Question Paper Code: 31259

B.E/ B.Tech DEGREE EXAMINATION, NOVEMBER/DECEMBER 2013

Seventh Semester
Chemical Engineering
CH2401 CHEMICAL REACTION ENGINEERING- II
(Regulation 2008/2010)
Time: Three hours Maximum: 100 marks
Answer ALL questions.
PART A—(10 x 2 = 20 marks)
1) Define RTD.
Residence Time Distribution Function:
 The time it takes a molecule to pass through a reactor is called the residence time of the
molecule in the reactor.
 It is clear that elements of fluid taking different routes through the reactor may take
different lengths of time to pass through it.
 So there is a distribution of residence time of the fluid material within the reactor.
 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.
2) What are the reasons for non-ideality in real reactors?
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).
3) Define adsorption and adsorbent.
It is a surface phenomenon, in which accumulation of any substance (Adsorbate) on the surface of
another substance (Adsorbent) takes place.
4) Differentiate between physical adsorption and chemisorption.
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.
5) Explain Knudsen diffusion.
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.
6) What factors are contributing for Effective thermal conductivity
The effective thermal conductivity is a function of volume fraction of the void phase and thermal
conductivities of the bulk fluid and solid phases, kf and ks.
The relationship is
7) What are the advantages of FBR? (NOV/DEC 2013)
Uniform Particle Mixing: Due to the intrinsic fluid-like behaviour 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 start-up conditions in batch processes.
8) Name the models used in gas-solid non-catalytic reactions.
For the Gas-Solid non-catalytic reactions, two idealized models are available;
(i) Progressive-conversion model [PCM]
(ii) Shrinking-core model [SCM]
9) Define Hatta number.
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.
10) Give examples for absorption with chemical reaction.
 PART B—(16 x 5 = 80 marks)
11) a) i) Derive the equation to fine out the conversion using dispersion model.
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)]}

ii) Derive the equation to fine out the conversion from direct use of tracer data.
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
 Or

b) The following data are obtained from liquid phase reactor. Find out what fraction of material of material
spends between 200 and 275 s.

t, sec 0 150 175 200 225 240 250 260 275 300 325 350
C*103 g/dm3 0 1 3 7.4 9.7 9.4 8.2 5 2.5 1.2 0.5 0

C*103
t, sec ∆t C∆t E, sec-1
g/dm3
0 0 0 0 0
150 1 150 150 0.000995
175 3 25 75 0.002984
200 7.4 25 185 0.00736
225 9.7 25 242.5 0.009647
240 9.4 15 141 0.009349
250 8.2 10 82 0.008155
260 5 10 50 0.004973
275 2.5 15 37.5 0.002486
300 1.2 25 30 0.001193
325 0.5 25 12.5 0.000497
350 0 25 0 0

∑ C∆t = 1005.5

E = C/ ∑ C∆t

The fraction of material of material spends between 200 and 275 s = 0.04197

12) a) Explain the various methods of finding pore size distribution of catalyst.
Pore volume distribution
 Mercury-Penetration Method
 Nitrogen-Desorption Method
Mercury penetration method
 The mercury-penetration method 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.
 The pressure varies inversely with a; 100 lb/in2 (approximately) is required to fill pores for
which a = 10,000oA, and 10, 000 lb/in.2 is needed for a = 100oA.
  Simple techniques and equipment are satisfactory for evaluating the pore-volume
distribution down to 100 to 200oA, but special high-pressure apparatus is necessary to go
below a = 100o A, where much of the surface resides.

 By equating the force due to surface tension (which tends to keep mercury out of a pore) to
the applied force, Ritter and Drake obtained

 Where θ is the contact angle between the mercury and pore wall (figure)
 Then the working equation for evaluating the radius corresponding to a given pressure is

Nitrogen-desorption method
 As the low temperature nitrogen-desorption experiment is continued to high pressures multilayer
adsorption occurs, and ultimately the adsorbed film are thick enough to bridge the pore. Then
further uptake of nitrogen will result in capillary condensation.
 Since the vapor pressure decreases as the capillary size decreases, decreases, such condensation will
occur first in the smaller pores. Condensation will be complete, as , (p/po= 0) when the entire void
region is filled with condensed nitrogen.
 Now, if the pressure is reduced by a small increment, a small amount of nitrogen will evaporate
from the meniscus formed at the ends of the largest pores.
 Pores which are emptied of condensate in this way will be those in which the vapor pressure of
nitrogen is greater than the chosen pressure.
 The Kelvin equation gives the relationship between vapor pressure and radius of the concave
surface of the meniscus of the liquid.
 Since some of the nitrogen is adsorbed on the surface, and therefore not present because of
capillary condensation, the Kelvin relationship must be corrected for the thickness of the adsorbed
layers.
 With this correction, the pore radius is related to the saturation pressure ratio (vapor pressure ’p’ in
the pore divided by the normal vapor pressure po) by

 Since nitrogen completely wets the surface covered with adsorbed nitrogen, θ = 0 and cos θ= 1. The
thickness δ depends on p/po . The exact relationship has been the subject of considerable study,
but Wheeler’s form

 For nitrogen at – 195.8o C (normal boiling point) , for a-δ in angstroms, becomes

 For a chosen value of p/po , the above equation give the pore radius above which all pores will be
empty of capillary condensate.
 Hence, if the amount of desorption is measured for various p/po, the pore volume corresponding to
various radii can be evaluated.
 Differentiation of the curve for cumulative pore volume vs. radius gives the distribution of volume.

 By combining mercury-penetration and nitrogen-desorption measurements, pore-volume

information can be obtained over the complete range of radii in a pelleted catalyst containing both
macro- and micropores.
 Figure shows the cumulative pore volume for two alumina pellets, each prepared by compressing
porous particles of boehmite (Al2O3.H2O). The only difference in the two is the pelleting pressure.
 Increasing this pressure causes drastic reductions in the space between particles (macropore olume)
but does not greatly change the void volume within the particles or surface area. The derivative of
the volume curves in figure (1) gives the pore volume distribution, and these results are shown in
figure (2).
b) During the adsorption of hexane on silica gel at 850 C the following data are obtained. Determine which
isotherm fits the data well for the system
Partial Pressure of hexane, atm 0.0020 0.0040 0.0080 0.0113 0.00156 0.0256
-5
Hexane Adsorped, gmol/g *10 11 16 27 35 43 48

13) a) Show that the Effectiveness factor (η) for a first order reaction in an isothermal spherical catalyst
pellet
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
b) Discuss the effect of heat and mass transfer on the performance of industrial catalytic reactors.

Mass and Heat transfer with reaction

 When the heat of reaction is large, intrapellet temperature gradients may have a larger effect on
the rate per pellet than concentration gradients.
 When heat of reaction is low, the center ad surface temperatures may differ appreciably,
because catalyst pellets have low thermal conductivities.
 The combined effect of mass and heat transfer on rp can still represented by the general
definition of the effectiveness factor.
 The non isothermal η may be calculated in the same way as the isothermal η, except that an
energy balance must be combined with the mass balance.

Nonisothermal Effectiveness Factors

14) a) Derive an expression for Shrinking core model in gas solid non catalytic reaction
Diffusion through Gas film
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
Diffusion through Ash Layer
By stoichiometry and material balance, with fundamentals, we get

-(dNB/dt) [(1/rc) – (1/R)] = 4π b De CAg

 Using dNB = 4π ρB rc2 drc into the above equation and on solving the integral, we get
t = (ρB R2)/(6 b De CAg) [1 – 3 (rc/R)2 + 2(rc/R)3]

 For rc =0 (complete conversion), we get

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)]
Chemical Reaction
By stoichiometry, we have
(-rA||) = (-rB||) / b
Or –(1/4π rc2) dNB/dt = b k|| CAg

 Using dNB = 4π ρB rc2 drc into the above equation and on solving the integral, we get
t = (ρB R)/(b k|| CAg) [1 – (rc/R)]

 For rc =0 (complete conversion), we get

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]
Or

b) Discuss about the mechanism of heterogeneous non catalytic gas solid system.

Gas-Solid non-catalytic reactions

Two cases

1. The particle size remains unchanged during the reaction

2. The particle size changes with progress of reaction
The particle size remains unchanged during reaction

1. Solid particles contain large amount of inert material which remain as a non-flaking ash or
2. A firm product material is formed by the reactions.

Example

(i). Roasting of sulphide ores in air to yield metal oxides

(ii). Similarly iron pyrites

(iii). The reduction of metal oxides to corresponding metals

(iv). The nitrogenation of calcium carbide

(v). Treatment of carbonaceous material

The particle size changes with progress of reaction

15) a) Give a brief account on surface renewal theories.
b) Elaborate briefly about the design principle of tower reactor.
12) b) During the adsorption of hexane on silica gel at 850 C the following data are obtained. Determine
which isotherm fits the data well for the system
Partial Pressure of hexane, atm 0.0020 0.0040 0.0080 0.0113 0.00156 0.0256
Hexane Adsorped, gmol/g *10-5 11 16 27 35 43 48

T= 850 C = 358 K
R = 0.0821
Cg = P/RT
 Langmuir isotherm {Cg/C = (I/Cm) Cg + [1/(Kc. Cm)]}

Cg x 10-4 Cg/C x 10-5

0.68 0.618
1.36 .85
2.72 1.00
3.84 1.09
5.30 1.23
8.70 1.81

 Freundlich isotherm {ln(C) = (1/n) ln(P) + ln(c. Cm)}

 ln(P) ln(C)
-6.214 -9.115
-5.52 -8.71
-4.828 -8.217
-4.48 -7.97
-4.16 -7.75
-3.66 -7.64

 Temkin isotherm {C = (k1Cm) ln(P) + (k1Cm)ln(k2)}

C ln(P)
11 -6.214
16 -5.52
27 -4.828
35 -4.48
43 -4.16
48 -3.66