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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.
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
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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.
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
1. Explain in detail how the pore volume distribution of a solid catalyst is determined by the mercury
penetration method. (May 2016) (Dec. 2014)
2. Explain in detail on catalyst preparation. (May 2015).
3. Explain various methods of finding pore size distributions of catalyst. (Nov. 2013)
4. During the adsorption of hexane on silica gel at 85 oC, the following data are obtained. Determine which
isotherm (Langmuir, Freundlich Temkin) fits the data well for this systems. (Nov. 2013)
Partial Pressure of hexane, atm 0.002 0.004 0.008 0.0113 0.0156 0.0256
Hexane Adsorbed, gmol/g 11 x 10-6 16 x 10-5 27 x 10-5 35 x 10-5 43 x 10-5 48 x 10-5
5. What is catalyst deactivation? How and why it occurs? What are the factors that are responsible for
deactivating a porous catalyst pellet? (May 2014)
6. The true density of the solid material in an activated alumina was reported as 3675 kg/m3. The density of
the particle obtained from mercury displacement was 1547 kg/m and surface area as 175 m2. Determine the
pore volume /gm, the porosity and mean pore radius of the particle. (May 2014)
7. Explain the effect of porosity of effective thermal conductivity. (May, 2012)
8. Explain briefly about determination of Pore-volume distribution by Mercury penetration method.
9. Explain in detail about the Preparation of Catalyst.
10. Explain the various types of molecular diffusion in porous catalyst.
3. What is Chemisorption?
a. It is specific and involves forces much stronger than in physical adsorption.
b. The process is often irreversible.
c. The energy of activation is low for non-activated adsorption and high for activated adsorption.
10. 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
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).
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 A(g) is unadsorbed gaseous molecule, B(s) is unoccupied metal surface and AB is Adsorbed gaseous
molecule.
Based on his theory, he derived Langmuir Equation which depicted a relationship between the number of
active sites of the surface undergoing adsorption and 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.
1. Derive the equation for effectiveness factor in a spherical pellet when the reaction is first order. (May2016)
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
Volume adsorbed, cm3at 0 oC 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 (m2/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)
5. (i) Explain the steps involved in catalytic chemical reactions.
(ii) Discuss the nature of catalytic reaction with suitable examples.
6. Explain the various theories of adsorption and derive the related equation.
7. Consider a solid catalyzed reaction A R + S. Assuming Langmuir-Hinshelwood model, derive the kinetic
Rate equation. Assume Surface reaction to be rate controlling.
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
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
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.
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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;
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.
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)
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.
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.
8. What are the limitations of Shrinking Core Model? (May 2015) (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.
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.
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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
tR 2
for ash layer diffusion controlling
tR chemical reaction controlling.
16. 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
17. Sketch the concentration profile for the gas-solid non-catalytic reaction in which the resistance
through the ash layer is rate controlling.
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
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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. 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
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.
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.
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.
11. Give examples for absorption with chemical reaction. (NOV/DEC 2013) (NOV/DEC 2014)
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
14. Brief the mechanism of Surface renewal theory. (May 2015) & [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.
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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. Explain Film penetration theory. (May 2015), [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
21. List the types of flow regime that are possible in trickle bed reactors.
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