
rate is increased to 125 kmol/hr.
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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
tR 2
for ash layer diffusion controlling
tR chemical reaction controlling.
16. In a gas-solid non-catalytic reaction, a 4mm solid is 7/8 th 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
17. Sketch the concentration profile for the gas-solid non-catalytic reaction in which the resistance
through the ash layer is rate controlling.
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 (k g), the gas film resistance (1/k g) can be reduced for non-
catalytic chemical reaction.
PART-B (Questions & Answers)
1. Obtain rate equation for non-catalytic chemical reaction when chemical reaction is controlling the rate of
reaction. (May 2016)
2. Develop the design expression for fluidized bed reactor with particle size for non-catalytic chemical
reaction. (May 2016)
3. Derive an expression for shrinking core model in a gas-solid non catalytic reaction. (May 2015)
4. Discuss about the mechanism of heterogeneous non catalytic gas-solid system. (May 2015)
5. (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.
6. 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’
7. 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.
8. (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?
9. 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.
10. 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.
11. 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
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.
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
20. 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.
21. 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
1. Derive a rate equation for an instantaneous reaction of any order between A and B, fluid-fluid reaction A
(gas ) + bB (liq) → product. And sketch the concentration profiles assuming a two-film theory. (May 2016)
2. Describe briefly on different reactors available for various types of gas-liquid reaction. (May 2016)
3. i) What are the reaction steps in a slurry reactor? ( May 2015)
ii) Write a note on the parameters based on which a good contactor for a Gas-Liquid solid catalyzed
reaction is selected.
iii) What are the parameters to be considered while selecting a fluid-fluid reactor?
4. i) What is Enhancement factor? (May 2015)
ii) Write a note on Absorption with slow and instantaneous reactions.
5. 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.
6. 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.
7. 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.
8. 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.
9. Discuss the various design equation available for the absorber, for various type reaction with various
contacting pattern.
10. (i) What are the various equipments used in Fluid-Fluid contacting with reaction?
(ii) Discuss in detail about Slurry reaction kinetics.
11. 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
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