BT6604 Cre PDF
BT6604 Cre PDF
BT6604 Cre PDF
DEPARTMENT OF BIOTECHNOLOGY
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BT6604 - Chemical Reaction Engineering Department of Biotechnology 2018–2019
DEPARTMENT OF BIOTECHNOLOGY
COURSE DETAILS
COURSE OUTCOMES
Knowledge
CO No Course Outcomes
Level
Understand how an experimental investigation carried out in order to
C316.1 K2
determine the rate equations.
C316.2 Describeabout material and energy balance for ideal flow reactor K2
C316.3 Understand about the RTD studies for non ideal flow reactors K2
Describe about the usage of standard statistical method to establish
C316.4 K2
quantitative method
C316.5 Understand about the design of reactors for bio based product K2
Mapping of Course Outcomes with Program Outcomes and Program Specific Outcomes
BT6604 PO1 PO2 PO3 PO4 PO5 PO6 PO7 PO8 PO9 PO10 PO11 PO12 PSO1 PSO2 PSO3 PSO4
C316.1 3 - - - - - - - - - - - - - - -
C316.2 1 - - - - - - - - - - - 1 - - -
C316.3 3 2 - - - - - - - - - 1 - - - -
C316.4 3 - - - - - - - - - 1 - 1 - - -
C316.5 3 2 - - - - - - - - 1 1 1 - - -
BT6604 PO1 PO2 PO3 PO4 PO5 PO6 PO7 PO8 PO9 PO10 PO11 PO12 PSO1 PSO2 PSO3 PSO4
C316 3 2 - - - - - - - - - - 3 - - -
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(b) We know, pA= CA R T or dpA = (RT) dCA. Then, the given expression becomes
- (RT) dCA/dt = 3.66 (CA R T)2 or - dCA/dt = (3.66 R T)CA2
or -rA = - (1/ V) dNA/dt = - dCA/dt = (3.66 R T)CA2.
On comparing, we get ‘k’ = 3.66 R T = 3.66 (0.0820575) (400) = 120.1322 lit/mol-hr
16. On doubling the concentration of a reactant the rate of reaction triples. Find the reaction order.
We know, the general rate of reaction is -rA = k CAn
For the given statement, On doubling the concentration of a reactant the rate of reaction triples,
the above rate can be written as 3 (-rA) = k (2CA)n
On combining the above rate expressions, we get
3 = 2n or n = log (3) / log (2) = 1.585
17. Differentiate constant volume and variable volume methods of analysis of reactors.
Constant volume method:
It refers to the volume of reaction mixture, and not the volume of reactor. It actually means a
constant density reaction system, that is, the composition of reaction mixture is constant.
Most of the liquid phase as well as gas phase reactions occurring in a constant volume bomb fall
in this class.
In a constant volume system, the measure of reaction rate of component ‘i’ (reactant or product)
becomes ri = (1 / V) (dNi/ dt) = dCi / dt.
Conversion of reactant ‘A’ in this method is given by XA = 1 – (CA/CAo).
Variable volume method:
It actually means the composition of reaction mixture varies with time by the presence of inerts.
Gas phase reactions involving the presence of inerts or of impure reactants occurring in a reactor
fall in this class.
The measure of reaction rate of component ‘i’ (reactant or product), in this method, becomes ri =
(Cio / i) [d (ln V)/ dt).
In variable volume system, the fractional change in volume of the system between the initial and
final stage of the reaction will be accounted. Thus, conversion of reactant ‘A’ becomes X A = [1
– (CA/CAo)] / [1 + A (CA/CAo)].
18. What is a zero order reaction? (Dec 2015)
When the rate of the reaction is independent of the concentration of the reactants, it is called as Zero
order reaction. Example: Decomposition of HI
19. What is a pseudo first order reaction? Give an Example.
A second order rate equation which follows the first order rate equation is defined as pseudo First
order reaction. Example: Ester hydrolysis.
CH3 COO C2 H5 + H 2O CH 3COOH + C 2H 5OH
(A) (B) (C) (D)
When C BO >>C Ao,Concentration of H 2O is very large, - rA = - dCA/dt =k ‘CA.
20. Explain bimolecular reactions with examples.
An irreversible bimolecular-type second-order reaction may fall on two categories;
(1) The reaction A + B Products with corresponding rate equation
-rA = - (dCA/dt) = - (dCB/dt) = k CA CB
Here the amounts of A and B that have reacted at any time‘t’ are equal.
(2) The reaction 2A Products with corresponding rate equation
-rA = - (dCA/dt) = k CA2
Here in practice that the reactant ratios either equal to or widely different from the
stoichiometric ratio.
21. Explain third order reaction with example.
An irreversible trimolecular-type third-order reaction may fall on two categories;
(1) The reaction A + B + D Products with corresponding rate equation
-rA = - (dCA/dt) = k CA CB CD.
If CDo is much greater than both CAo and CBo, the reaction becomes second order.
(2) The reaction A + 2B Products with corresponding rate equation
-rA = - (dCA/dt) = k CA CB2.
22. Write the empirical rate equation of nth order.
The empirical rate equation of nth order, -rA = - dCA/dt = k CAn (constant volume). Separating the
variables and integrating, we get CA1-n - CAo1-n = (n - 1) k t.
Case i) n>1, CAo1-n = (1 - n) k t. The slope is (1 - n)
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Ea for A →3R:
One mole of reactant on complete conversion yields three moles of product.
Basis: 1 mole of A
From the reaction, 1 mole A= 3 mole R
Moles of R formed on complete conversion of A = (3/1)*1 = 3 mole
Initial total moles = Total moles at no conversion
= 1 mole A
Total moles on complete conversion = 3 mole of R = 3 mole
Ea = (3-1)/1 =2
Answer: Ea = 2
31. Define Activation Energy. (Dec 2015)
Activation energy is a term used to describe the minimum energy which must be available to a
chemical system with potential reactants to result in a chemical reaction.
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Activation energy may also be defined as the minimum energy required to start a chemical reaction.
The activation energy of a reaction is usually denoted by Ea and given in units ofkilojoules per
mole (kJ/mol) or kilocalories per mole (kcal/mol).
32. Write the units of rate constant. (May 16)
The units of the rate constant depend on the global order of reaction:[2] If concentration is
measured in units of mol·L−1 (sometimes abbreviated as M), then
For order (m + n), the rate coefficient has units of mol1−(m+n)·L(m+n)−1·s−1
For order zero, the rate coefficient has units of mol·L−1·s−1 (or M·s−1)
For order one, the rate coefficient has units of s−1
For order two, the rate coefficient has units of L·mol−1·s−1 (or M−1·s−1)
And for order three, the rate coefficient has units of L2·mol−2·s−1 (or M−2·s−1)
33. Define collision theory. Write the expression relating the rate of the reaction with temperature.
The collision theory states that when suitable particles of the reactant hit each other, only a
certain percentage of the collisions cause any noticeable or significant chemical change;
these successful changes are called successful collisions. The successful collisions have
enough energy, also known as activation energy,
The rate constant for a bimolecular gas phase reaction, as predicted by collision theory is:
where:
Z is the collision frequency.
ρ is the steric factor.
Ea is the activation energy of the reaction.
T is the temperature.
R is the gas constant.
PART-B QUESTIONS
1. (i) Derive the Michaleis-Menten equation for the enzyme substrate reaction.
E + AX E + P.
State also the assumptions made. (Dec13, 15 &May 13, 16)
Enzymes are nature’s catalysts. The vast majority of chemical reactions that keep living things alive
are much too slow to sustain life. An example is oxidation of a sugan –say glucose to give water,
carbon dioxide and energy. You can leave glucose open to the air for years without any appreciable
oxidation, yet this is one of the reactions that provides the energy to walk and run in daily life. There
are diseases caused by the failure of the body to produce a specific enzyme.
The Michaelis-Menten mechanism for the catalysis of biological chemical reactions is one of the
most important chemical reaction mechanisms in biochemistry.
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𝑑[𝑝𝑟𝑜𝑑𝑢𝑐𝑡] 𝑘1 [𝐸][𝑆]
𝑅𝑎𝑡𝑒 = = 𝑘2
𝑑𝑡 𝐾−1 + 𝐾2
Introducing the Michaelis-Menten Constant, KM
1 𝑘1
=
𝐾𝑀 𝐾−1 + 𝐾2
[𝐸]0 [𝑆]
= 𝑘2 [𝑆]
(1 + )
𝐾𝑀
Define the reaction velocity as 𝜈 = Rate. So,
[𝐸]0 [𝑆]
ν = 𝑘2
(𝐾𝑀 + [𝑆])
Note that the reaction velocity, 𝜐, is zero whe [S] is zero and that the reaction velocity increases as we
increase [S]. The reaction velocityreaches a maximum when [S] becomes very large. Define the
maximum velocity, υmax,as
[𝐸]0 [𝑆]
ν𝑚𝑎𝑥 = lim 𝑘2 = 𝑘2 [𝐸]0
[𝑆]→0 (𝐾𝑀 + [𝑆])
Then,
𝜈𝑚𝑎𝑥 [𝑆]
𝜈=
𝐾𝑀 + [𝑆]
Note, the kinetics of the reaction are characterized by two parameters, υ max and KM
1 𝐾𝑀 1
= +
𝜈 𝜈𝑚𝑎𝑥 [𝑆] 𝜈𝑚𝑎𝑥
In this experiment one measures 𝜈 as a function of [S]. if we plot 1/ 𝜈against 1/[S] we should get
straight line with slope, KM/𝜈𝑚𝑎𝑥 and intercept 1/𝜈𝑚𝑎𝑥 .
𝑠𝑙𝑜𝑝𝑒
𝐾𝑀 = 𝑠𝑙𝑜𝑝𝑒 × 𝜈𝑚𝑎𝑥 =
𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡
(ii) Explain the effect of temperature on the reaction rate according to collusion theory.
(Dec15, May 16)
where the are number of molecules /particles per unitvolume. We can see
the following:
Here we see that the concepts of collisions from simple kinetic theory can befundamentally related to
ideas of reactions, particularly when we considerthat elementary reactions (only for which we can
write rate expressionsbased on molecularity and order mapping) can be thought of proceeding
due to collisions (or interactions of some sort) of monomers (unimolecular),dimers(bimolecular),
trimers (trimolecular), etc.
If we are to naively say that reactions occur due only to collisions of particles(keep in mind the nature
of the system { gas-phase,elementary reaction),then we can at the zero'th order equate the maximum
reaction rate to thetotal collisional frequency for heterogeneous pairs:
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Thus, we need to consider the effects of collision energy and collisionsterics and/or orientation in our
discussion of simple collision theoryand its application to de_ningthe reate constant, k.
For energetic considerations, we can empirically add a factor to accountfor the probability of a
collision having a suffcient energy,vis-a-vis, Emin, for collision. When we multiply the total
collisionalfrequency by this probability, we can describe the fraction of collisionsthat will
energetically be able to progress from reactants to products.
The energy probability is take to be Boltzmann-like:
Thus we arrive at a corrected Simple collision theory expression for the rateconstant:
In general, we can write this expression for the rate constant as:
2. The irreversible reaction A + B AB has been studied kinetically and the rate of formation of
product has been found to be well correlated by the following equation; rAB = k CB2
(independent of CA). What reaction mechanism is suggested by this rate expression, if the
chemistry of the reaction suggests that the intermediate consists of an association of reactant
molecules and that chain reaction does not occur? (May-2008)
Refer, Chemial Reaction Engineering by Octave Levenspiel, 3rd Edition Page NO. 23 – 25.
3. The decomposition of reactant A at 400oC for pressures between 1 and 10 atm follows a first-
order rate law. Show that the mechanism,
A + A A* + A & A* R + S
is consistent with observed kinetics. (Dec-2003 & May-2006)
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4. Explain the effect of temperature on reaction rate according to the transition state theory and
compare with other theories. (May-2016, May 2013)
For elementary reactions, the rate expression can be written as a product of a temperature-dependent
term and a composition –dependent term,
For such reactions the temperature-dependent term, the reaction rate constant, has been found in
practically all cases to be well represented by Arrhenius’ law:
k = k0e-E/RT
Where k0 is called the frequency or pre-exponential factor and Eis called the activation
energy of the reaction.
At the same concentration, but at two different temperatures, Arrhenius’ law indicates that
Summarizes the predictions of the simpler versions of the collision and transition state theories for
the temperature dependency of the rate constant. For more complicated versions m can be as great as
3 or 4. Now, because the exponential term is much more temperature-sensitive than the pre-
exponential term, the variation of the latter with temperature is effectively masked
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5. (i) The pyrolysis of ethane proceeds with an activation energy of about 300 kJ/mol. How much faster
is the decomposition at 650°C than at 500"C? (Dec 2015)
(ii) Milk is pasteurized if it is heated to 63oC for 30 minutes, but if it is heated to 74oC it only
needs 15 seconds for the same result. Find the activation energy for this sterilization
(May-2006)
Assuming Arrhenius temperature dependency for the process
Now the rate is inversely proportional to the reaction time or rate ∝ 1/time
or
E = 422000 J/mol
6. Explain the Integral and Differential method of analysis for finding the rate of reaction.
(May05)
One of the purposes for which batch reactors are used is rate law determination.
Concentration (or any other convenient variable) measured as a function of time is the data typically
available
Several methods are available for this analysis - differential, integral, initial rate, half life, etc.
Differential Method
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or
From the data, we will get a straight line whose slope gives the order of the
reaction and whose intercept gives the logarithm of the rate constant.
But how to get
𝑑𝐶𝐴
given data of CAvs. time?
𝑑𝑡
several methods exist for this as well - numerical differentiation, graphical method, and polynomial
fit method
Numerical Differentiation
in this method, the derivative is evaluated using finite difference formulas –
, where i refers to the number of the data point. Such formulas can be forward or
backward difference.
A three-point differentiation formula in general will give more accurate results than the above:
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Thus,
Or,
and thus a straight line plot can be obtained to get the order or reaction from V vs. t data
Integral Method
* an order of reaction has to be assumed
* then the batch reactor equation is integrated with the rate law of assumed order
* the quantities are bunched together in such a manner as to get a linear equation
* plot the data for this line
* the assumed order is correct if the data actually fall on this line, if not, another trial is required
* the slope and intercept of this straight line should give the rate constant value
7. Aqueous A at a concentration CAo = 1mol/lit is introduced into a batch reactor where it reacts
away to form product R according to stoichiometry A R. The concentration of A in the
reactor is monitored at various rates as shown below;
t (min) 0 100 200 300 400
3
CA (mol/m ) 1000 500 333 250 200
For CAo = 500mol/m3 find the conversion of reactant after 5 hours in the batch reactor. Find the
rate for the reaction also. (Dec-2003)
Solution:
For 1st order reactionA R, the rate equation is
𝐶𝐴
−𝑙𝑛 ( ) = − ln( 1 − 𝑥𝐴 ) = 𝑘𝑡
𝐶𝐴0
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Slope gives; k- rate constant, rate constant is a constant value for same order reactions. Therefore,
equate the value for initial concentration CA0 = 500 mol/m3.
𝐶𝐴
−𝑙𝑛 ( ) = 𝑘𝑡
𝐶𝐴0
𝐶𝐴
−𝑙𝑛 ( ) = 𝑘(𝑠𝑙𝑜𝑝𝑒 𝑣𝑎𝑙𝑢𝑒) × 5
500
𝑪𝑨 = 𝒄𝒂𝒍𝒄𝒖𝒍𝒂𝒕𝒆 𝒕𝒉𝒆 𝒗𝒂𝒍𝒖𝒆.
8. The following data are obtained at 0oC in a constant-volume batch reactor using pure gaseous A;
t, min 0 2 4 6 8 10 12 14
pA, mmHg 760 600 475 390 320 275 240 215 150
The stoichiometry of the decomposition is A 2.5 R. Find a rate equation. (May-2006)
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9. The first order reversible liquid reaction A P, CAo = 0.5 mol/lit &CPo = 0, takes place in a batch
reactor. After 8 minutes, conversion of ‘A’ is 33.3% while equilibrium conversion is 66.7%. Find the
rate equation for this reaction. (May-2009)
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10. When a concentrated urea solution is stored it slowly condenses to biuret by the following elementary
reaction:
2 NH2-CO-NH2→ NH2-CO-NH-CO-NH2 + NH3
To study the rate of condensation a sample of urea (C = 20 milliliter) is stored at 100°C and after 7 hr
40 min we find that 1 mol% has turned into biuret. Find the rate equation for this condensation
reaction.
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11. Substrate A is converted to product by the action of enzyme, a high molecular weight (mw > 10000)
protein like substance. An enzyme highly specific, catalyzing one particular reaction or one group of
𝑒𝑛𝑧𝑦𝑚𝑒
reactions. Thus A→ R (May 2012)
Many of these reactions exhibit the following behavior:
i. A rate proportional to the concentration of enzyme introduced in to the mixture [E0].
ii. At low reactant concentration the rate is proportional to the reactant concentration, [A].
iii. At high reactant concentration the rate levels off and becomes independent of reactant
concentration.
(Propose a mechanism to account for this behavior)
Refer
12. Explain : (May 2012)
i. Arrhenius theory
In general, experiments do not suggest a T1/2 temperature dependence of therate constant. Moreover,
experiments demonstrate for most reactions thatthe temperature dependence of ln(k) is linear with
1/T . Thus, Arrhenius proposed the following relation between temperature and the rate constant:
Thus,
The energy is the activation energy (as discussed above) and the A value isa temperature-independent
frequency factor, or pre-exponential factor.
−E
Plotting ln(k) versus T-1 will yield a straight line with slopeequal to R aR and y intercept of ln(A).
The pre-exponential factor in this case if independent of temperature, contrastedwith the SCT result
from above. Though many reactions (across thespectrum of reaction orders, mechanisms, etc.) follow
Arrhenius behavior,there are exceptions (as always).
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Where,
Ni = molar amount remaining of species I
Ni0 =initial amount in the feed
vi=stoichiometric coefficient (+ for product, - for reactants)
ε = extent of reaction
iv. Single reactions and multiple reactions.-
13. Find the overall order of the irreversible reaction
(Dec 2012)
2H2 + 2NO →N2 + 2H2O
From the following constant-volume data using equimolar amounts of hydrogen and nitric
oxide:
Total pressure, mm Hg 200 240 280 320 360
Half-life, sec 265 186 115 104 67
Solution:
0.5(1−𝑛) − 1 (1−𝑛)
𝑡1/2 = 𝐶
𝑘(1 − 𝑛) 𝐴0
(1−𝑛)
𝑡1/2 ∝ 𝐶𝐴0
𝑃𝐴0 (1−𝑛)
𝑡1/2 ∝ ( )
𝑅𝑇
1 (1−𝑛) (1−𝑛)
𝑡1/2 = ( ) 𝑃𝐴0
𝑅𝑇
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15. (i) At 500K the rate of bimolecular reaction is ten times at 400 K. Find the activation energy for
this reaction from Arrhenius law and collision theory. If the rate of reaction at 600 K
thepercentage difference by this two methods. (May & Dec 2015)
Arrheniu’s law
𝑟2 𝐸 1 1
𝑙𝑛 = ( − )
𝑟1 𝑅 𝑇1 𝑇2
r1 = rate at 400K
r2 = rate at 500K
Given r2 = 10r1
Sub in equation and find r1 and then K.
Rate constant (K) is constant for same order reaction. Therefore, we can sub in rate equation to find
rate at 600K.
Similarly do for Collision Theory for the given rate equation.
(ii)Rahul likes to play the gambling tables just to get relaxed. He never expects to win and he
does not, so he selects games in which he losses are given small fraction of the money bet. He
plays steadily without a break, and the sizes of his bets are proportional to the money he has, if
at gambling table -1 it takes four hours to lose half of his money and at table-2 it takes two
hours to lose half of his money, how long can he play at both the tables simultaneously if he
starts with Rs. 1000 and quit when he has 10? (Dec 2015)
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(ii) Write the difference between molecularity and order of the reaction. (May 2015)
S.NO MOLECULARITY OF REACTION ORDER OF REACTION
1 It is defined as the number of molecules It is defined as the sum of the
atoms or ions participating in rate exponents of the concentration terms
determining step of the reaction. in rate equation.
2 It is theoretical quantity to satisfy the It is entirely an experimental
experimental findings. quantity.
3 It must be a whole number and never be It may be a whole number, zero or a
zero or a fraction. fraction.
16. (i) Explain in detail about industrial scale bioreactors with suitable diagrams. (May 2015)
Based on flow pattern: Plug flow and Tubular flow reactors.
Based on mode of operation: Batch, fed batch, CSTR.
Eg.Fluidised bed reactors
(ii) 2N2O→ 2N2+O2 according to second order rate reaction. The reaction rate is 977
cm3/(mol.s) at 895C. Calculate the fraction decomposed at 1s 10s and 10 minutes in a constant-
volume batch reactor. The initial pressure is 1 atm.
Write and take photo
we often try to design real reactors so that their flows approach these ideals.
3. What is a Batch reactor? (Dec 2012)
A batch reactor (BR) is one in which reactants are initially charged into a container, are well mixed,
and are left to react for a certain period. The resultant mixture is then discharged. This is an unsteady
state operation where composition changes with time; however at any instant the composition
throughout the reactor is uniform.
4. What are the advantages and disadvantages of a batch reactor?
The advantages of a batch reactor are (i) small instrumentation cost and (ii) flexibility of operation.A
batch reactor has the disadvantages of (i) high labour (ii) poor quality control of the product and (iii)
considerable shutdown time has taken to empty, clean out and refill.
5. What is a Mixed flow reactor?
Mixed flow reactor (MFR) is also called as back mix reactor or continuous stirred rank
reactor (CSTR) or constant flow stirred tank reactor (CFSTR).
In this reactor, the contents are well stirred and uniform throughout. The exit stream from the
reactor has the same composition as the fluid within the reactor.
6. What is a Plug flow reactor? (May 2011)
Plug flow reactor (PFR) is also referred as slug flow, piston flow, and idealtubular and
unmixed flow reactor. It specifically refers to the pattern of flow as plug flow.
It is characterized by the fact that the flow of fluid through the reactor is orderly no element
of fluid overtaking or mixing with any other element ahead or behind.
Actually, there may be lateral mixing of fluid in a PFR; however, there must be no mixing or
diffusion along the flow path.
The necessary and sufficient condition for plug flow is the residence time in the reactor to be
the same for all elements of fluid.
7. Differentiate between MFR and PFR.
MFR: i) there is no concentration gradient within the reactor, since there is uniform mixing.
ii) Rate of reaction varies with concentration alone.
PFR: i) There is concentration gradient within the reactor in the axial direction, since there
is no mixing in this direction.
ii) Rate of reaction varies with position.
8. Define space time & space velocity. (May 2013, 14, 15& 16, Dec 15)
The time required to process one reactor volume of feed measured at specified conditions is called
space time.
Space velocity is defined as the number of reactor volumes of feed at specified conditions which can
be treated in unit time.
9. Explain conservation of mass in reactors.
Rate of accumulation of the component within the system = Rate of flow of a intothe system — Rate
of flow of A out of the system — Rate of consumption of component a in the System.
10. Write the classification of chemical reactors based on the method of operation and the number
of phases in the reaction mixture.
Method of operation: Unsteady state reactorsbatch and Semi-batch
Steady state reactor Tubular reactor, Back mix
Phases: Homogeneous reactor Batch, PFR, MFR reactors
Heterogeneous reactor Biochemical Reactor
11. Distinguish between Holding time and Space time for flow reactors.
Holding time: It is the mean residence time of flowing material in the reactor. It is given by the
expression t = CAodXA / [(-rA) (1 + A XA)]
Space time: It is the time needed to treat one reactor volume of feed at specified conditions. It is
given by the expression, = V/vo = (CAo V) / FAo
For constant density systems (all liquids and constant density gases) t = = V/v. Where ‘V’ is the
volume of the reactor and ‘v’ is the volumetric flow rate of reacting fluid.
12. Consider a gas phase reaction 2A R+2S with unknown kinetics. If a space velocity of 1min-1
is needed for 90% conversion of A in a PFR find the corresponding space time and mean
residence time or holding tome of the fluid in the reactor.
Given, XA=0.9, space velocity=1 min-1.
(i) Space time=1/space velocity=1 min.
(ii) = V/vf = V/vo (1 + AXA ); where A = (3 - 2)/2 = 0.5 and V/v0 = 1
Therefore, = V/vf = V/vo (1 + A XA) = 1/1.45=0.6897 min.
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13. A 2nd order reaction is to be carried out in 3 CSTR’s of Volume 100 lit, 150 lit and 200 lit.
Explain how they are connected.
For 2nd order (n > 1) reaction, to be carried out in CSTR’s of different sizes,the reactors should be
ordered so as to keep the concentration of reactant as high as Possible. This can be performed by
arranging them in the ascending order with respect to volume or size. Hence, the best arrangement
should be 100 liter 150 liter 200 liter
14. Differentiate between PFR and Batch reactor.
PFR: (i) It is a steady state flow reactor
(ii) As space time increases concentration of reactant decreases
(iii) Better quality control
(iv) For high rate of reaction PFR is employed.
Batch reactor: (i) It is unsteady state reactor
(ii) As reaction time increases concentration of reactants decreases
(iii) No better quality control
(iv) For very slow reactions or low rate of reaction batch reactors are employed.
15. What are steady and unsteady state reactors? Explain.
Steady state reactor: Reactors those in which the properties of the system do not change with time is
said to be a steady state reactor. Example: Continuous stirred Tank reactor, plug flow reactor.Total
mass inflow = Total mass outflow
Unsteady state reactor: Reactors are those in which the properties of the system changes with time
and rate of reaction decreases with time expect for zero order reaction are said to be unsteady
state reactor. Example: Batch reactor, Semi-batch reactor. There is accumulation in these reactors.
Accumulation = input - output + generation - consumption.
16. What are semi batch reactors? Give the different types. (Dec 2012)
It is an unsteady state reactor. Reactors which are partially batch and partially continuous are referred
to as semi-batch reactor. The semi batch reactors offers good control of reaction speed, because the
reaction proceeds as reactants are added. Types: (i) volume changes but composition is unchanged
(ii) composition changes but volume is constant.
17. Which achieves higher conversion among the flow reactors for identical conditions? Why?
For identical conditions i.e. for some reactor volume conversion achieved in PFR is higher than in
MFR. Since in a PFR, all the properties vary gradually along the length of the reactor. Hence
concentration is maintained at high value throughout and the rate of reaction is maintained at high
value. Therefore Conversion achieved in PFR for same volume is greater or higher than in MFR.
18. Why does rate of reaction vary in a PFR? How does it vary in a MFR?
Rate of reaction varies, for isothermal reactions, in PFR as there is no mixing in the axial direction
since rate of reaction is directly proportional to concentration. As concentration of reactant varies
with distance rate of reaction also varies. In PFR, rate of reaction is independent of time and
dependent on position or distance.In MFR, rate of reaction is independent of position &dependents on
concentration of reactants.
19. For two CSTR’s operating in series, state the principle involved to determine the minimum
volume of reactors. Given, feed concentration is CAO and final concentration is CA2. The
reaction is first order.
For a system of two CSTR’s connected in series, in which first order reaction is taking place and for
the given conversion, the minimum volume of reactors will be obtained when both the reactors are
operated with equal volume. This was obtained by using the minimum concentration of ‘A’ as CA, MIN
= SQRT (CAO CA2) inthe performance equation.
20. How does intermediate conversion affect the volume of the multiple reactor system for single
reactions?
Intermediate conversion affects the volume of the multiple reactor system for single reactions in case
of MFR only .In case of PFR intermediate conversion does not determine the total reactor volume; in
the case of PFR’s whatever be the intermediate conversion the total reactor volume required to
achieve a given conversion is identical .In case of MFR, there is a particular intermediate conversion.
At this conversion the total volume of the reactor required is minimum. Thisconversion is called as
“the best intermediate conversion“. If the intermediate conversion is changed the size ratio and
volume of the units will change.
21. A large CSTR, small CSTR and PFR of fixed volume are available. In general, how would you
arrange them for getting maximum conversion for reactions of order >1 and <1. Why?
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For n>1 arrangement is PFR followed by small CSTR followed by large CSTR to maintain
the reactant concentration as high as possible.
For n<1 arrangement is large CSTR followed by small CSTR followed by PFR.
For n=1 arrangement for first order reaction sequencing does not affect conversion. It can be
either PFR followed by MFR or MFR followed by PFR.
22. If 1/(-rA) versus XA graph decreases to a minimum from XA = 0 to XA = 0.4 and then increases,
suggest a multiple reactor system with minimum volume for a desired conversion of XA = 0.6.
For the given situation, the best reactor setup should be PFR followed by CSTR. That is, PFR should
be operated up to the point of minimum (up to XA = 0.4) followed by a CSTR to fulfill the desired
conversion (XA = 0.6).
Because minimum the area under the curve of 1/(-rA) versus XA will lead to the minimum volume for
the desired conversion. This was obtained only by the above said reactor arrangement.
23. What is a Recycle reactor?
In some reaction system, it is advantageous to divide the product stream and a part returned to reactor
as recycle to increase the conversion rate. These reactors are called recycle reactors. The recycling
provides a means for obtaining various degree of backmixing.
24. Define Recycle ratio and give its significance
Recycle ratio ‘R’ can be defined as the ratio of the volume fluid returned to the reactor entrance to
the volume of fluid leaving the system or reactor.
Significance: Recycle ratio can be made to vary from zero to infinity. Reflection suggests that as the
recycle ratio is raised, the behavior shifts from plug flow (R = 0) to mixed flow (R = ).
25. What do you mean by optimum recycle operation?
When material is to be processed to some fixed final conversion in a recycle reactor, there must be a
particular recycle ratio ‘R’ that minimizes the reactor volume or space time. That recycle ratio is said
to be optimum and the operation is said to be optimum recycle operation.
26. Suggest the most suitable reactor setup for all autocatalytic reactions.
The most suitable reactor setup for autocatalytic reactions is MFR operating at the point of maximum
rate (low conversion) followed by a PFR (high conversion); that is, MFRoperating to maximum rate
followed by PFR. Because this will lead to a system with minimum volume for a desired conversion.
27. Define instantaneous and overall fractional yield.
Instantaneous fractional yield () is the ratio of moles of desired product formed at any instant to
moles of reactant (A) reacted at any instant. ‘’ is a function of CA. As CA varies throughout the
reactor, ‘’ will also vary with position in the reactor.
Overall fraction yield () is the mean of the instantaneous fractional yields at all points within the
reactor.Both the yields depend on the type of flow within the reactor.
28. Explain the term “Selectivity” and “Yield”.
Selectivity is defined as the ratio of moles of desired product to moles of undesired product.Yield is
defined as the ratio of moles of product formed to moles of reactant either fed or consumed.
29. What are the factors affected by the pattern of flow within the vessel for multiple reactions?
The factors affected by the pattern of flow within the vessel for multiple reactions are (i) The Volume
of the vessel, (ii) The product distribution, (iii) Selectivity and yield of product.
30. How will you control the product distribution for reactions in parallel using k2/k1?
The product distribution for reactions in parallel can be controlled by varying the ratio k2/k1
(ratio of the rate constants of the formation of undesired product to the desired product). This
can be done in two ways;
By changing the temperature level of operation. (If the activation energy of the two reactions
are different, k2/k1 can be made to vary.)
By using a catalyst. (One of the most important features of catalyst is its selectivity in
depressing or accelerating specific reactions. This may be a much more effective way of
controlling product distribution than any other way.)
31. How does the concentration level of reactants affect the product distribution in parallel
reactions? (May 2012)
For reactions in parallel, the concentration level of reactants is the key to proper control of product
distribution. That is,
i) High reactant concentration favors the reaction of higher order.
ii) Low reactant concentration favors the reaction of lower order.
iii) The concentration level has no effect on the product distribution for reactions of the same
order.
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T
T is Parallel with respect to A and series with respect to A, R, and S.
(ii) A+BR and R+BS
Parallel with respect to B and Series with respect to A, R, and S.
33. Explain the best operating conditions for parallel reactions.
For a desired conversion, the best operating condition for parallel reactions is that the reaction should
be performed in the MFR first, up to the maximum yield withrespect to theconcentration of reactant
in the (S/A) versus CA, and the followed by a PFR up to the desired conversion. Here, ‘S’ is the
desired product.
34. Describe briefly on multiple reactions.
There are three basic types of multiple reactions: series, parallel, and independent. In parallelreactions
(also called competing reactions) the reactant is consumed by two different reactions to form different
products:
In series reactions, also called consecutive reactions, the reactant forms an intermediate product,
which reacts further to form another product:
Multiple reactions involve a combination of both series and parallel reactions,
Independent reactions are of the type and occur in feed stocks containing many reactants. The
cracking of crude oil to form gasoline is an example of an independent reaction.
35. Write the assumptions made in the design equation of (May 2014& Dec 15)
(i) Batch reactor
(ii) Plug flow reactor
Batch Reactor:
Closed system: no streams carrying mass enter of leave the system. No ideal flow or out
flow, FA0 = FA = 0
Well mixed, no spatial variation in system properties
Constant volume, V= V0or Constant pressure
Plug Flow Reactor:
Steady state
No radial variation in properties of the system.
36. Write the simpson 1/3 rule and explain the variables. (May 2016)
Simpson's rule is a Newton-Cotes formula for approximating the integral of a function
using quadratic polynomials (i.e., parabolic arcs instead of the straight line segments used in
the trapezoidal rule). Simpson's rule can be derived by integrating a third-order Lagrange
interpolating polynomial fit to the function at three equally spaced points. In particular, let the
function be tabulated at points , , and equally spaced by distance , and denote .
Then Simpson's rule states that
PART-B QUESTIONS
1. Derive the performance equation forMixed flow reactor.(Dec-2004 & Dec-2005)
We know the composition is uniform throughout the reactor. Select reactant ‘A’
Input = output + disappearance by reaction + accumulation
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2. A homogeneous gas reaction A 3R has a reported rate at 215oC as -rA = k CA1/2mol/lit-sec.
Where k =10-2. Find the space time needed for 80% conversion of 50% ‘A’ and 50% inert feed
to PFR operating at 215oC and 5 atm. (May-2008)
Solution:
For 50% inerts,
𝜀𝐴 = 4−2=1
2
Substitute in Plug flow performance equation,
The integral is evaluated by graphical method by assuming the values of A in an equal interval.
XA = 0→1
1+𝑋𝐴 1/2
Plot graph by taking XA in x-axis and ( ) in y-axis. Find out the area under the square to
1−𝑋𝐴
determine the space time.
3. The kinetics of the aqueous phase decomposition of ‘A’ is investigated in two mixed reactors in
series, the second having twice the volume of the first reactor. At steady state with a feed
concentration of 1 mol(A)/liter and mean residence time of 96 seconds in the first reactor, the
concentration in the first reactor is 0.5 mol(A)/liter and in the second is 0.25 mol(A)/liter. Find
the kinetic equation for the decomposition. (Dec-2005)
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4. A liquid reactant stream (1 mol/lit) passes through two MFR’s in series. The concentration in the exit
stream of the first reactor is 0.5mol/lit. Find the concentration in the exit stream of the second reactor.
The reaction is second order with respect to ‘A’ and V2/V1 =2 (May-2008)
5. Originally we had planned to lower the activity of a gas stream containing radioactive Xe-138 (half-
life = 14 min) by having it pass through two holdup tanks in series, both well mixed and of such size
that the mean residence time of gas is 2 weeks in each tank. It has been suggested that we replace the
two tanks with a long tube (assume plug flow). What must be the size of this tube compared to the
two original stirred tanks, and what should be the mean residence time of gas in this tube for the same
extent of radioactive decay? (Dec-2007)
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6. Consider the parallel decomposition of A of different orders, S is desired product andCAo = 4mol/lit,
R rR = 1
A S rS = 2 CA
T rT = CA2
Find the maximum expected CS for isothermal operations (i) in a MFR & (ii) in a PFR
7. A concentrated aqueous A-solution of the previous examples (CA0 = 4 mol/liter,FA0= 1000 mol/min)
is to be 80% converted in a mixed flow reactor.
(a) What size of reactor is needed?
(b) What is the heat duty if feed enters at 25°C and product is to be withdrawn at this temperature?
Note that
1000 cal 1 kg 1 liter cal
CpA = . . = 250
kg. K 1 liter 4 mol A mol A . K
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8. We wish to treat 10 liters/min of liquid feed containing 1 mol A/liter to 99% conversion. The
stoichiometry and kinetics of the reaction are given by
𝐂𝐀 𝐦𝐨𝐥
𝐀 → 𝐑, − 𝐫𝐀 =
𝟎. 𝟐 + 𝐂𝐀 𝐥𝐢𝐭𝐞𝐫. 𝐦𝐢𝐧
Suggest a good arrangement for doing this using two mixed flow reactors, and find the size of
the two units needed. Sketch the final design chosen.
9. Derive the space time and space velocity equations for the steady state MFR and PFR and also
give the graphical representations of the design equations. (Nov 2010& Dec 15)
10. At present we have 90% conversion of a liquid feed (n = 1, CA0, = 10 mol/liter) to our plug flow
reactor with recycle of product (R = 2). If we shut off the recycle stream, by how much will this
lower the processing rate of our feed to the same 90% conversion? (Dec 2011)
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11. A batch reactor is designed to convert A into R. this is aliquid reaction. The stoichiometry is given by
A → R and the rate of reaction is given in the following table. How long must the batch for the
concentration to drop from 1.3 mol per liter to 0.3 mol per liter. (May 2013)
CA (mol/lit) 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 1.0 1.3 2.0
-rA(mol/lit.min) 0.1 0.3 0.5 0.3 0.5 0.25 0.1 0.06 0.05 0.045 0.042
12. (i) Discuss different types of reactors used for carrying out reactions. (Dec 2012)
(ii) Derive the equation to find out optimum T and CR/CAo in mixed flow reactor for the reaction.
A→R→S
Refer Octave levenspiel page no: 175-178
13. A gaseous feed of pure A with CA0 = 1 mol/L enters a mixed flow reactor of 2-liter volume and reacts
to give R. The reaction kinetics and stoichiometry are given by 2A -> R, -rA=0.05CA2mol/(l.s). Find
the feed rate (l/min) that will give an outlet concentration CA=0.5 mol/L. (May 2015)
14. Derive the design equation for ideal batch reactor and CSTR. (May 2016)
Refer Class Notes.
15. A homogeneous liquid phase reaction A→R with reaction rate −𝑟𝐴 = 𝑘𝐶𝐴2 takes place with 50%
conversion in a mixed reactor. (May 2016)
(i) What will be the conversion if this reactor is replaced by one, six times as large, other
factors remaining unchanged?
(ii) What will be the conversion if the original reactor is replaced by a PFR of equal size,
other parameters unchanged?
𝑠𝑢𝑐𝑟𝑎𝑠𝑒 𝐾𝐶𝐴 𝐶𝐸𝑜
16. In a hydrolysis reaction 𝑆𝑢𝑐𝑟𝑜𝑠𝑒 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡 with reaction rate,−𝑟𝐴 = , where M is
𝐶𝐴 +𝑀
the Michaeli’s menten constant. Show by calculation whether the following data can be reasonably fit
the kinetic equation. Evaluate the constants k and M. (Dec 16)
Time (t) 1 2 3 4 5 6 7 8 9
CAmmol/l 0.84 0.68 0.53 0.38 0.27 0.16 0.09 0.04 0.018
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called?
The distribution of different lengths of time for the stream of fluid leaving the vessel is called (i) The
Exit age distribution ‘E’ (ii) The residence time distribution ‘RTD’ of fluid.
19. Define Turnover time.
The time between successive peaks characterizes fluid regulation is called turnover time.
20. Give the relationship between ‘E’ and ‘F’ curves.
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 = [Fraction of effluent which has been in the reactor for less than time ‘t’]
0
= F(t) (or) dF/dt = E(t)
21. State the one parameter in the dispersion model and state its limitations.
The one parameter in the dispersion model is “Vessel dispersion number [D/(U L)]”, which measures
the extent of axial dispersion. When D/(U L) 0, real reactor will behanve as ideal PFR and D/(U L)
∞, real reactor will behanve as ideal MFR.Where ‘D’ is the dispersion or diffusion coefficent, ‘U’
is the linear velocity of fluid flow, and ‘L’ is the characteritic dimension of the reactor.
22. Define E() and F(). Sketch E() vs. for (i) ideal PFR and (ii) ideal CSTR.
The dimensionless function of exit age distribution E() is defined as E = t E = (V/M) C.
Where‘t’ is the mean residence time, ‘V’ is the volume of the reactor, ‘M’ is the quantity of tracer,
and ‘C’ is the effluent concentration of tracer (by pulse input).
The dimensionless form of CStep curve is called the F-curve. It is given by F = (v/m) CStep.
Where ‘v’ is the volume rate of flow of the reacting fluid, and ‘m’ is the mass rate of flow of the
tracer. Note: draw the E() vs. for ideal PFR and ideal CSTR.
23. What is tank’s-in-series model? State its limitations. (Dec 2012)
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.
24. Define peclet number. What is the value of peclet number for (i) ideal CSTR and (ii) ideal PFR.
The reactor Peclet number (NPe,R) 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,R = (U L)/D.Where ‘U’ is the
velocity of reacting fluid flow, ‘L’ is the length of the reactor, and ‘D’ is the dispersion or diffusion
coefficient.For ideal CSTR, NPe,R = 0 and for ideal PFR, NPe,R = ∞.
25. Define Schmidt number and Sherwood 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.
26. Give Two examples for non – ideal flow. (May2011)
Short circuiting and formation of stagnant zones.
27. What are the models used to characterize non-ideal flow? (May 2015)
The models for non-ideal reactors are
Dispersion model
Tank in series model
Segregation model
Compartment model
28. Define axial mixing and radial mixing. (Dec 2015)
Axial (down and up) pumping is an important flow pattern because it addresses two of the most
common challenges in mixing; solid suspension and stratification. In this process both the superficial
and annular velocities can be calculated to determine and control the level of mixing
Radial impellers are commonly selected for low level mixing (known as a tickler blade) or elongated
tanks. They typically give high shear rates because of their angle of attack. They also have a
relatively low pumping number, making them the most sensitive to viscosity. Radial impellers do not
have a high tank turnover flow like axial flow impellers.
29. What are the factors which make up contacting in the reactor stream? (Dec 2015)
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There are three interrelated factors make up the contacting or flow pattern:
The RTD or residence time distribution of material which is flowing through the vessel
The state of aggregation of the flowing material, its tendency to clump and for a group of
molecules to move about together
The earliness and lateness of mixing of material in the vessel.
30. Define selectivity for parallel reactions. (May 2016)
Assume a reactant ‘A’ which can form a desired product ‘D’, and an undesired side-product ‘U’ in
parallel reactions.
PART-B QUESTIONS
1. Explain the different experimental methods for finding E-curve. (May 2013& Dec 15)
Refer Octave Levenspiel notes page no:260-264
2. Explain C-curve, E-curve and F-curve. Derive the relation between them.(May 2013, 15)
Refer Octave Levenspiel notes page no:260-266
3. The concentration reading in the table represents a continuous response to a pulse input into a closed
vessel which is to be used as a chemical reactor.
t, min 0 5 10 15 20 25 30 35
C, gm/lit 0 3 5 5 4 2 1 0
(i) Tabulate and plot the exit age distribution E.
(ii) If the vessel used as a reactor for a liquid decomposing with rate
-rA = k CA k = 0.307 min-1,
Find the fraction of reactant unconverted in the real reactor and compare this with the fraction
unconverted in a PFR of the same size. (Dec-2004 & Dec-2005)
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5. Discuss the Dispersion model and Tanks-in-series model to represent the non-ideality in real reactors.
(May-2009& 2016)
Refer Class Notes of Unit III
6. A small diameter pipe 32m long runs from the fermentationroom of a winery to the bottle filling
cellar. Sometimes red wine is pumped through the pipe, sometimes white and whenever the switch is
made from one to the other, a small amount of house blend is produced (8 bottles). Because of some
construction in the winery, the pipe length to be increased to 50m. For the same flow rate of wine,
how many bottles of red may we expect to get each time we switch the flow? (May-2009)
Solution:
Original : L1 = 32m, σ1 = 8
Longer Piper : L2 = 50m, σ2= ?
7. Kerosene and gasoline are pumped successively at 1.1 m/s through a 25.5-cm ID pipeline 1000 km
long. Calculate the 5195%-9515% contaminatedwidth at the exit of the pipe given that the kinematic
viscosity for the 50150% mixture is
μ 2
= 0.9 × 10−6 m ⁄s
ρ
(Data and problem from Sjenitzer, Pipeline Engineer, December 1958).
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8. Assuming plug flow we calculate that a tubular reactor 12 m long would give 96% conversion of A
for the second-order reaction A --+ R. However, the fluid is very viscous, and flow will be strongly
laminar, thus we expect the convection model, not the plug flow model, to closely represent the flow.
How long should we make the reactor to insure 96% conversion of A? (Dec 2011)
9. Fluid flows at a steady rate through 10 tanks in series. A pulse of tracer is introduced into the first
tank, the time this tracer leaves the system is measured giving. Maximum concentration =100
mmol/lit, tracer soread = 1 min, if 10 more tanks are connected in series with the original 10 tanks
what would be (i) the maximum concentration of leaving tracer? (ii) The tracer spread? (iii) How
does the relative spread change with number of tanks? (May 2012)
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10. (i) Discuss the effects of non-ideal with examples. (Dec 2012)
(ii) Explain the methods of conducting stimulus responses experiments with various inputs.
Refer Class Notes
11. From a pulse input in to a vessel, the following output signal is obtained.
Time (t) 1 3 5 7 9 11 13 15
Conc. (g/l) 0 0 10 10 10 10 0 0
This has to be represented the flow through the vessel with tank-in-series model. Using the variance
matching procedure, determine the number of tanks in use. Also, calculate the vessel dispersion
number (D/UL). (May 2013)
12. Aqueous A (CAO = 50 mol/m3) with physical properties close to water (ρ = 1000 kg/ m3, Diffusivity =
10-9 m2/s) reacts by a second order reaction (k = 10-3 m3/ mol .s) as it flows at 10 mm/s through a
tubular reactor (dt = 10 mm, L = 20 m). Find the conversion of reactant A from this reactor.
13. A liquid reactant stream with CA0 = 1 mol/lit passes through two CSTR in series. The concentration
of A in the stream leaving the first reactor is 0.5 mol/lit. Find the concentration of A in the exit stream
for the second reactor. The reaction is second-order with respect to reactant A and the volume of the
second reactor in series twice that of the first reactor. (May 2015)
14. An aqueous reactant stream with CA0 = 4 mol/lit passes through a mixed flow reactor followed by a
plug flow reactor. Determine the concentration at the exit of the plug flow reactor if C A = 1 mol/lit in
the mixed reactor. The reaction is second order with respect to A and Vplug/Vmixed = 3. (May 2015)
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15. The concentration reading given below represents a continuous response to a pulse input in to a
closed vessel. (Dec 15)
Time (t) 0 1 2 3 4 5 6 7 8 9 10 12 14
Cpulse(g/m3) 0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
This vessel is to be used as a reactor for decomposition of liquid A. the reaction kinetics and
stoichiometry are given by A → Products, −𝑟𝐴 = k𝐶𝐴 , k = 0.10 min-1. Calculate the conversion of
reactant A in the real reactor.
16. A reactor has the flow characteristics given by the non-normalized C-Curve in table below and by the
shape of this curve; we feel that the dispersion on tank-in-series model should satisfactorily represent
flow in reactor. (May 2016)
Time (t) 1 2 3 4 5 6 7 10 15 20 30 41 52 67
Conc. 9 57 81 90 90 86 77 67 47 32 15 7 3 1
(g/l)
i) Find the conversion expected in the reactor, assuming that the dispersion model holds good.
ii) Find the number of tank-in-series which will represent the reactor and the conversion
expected, assuming that tank-in-series holds well.
iii) Find the conversion by direct use of tracer curve given XA = 99% for a PFR.
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reaction. This is because intrapellet temperatures will be greater than surface values. For endothermic
reactions, both temperature and concentration gradients reduce the rate below that evaluated at outer-
surface conditions.
5. When bulk and Knudsen diffusion occurs?
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.
6. 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.
7. What do you mean by effective diffusivity?
In a porous catalyst the pores in a catalyst are not straight and they follow tortuous, 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.
8. Define effective thermal conductivity.
The effective thermal conductivity (ke) is the energy transferred per unit of total area of pellet
(perpendicular to the direction of heat transfer).
9. Define effectiveness factor.
The effectiveness factor (η) is defined as the ratio of actual rate for the whole pelletto the rate
evaluated at outer surface conditions.
10. Write the expression for Thiele modulus with respect to spherical catalyst.
Thiele modulus for spherical catalyst is
Фs = rs/ 3 (k’ p / De)1/2
Where rs - Radius of the spherical catalyst
k’ - First order reaction rate constant
p - Density of the catalyst pellet;De - Effective diffusivity
11. Write the expression for effectiveness factor for a single cylindrical pore on the catalyst.
The effectiveness factor for a single cylindrical pore on the catalyst pellet (in which first
orderreaction occurs) is
η = tanh (ФL) / ФL
Where ФL is the Thiele modulus and is given by ФL = L / (k1 p / De)1/2
L is the thickness of cylindrical pore.
12. Give the industrial importance of Gas-Solid non-catalytic reactions. (Dec 2012)
Gas-Solid non-catalytic reactions are employed in;
Roasting of ores.
The preparation of metals from their oxides in reducing atmospheres.
The platting of metals.
Reactions of carbonaceous materials.
13. List the sequence of steps involved in determining the global rate for an irreversible Gas-Solid
non-catalytic reactions.
For an irreversible Gas-Solid non-catalytic reaction, the global rate will be determined by the four
steps;
Mass transfer from bulk fluid to the outer surface of the particle.
Intra-particle diffusion into the particle.
Adsorption at an active site of solid reactant.
Intrinsic (surface) reaction at the site.
14. List the models explained for Gas-Solid non-catalytic reactions.
For the Gas-Solid non-catalytic reactions, the two idealized models are;
Progressive-conversion model
Shrinking-core model
15. Compare the Progressive-conversion and Shrinking-core model.
Progressive-conversion model:
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28. Draw the energy diagram of catalyzed and Uncatalyzed reaction. (May 2014)
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29. What is the pore resistance limits for porous catalytic particles? (May 2015)
When reactant fully penetrates the particle and bathes all its surfaces, then the particle is in the
diffusion free regime. This occurs when MT<0.4 or MW<0.15. At some extreme when the centre of
the particle is starved for reactant and is unused then the particle is in the strong pore resistance
regime. This occurs when MT>4 or MW>4.
30. Define Damkohler Number. (May 2016)
The Damköhler numbers (Da) are dimensionless numbersused in chemical engineering to relate
the chemical reactiontimescale (reaction rate) to the transport phenomena rate occurring in a system.
Reaction rate Diffusion time
Da = =
Diffusion rate Reaction time
Da is associated with characteristic diffusion and reaction times therefore scaling is necessary.
For Da >>1 the reaction rate is much greater than the diffusion rate distribution is said to be
diffusion limited (diffusion is slowest so diffusion characteristics dominate and the reaction is
assumed to be instantaneously in equilibrium)
For Da <<1 diffusion occurs much faster than the reaction, thus diffusion reaches an
‘equilibrium’ well before the reaction is at equilibrium.
31. Describe the features of random pore model. (May 2016)
For fluid-solid reactions, a random pore model is developed which allows for arbitrary pore size
distributions in the reacting solid. The model can represent the behavior of a system that shows a
maximum in reaction rate as well as one that does not, and it identifies an optimal pore structure for
either of such systems.
PART-B QUESTIONS
1. What do you understand by “Thiele modulus” and “Effectiveness Factor” for catalyst particles?
2. The catalytic reaction
𝐴 → 4𝑅
is run at 3.2 atm and 117°C in a plug flow reactor which contains 0.01 kg of catalyst and uses a feed
consisting of the partially converted product of 20 liters/hr of pure unreacted A. The results are as
follows:
Run 1 2 3 4
CAin, mol/lit 0.100 0.080 0.060 0.040
CAout, mol/lit 0.084 0.070 0.055 0.038
Find a rate equation to represent this reaction. (May 2015)
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3. Determine the amount of catalyst needed in a packed bed reactor for 75% conversion of 1000 mol
A/min of a CA0 = 8 mol/m3 feed.
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4. Derive the rate expression for finding out effectiveness factor for spherical catalyst particle. Assume
first order irreversible reaction takes place on the catalyst.
5. Derive the equation to find out conversion for particle of unchanging in size, when ash layer and
chemical reaction controls the rate of reaction. Assume unreacted core model. (May 09, 16, Dec 12)
6. 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 hr, conversion is complete in two hours. What mechanism is rate controlling?
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7. Explain the parameter used to identify the kinetic regimes in Fluid-Fluid reactions and how is it used?
8. A first order reaction takes place between species ‘A’ (in gas phase) and species ‘B’ (in liquid phase).
The reaction is fast. Derive the overall rate expression.
9. Derive the rate equation for fluid-fluid reaction for the following cases;
(i) Instantaneous reaction with low and high CB
(ii) Fast reaction with low and high CB
10. For the reaction𝐴(𝑔) + 𝑏𝐵(𝑠) → 𝑐𝐶 (𝑔) + 𝑑𝐷(𝑔) described by unreacted core model when ash layer
is the rate controlling step for particles of unchanging size, establish the relationship between
conversion and time. (May 2013)
11. A feed consisting of , 30% of 50 μm- radius particles, 40% of 100 μm-radius particles, 30% of 200
μm-radius 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
of solids to the grate for a residence time of 8 min in the reactor. (May 2013)
12. Describe pore diffusion resistance combined with surface kinetics. (May 2015)
13. Derive the rate equation for two resistances in series to transfer A from gas to liquid.(Dec 2015)
14. Derive the equation for resistance in series in the G/L reaction on a catalyst surface.(Dec 2015)
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It is a heterogeneous reactor in which solid (S) is fluidized by the gas (G), on top of it liquid (L) is
sprayed counter-currently. The performance of it varies widely in G/L ratio from gas (G) bubbling
through an liquid (L) slurry to a gas (G) fluidized bed of damp solid (S) particles and it lies between
the performances of slurry and trickle bed reactors.
22. On what factors the selection of contactor for G/L reactions on solid catalyst depends?
The selection of good contactor for G/L reactions on solid catalyst depends on;
Where the controlling resistance lies in the rate expression,
The advantages of one contacting pattern over another, and
The difference in auxiliary equipment needed.
The overall economics which accounts for these three factors will determine which set up and reactor
type is best.
23. List the industrial applications of reactors for G/L reactions on solid catalyst.
The catalytic hydrogenation of petroleum fractions to remove sulfur impurities.
The catalytic oxidation of liquid hydrocarbons with air or oxygen.
The removal of dissolved organics from industrial waste water by catalytic oxidation as an
alternative to bio-oxidation.The removal of airborne pollutants by adsorption and/or reaction.
24. Write short notes on ‘Reactors for Fluid-Fluid reactions’. (May2011)
The reactor for Fluid-Fluid (Gas-Liquid) reactions is named as “‘Double mixed reactor”. The
particular features of this reactor are;
Mixed flow of gas and of liquid, hence uniform composition in the bulk of each phase.
The agitation rate in the phase can be changed independently.
The surface to volume ratio can be varied by changing the interfacial contact area.
The concentration level of reactants can be raised or lowered by changing the feed rate or
feed composition.
Because of mixed flow of the phases the rate of absorption and reaction can be found directly by
means of a material balance.
25. Define Jet impact factor. (May 14)
The idea here is to force two streams, one of reactant, the other of a very hot heat carrier or catalyst,
to collide at very high velocity and thereby mix intensely and react at high temperature. For an all-gas
product, the product stream is rapidly quenched, while for a gas-solid product, a cyclone separates the
two phases, after which the gas is rapidly cooled. By using the word "rapidly" we mean that the
whole operation-mixing, reacting, separating and quenching-is done in 0.1 to 0.3 seconds
26. Give three examples of non catalytic reactions. (May2011)
1. Addition of hydrogen to maleic acid.
2. Reaction of isonitriles
3. Reaction of carboxylic acids
27. What is pulse input? (May 2015)
In a pulse input, an amount of tracer is suddenly injected in one shot into the feed stream entering the
reactor in as short time as possible for RTD analysis.. The outlet concentration is then measured as a
function of time. Theconcentration-time curve is referred to as the C curve.
PART-B QUESTIONS
1. Discuss the operation of fixed-bed catalytic reactor. (May-2007)
2. (i) Explain the operation of fluidized bed reactor. (Dec 2015)
(ii) Derive the design equation of fluidized bed reactor based on two phase fluidized bed model.
(May 14& 16)
3. Dilute aqueous ethanol (about 2-3%) is oxidizedto acetic acid by the action of pure oxygen at 10 atm
in a trickle bed reactorpacked with palladium-alumina catalyst pellets and kept at 30°C. The reaction
proceeds as follows:on
with rate
Find the fractional conversion of ethanol to acetic acid if gas and liquidare fed to the top of a reactor
in the following system:
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4. Consider the solid catalyzed reaction A(g) + b B(l)X C(i) being carried out in a slurry reactor.
Develop the design equation. State all assumptions. (May-2008)
5. Write briefly by giving suitable examples of industrial reaction carried out in the following reactors;
(i) Trickle bed reactor (May-2016)
(ii) Fluidized bed reactor (May-2012)
6. Explain the operation of a slurry reactor. Predict the rate equation for a first order reaction in a slurry
reactor.
7. Calculate the time needed to burn to completion particles of graphite (R0 = 5 mm, pB= 2.2 gm/cm3, k"
= 20 cm/sec) in an 8% oxygen stream. For the high gas velocity used assume that film diffusion does
not offerany resistance to transfer and reaction. Reaction temperature = 900°C.
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8. Explain the various types of reactors (tank reactors) for fluid-fluid reactions.
9. (i)State the advantages and disadvantages of trickle bed reactor. (Nov 2010)
(ii) Explain the different models to predict the design equation of a fluidized bed reactor.
10. Uniform-sized spherical particles UO3 arereduced to UO2 in a uniform environment with the
following results:
t, hr 0.180 0.347 0.453 0.567 0.733
XB 0.45 0.68 0.80 0.95 0.98
If reaction follows the SCM, find the controlling mechanim and a rate equation to represent the
reduction.
11. Explain the operation of slurry reactor. Predict the rate equation of first order reaction in a slurry
reactor. (May 2013& 2016)
12. Explain the different models to predict the design equation of a fluidized bed reactor. (May 2013)
13. What are the factors to consider a design of tank reactors? And explain various types of tank
contactors with neat diagram. (May 2015)
14. Explain in detail about the interphase behavior for the liquid phase reaction A (from gas)+B(liquid)
and write down the steps involved in gas liquid mass transfer reactions. (May 2015)
15. Explain the operation using solid catalyst in the trickle bed reactor. (Dec 2015)
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