PROBLEMS

SET O

2. Thermodynamics of Chemical Reactions

2.1 The gas phase reaction, A 2B, is maintained at 450 K and 10 atm. The reaction is
started with 1 kmol of pure A. The heat of reaction is Hr = 1390 cal/gmol-A
reacted at 290 K, and Go = 56 cal/gmol-A reacted at 298 K. Heat capacities of A
and B are 20 and 12 cal/gmol/K, and the pure component fugacity coefficients at 10
atm. are 0.97 and 0.49. Find the equilibrium composition.

2.2 Ethylene oxide is made from ethylene by the reaction

C2H4 + 0.502 C2H4O

The heat of reaction at 291 K is H = -28.611 kcal/gmol. The oxide is made at the
rate of 5000 kg/day by feeding oxygen at 423 K with 10% in excess and ethylene at
463 K. The products leave at 548 K. Calculate the hourly heat removal from the
reactor for converting 80% of the ethylene feed. Equations for the specific heats in
cal/gmol-K are,

Cp = a + bT + cT2 + dT3

a 102b 105c 109d

C2H4 0.944 3.735 -1.993 4.22
C2H4O -1.12 4.925 -2.389 3.149
O2 6.732 0.1505 -1.01791 0

2.3 Butadiene is made by the gas phase catalytic dehydrogenation of 1-butene.

C4H8 C4H6 H 2

In order to suppress side reactions and to maintain the temperature level, high
temperature steam is added to the feed. The reactor pressure is 2 atm and the feed
consists of 12 mol of steam per mol of butene. Steam remains unchanged and does
not condense during the process. The equilibrium constant as a function of
temperature is

Kp = exp(14.3417 13997/T), atm.

Find the equilibrium temperature at which 30% of the butene is converted to

butadiene.

1
2.4 The gas phase reaction, B A , is maintained at 450 K and 10 atm. The reaction
2
is started with 1 kmol of pure A. The heat of reaction is Hr = -695 cal/gmol B
reacted at 290 K, and Go = -28 cal/gmol B reacted at 298 K. Heat capacities of A
and B are 20 and 12 cal/gmol/K, and the pure component fugacity coefficients at 10
atm. are 0.97 and 0.49. Find the equilibrium composition.
3. Reaction rates and Stoichiometry
3.1 The rate law for the reaction C2H4Br2 + 3KI C2H4 + 2KBr + KI3 in an inert
solvent, which can be written as A + 3B products, has been found to be (-rA) =
kACACB, with the rate constant kA = 1.34 L mol-1 h-1 at 74.9oC.

(a) For the rate of disappearance of KI, (-rB) what is the rate constant kB?
(b) At what rate is KI being used up when the concentrations are CA = 0.022 and
CB = 0.22 mol L-1?
(c) Do these values depend on the nature of the reactor in which the reaction is
carried out? (They were obtained by means of constant-volume batch
reactor.)

3.2 The hydrolysis of a disaccharide C12 H22 O11 (A) + H2O 2C6H12O6, takes
place in a constant volume 20-L container. Results of the analysis of the
concentration of disaccharide as a function of time are:

t/s 0 5 10 15 20 30 40 50
cA /mol L-1 1.02 0.819 0.670 0.549 0.449 0.301 0.202 0.135

(a) What is the relationship between the rate of disappearance of disaccharide (A)
and the rate of appearance of monosaccharide (C6H12O6)?
(b) For each time interval, calculate the rate of disappearance of disaccharide (A),
in terms of both the total or extensive rate, (-RA), and the volumetric or
intensive rate, (-rA).
(c) Plot the intrinsic rate calculated in (b) as a function of CA. What conclusions
can you draw from this plot? fit a rate law and determine the order
r - k[A] or r = k[A]^2
3.3 The maximum allowable temperature for a reactor is 800 K. At present our operating
set point is 780 K, the 20-K margin of safety to account for fluctuating feed, sluggish
controls etc. Now, with a more sophisticated control system we would be able to
raise our set point to 792 K with the same margin of safety that we now have. By
how much can the reaction rate, hence, production rate, be raised by this change if
the reaction taking place in the reactor has an activation energy of 175 kJ / mol?

3.4 On typical summer days, field crickets nibble, jump and chirp now and then. But at
night when great numbers congregate, chirping seems to be a serious business and
tends to be in unison. In 1897, A.E. Dolbear (Am. Naturalist, 31, 970) reported that
this social chirping rate was dependent on the temperature as given by

(number of chirps in 15 s) + 8 = 1.8T, (T = temperature, oC)

Assuming that the rate of chirping is a direct measure of the metabolic rate, find the
activation energy in kJ/mol of these crickets in the temperature range of 15-30C

3.5 (a) For a certain reaction on doubling the concentration of reactant, the reaction
rate triples. Find the reaction order.
 (b) For the stoichiometry A+ B products find the reaction orders with
respect to A and B.

CA 4 1 1 CA 2 2 3
(i) CB 1 1 8 (ii) C B 125 64 64
rA 2 1 4 rA 50 32 48

3.6 In ethanol production by fermentation of corn, hydrolyzed ground corn in a water

suspension containing 50% corn by weight is mixed with sufficient enzyme to
produce ethanol by the approximate reaction.

C6H12O6 2C2H5OH + 2CO2

When the solution reaches 12 wt% ethanol, the yeast dies and the reaction stops.

(a) How many bushels of corn are required to produce 500 tons of pure ethanol
per day? (1 bushel = 25 kg, 1 ton=907 kg as opposed to 1 tonne=1000 kg)
(b) The process requires 72 hours to go to completion. What size batch-reactor
tank or tanks are required for this process? Assume density of starch = 1000 kg/m3.

3.7 The reaction

A2 + 2B 2C

occurs by the mechanism:

k1
1. A 2 . . 2A
k1'

k2
2. A + B C
'
k2
Derive an expression for the net rate of disappearance of A2, assuming

(a) the first step is reversible and slow with respect to the second reversible step,

(b) stationary state for the intermediate A.

3.8 The reaction

A2C

has the mechanism

A 2B (1)
k2
B C (2)

Determine the overall rate equation for formation of C, if

 (a) Reaction (2) is rate controlling while reaction (1) is at equilibrium. The
equilibrium constant of reaction (1) is K

(b) The stationary state hypothesis holds for the intermediate B.

4. The Batch Reactor

4.1 An irreversible aqueous reaction gave 90% conversion in a batch reactor at 40C in
10 min and required 3 min for this conversion at 50C.

(a) What is the activation energy for this reaction?

(b) At what temperature can 90% conversion be obtained at 1 min.?
(c) Find the rate coefficient assuming first order kinetics.
(d) Assuming first order kinetics, find the times for 99% conversion at 40 and
50C.
(e) Assuming first order kinetics, find the temperature to obtain 99% conversion
in a time of 1 minute.
(f) Assuming second order kinetics, find the times for 99% conversion at 40 and
50C.
(g) Assuming second order kinetics, find the temperature to obtain 99%
conversion in a time of 1 min

4.2 The first order reaction A B is conducted in a batch reactor at 500K. The rate
constant is given by k = 4.852108e-10,000/T [hr-1]. Here T is the temperature in oK.
After 15 min., due to a drop in coolant flow, the temperature suddenly rises to 518 K
and remains at this level. Determine the conversion after a total operating time of 1
hr. (i.e. 45 min. after the temperature jump).

4.3 The first order reversible reaction AB is conducted in a batch reactor. A

temperature control system is to be used such that at any instant the reaction rate is
maximum. Derive an expression for the variation of temperature with conversion.

4.4 The decomposition of nitrogen dioxide follows a second-order rate equation. Data at
different temperatures are as follows:

T, K 592 603 627 651.5 656

k2, cm3/(g mol)(s) 522 755 1700 4020 5030

Compute the energy of activation E from this information. The reaction is written

2NO2 2NO + O2

4.5 The fermentation of glucose to ethanol is conducted in a batch reactor at 298 K, with
an initial biomass charge of 2.5 g/L in the broth. The following reaction occurs

C6 H12 O 6
enzyme
2C 2 H 5OH+2CO 2
It is assumed that Michaelis-Menten kinetics holds, with production rate of alcohol
(mol/L/day) given by

2k2YEBCS CB
rA
M CS

and the biomass grows with rate (g-biomass/L/day) given by

k BCBCS
rB
( M B CS )

Here k2 and kB are rate constants, CS is substrate (glucose) concentration, CB is

biomass concentration, YEB is the yield of enzyme per unit amount of biomass (g-
enzyme/g-biomass), and M, MB are the MM constants. The following values of
various constants are specified

M = 1.1 mol/lit
MB = 1.1 mol/lit
k2YEB = 0.025 mole/g-biomass/day
kB = 0.2 day-1
YBS = 0.06 g-biomass/g-glucose (amount of biomass produced per unit mass of
glucose consumed)
Solution density = 1 kg/lit

(a) Using the ODEs derived in class

dCS kY C C 1 k B C B CS
2 EB B S , CS (t 0) CSo
dt ( M CS ) YBS MWS ( M B CS )
dCB k C C
B B S , CB (t 0) CBo
dt ( M B CS )

derive the following relation between the amount of glucose consumed and the
amount of biomass grown, for the case when M = MB (as in the data).

k Y 1
CSo CS (t ) 2 EB [CB (t ) CBo ]
kB YBS MWS

Hint: Take the ratio of the two ODEs, and derive an ODE relating CS and CB.

(b) Using the result of part (a) show that the minimum initial glucose molar
concentration CSo required to produce a final ethanol molar concentration CAf is
given by

kB C Af
CSo 1
k2YEBYBS MWS 2

Hint: When the initial glucose concentration is the minimum required, there will
be no glucose remaining when CA(t) = CAf.

(c) Using the MATLAB code provided solve the material balance equations for
glucose and the biomass, and plot the time required to reach 5%wt alcohol versus
 initial glucose concentration in wt%, for initial glucose content in the range of 10-
45%. Use the result of (b) to choose the minimum value of CSo for the plot.

(d) How would you expect the minimum required initial glucose concentration to
change if MB < M or if MB > M ?

(e) In the above calculations in (c) it has been assumed that the biomass grows while
consuming the substrate, but no provision is made for biomass death or
deactivation. In reality living cells do die, and this must be considered in the
material balance equations solved in the MATLAB code. It is common to assume
that the kinetics of cell death is first order, so that the rate of biomass death, (-rD),
(g/L/day) is given by

rD kd CB

(i) Derive the differential equations necessary to solve for the amount of
glucose, biomass and alcohol in the system as a function of time. (Hint: to
determine the amount of alcohol it is necessary to also keep track of the
mass of dead cells in the system, so a third ODE is needed).

(ii) Modify the MATLAB code to account for cell death, and repeat the
calculations in (c), assuming kd = 0.05 day-1, with the other constants
unchanged from (c). This time choose the minimum value of CSo by trial and
error with the computer code, as the expression derived above in (b) is only
valid in the absence of cell death.

5. Isothermal Flow Reactors

5.1 A first order reaction
A B

is carried out isothermally in a series of two CSTRs. The rate constant has the
Arrhenius form
k 4.852 x108 e 10,000/T hr -1

The first reactor is operated at a temperature of 500 K, while the second reactor is operated
at 518 K. Given that the total residence time in the 2-reactor system is 1 hr, determine the
maximum overall conversion that can be achieved in the system.(Hint : set 2=tot -1, where
tot is the total residence time. Now determine the value of 1 that minimises the final
concentration of the reactant A). Tute Sheet 4

5.2 The consecutive irreversible reactions:

A
k1
B
k2
C

are known to follow first order kinetics in a batch reaction:

dC A
kl C A
dt
 dCB
k l C A k 2C B
dt

dCC
k 2C B
dt

It is decided to run the system isothermally with pure A feed at a temperature for
which
k1 1.00 min -1
k2 2.25 min -1

but there is some uncertainty as to whether a CSTR or a PFTR can produce a greater
yield of the desired intermediate B.

a) What is the maximum yield of B that can be obtained from the PFTR? What
residence time is required?
b) What is the maximum yield of B that can be obtained from the CSTR? What
residence time is required?
c) What can you say about the relative volumes required for the CSTR and
PFTR for a given production rate of product? Assume that each reactor is
operated to achieve its optimum yield.

5.3 The system of consecutive first order liquid phase reactions ABC occurs
isothermally in a CSTR. During start up the CSTR is fed with a stream of pure A at
a concentration of 1 mole/lit, and there is initially only a clear inert liquid with no A
or B in the reactor. A constant inlet flow rate of 1 lit/min is maintained and the liquid
volume is also kept constant at 10 lit. If each reaction has rate constant 0.1 min-1

(a) Derive an equation for the outlet concentration of B as a function of time.

(b) How long does it take for the concentration of B to reach 80% of its steady state
value?

5.4 A total of 2500 gal/h of metaxylene is being isomerized to a mixture of orthoxylene,

metaxylene, and paraxylene in a plug flow tubular reactor containing 1000 ft3 of
catalyst. The reaction is being carried out at 750F and 300 psig. Under these
conditions 37% of the metaxylene fed to the reactor is isomerized. At a flow rate of
1667 gal/h, 50% of the metaxylene is isomerized at the same temperature and
pressure. Energy changes are negligible.
It is now proposed that a second plant be built to process 5500 gal/h of metaxylene at
the same temperature and pressure as above. What size of reactor (i.e. what volume
of catalyst) is required if conversion in the new plant is to be 46% instead of 37%?
Justify any assumptions made for the scale-up calculation.

5.5 The homogeneous gas-phase reaction

3A 2 B 2 2BA 3

has zero order kinetics. In an isothermal constant pressure batch reactor a

stoichiometric mixture of the reactants at 2 atm absolute pressure and 93.33C gave
 70 percent conversion in 1.5hrs. It is now desired to design an isothermal plug flow
reactor based on this data. What is your recommendation for the plug flow volume,
if the conversion in the tubular reactor is to be 98 percent at a production rate of BA3
of 0.1 moles/hr? If necessary for your calculations take BA3 to be ammonia.

5.6 a) The reaction sequence

A
k1
B
k2
C

in which each step has first order kinetics occurs in a well mixed CSTR.
Assuming k1=k2=2 hr-1 determine the optimum residence time for maximum
conversion of A to B.

b) If instead the residence time is fixed at = 1 hr determine the optimum isothermal

reaction temperature for the CSTR. The rate constants follow the Arrhenius forms

k1 1015 exp( 12,000 / T ) hr -1

k2 1016 exp( 15,000 / T ) hr -1

5.7 A rapid liquid phase reaction

AB C

is to be conducted in the flow reactor shown below to minimize thermal effects.

QB, CBO B 1

QA, CAO A 2

Pure A is fed into the inner pipe at concentration CAO and volumetric flow rate QA,
and a solution containing reactant B at concentration CBO is fed at volumetric flow
rate QB into the annular region surrounding the inner pipe. The inner pipe wall is
semipermeable and permits B to enter into the flowing A stream with a molar flux
(per unit area)

j = K (CBl CB2)

where CB1 is the local concentration of B at any position in the annulus and CB2 the
concentration of B in the inner pipe. No transfer of A occurs through the pipe wall.
It may be assumed that in the inner pipe A is far in excess and has uniform
concentration CAO, and that the reaction rate is then essentially first order in the
concentration of B, i.e.

rB = - kCB

Given that the inner pipe wall is thin and has a perimeter P and length L.

a) Determine an expression for the production rate of C assuming isothermal

operation.
 b) Write a differential energy balance that can be used to obtain the temperature
profiles in the pipe and annulus under nonisothermal operation. Explain any
symbols and notation introduced.

5.8 The first order reversible reaction (SEE E5.4)

AB

is conducted in a completely micromixed steady state CSTR. The feed comprises

pure A at concentration CAo:
(a) Write down the relation between the concentrations of B and A, CB and CA
respectively, at the reactor outlet. (3
marks)

(b) Starting from the balance equation for A, and combining with the result of
(a), show that the outlet concentration of A is given by

( K C k )C Ao
CA
[ K C k (1 K C )]
Here k is the forward rate constant, KC is the equilibrium constant, is the
mean residence time, and CAo is the concentration of A in the feed stream.
(15 marks)
(c) Given that the mean residence time is 1 min, and the forward and reverse
rate constants have value k = k= 1 min-1, determine the outlet conversion of
A. (5 marks)

(d) Based on the result of (b) and the values of the constants k = k= 1 min-1,
what is the maximum possible conversion of A, over all possible residence
times?
(7 marks)

6. Non-ideal Reactor Behaviour

6.1 A half order liquid phase reaction A 2B, occurs in a CSTR. Find the limits for the
conversion if the feed concentration is 1 mole/lit, residence time is 1 hr, and the rate
constant is 2 mole1/2/lit1/2-hr.

6.2 The response to step input of tracer to a certain reactor is given in the figure below

C
(mol/lit.)

1.0
 1.0 Time (hr.)

(a) What is the residence time distribution for these conditions?

(b) For a first order isothermal reaction with rate constant 1 hr.1 calculate the expected
conversion from the reactor.
(c) If the above residence time distribution was not given, but only the mean residence
time was known, estimate the bounds to reactor conversion for the above first order
reaction.
(d) Estimate the expected segregated flow outlet conversion for a second order reaction
with feed concentration 1 mol./lit. and rate constant of 1 lit/.hr-mol.

6.3 The liquid phase half-order reaction A2B is conducted isothermally in a laminar
flow reactor. The inlet concentration of A is 1 gmole/lit, the reaction rate constant is
known to have the value 1 gmole1/2-lit-1/2-min-1 , and the mean residence time is 1
min. Calculate the outlet conversion of A. State all assumptions.

6.4 For turbulent flow in pipes the one-seventh-power law model is often used to
describe the velocity profile, i.e.
u u max (1 r / R ) 1/ 7
a) Derive the residence time distribution for turbulent flow in a tubular reactor.
b) Calculate the conversion if an elementary isomerisation occurs. The specific
reaction rate is k = 0.1 sec-1. The centerline velocity is 1 m/sec, and the reactor
length is 10m. The tube diameter is 1 met.

6.5 When a certain nonideal reactor, in which a first order reaction occurs, is modelled as
comprising of a series of three CSTRs of equal volume a conversion of 75 per cent
is predicted. What conversion would you predict if instead it was modelled as an
axially dispersed tubular reactor?

6.6 The volume of a blood vessel in the shoulder region is 7.85 x 10-6 m3. Tracer
experiments with a pulse input give the following concentration versus time data.
Compute the volumetric flow rate of the blood stream through the vessel. What is
the total amount of the tracer injected? Plot the RTD-curve for this blood vessel
qualitatively. Data:

t(s) C(mg/cm3) t(s) C(mg/cm3)

0 0 3.0 3.00
0.5 1.75 3.5 1.75
1.0 3.00 4.0 0.50
1.5 3.75 4.5 0.25
2.0 4.00 5.0 0.001
2.5 3.75

6.7 Derive the E-curve for a reactor which may be viewed as a combination of a CSTR
sandwiched between 2 PFRs, all the reactors being of equal volume. What is the
 conversion for a second order reaction in the two limits of complete segregation and
complete micromixing, respectively, given that k2CAO = 1? (Use numerical integration
with at least 10 points wherever analytical solution is not possible).

6.8 Find the E-curve (RTD) for channel flow in which the velocity profile is given by:
z
Vy ( z) Vmax (1 )
H
Z=0
Vy(z)
Z=H
y
What is the expression for the cumulative distribution F-curve, given by F(t)
t
= E(t')dt' ? Show that E(t)dt 1 for the above channel reactor.
0 o

Derive the equation for conversion for completely segregated flow for the case of
second order kinetics in the above reactor.

6.9 Develop the expression for the E-curve for a reactor for which the mixing pattern is
shown below:

V1
fF CSTR

V2 PFR

7. Non-Isothermal Chemical Reactors

7.1 A batch reactor is to be designed for the second order reaction
A+BC+D

under the following conditions.

Initial charge: A and B each at a concentration of 25 gmole/lit.

Reactor volume: 5,000 lit.
Heat capacity of reaction mixture: 0.75 kcal/kg.-C
Density of reaction mixture: 0.8 kg/lit.
Initial temperature: 100C
Heat of reaction: -3 kcal/gmol
It is essential to keep the temperature below the danger level of 250C and a
computer study is to be made of the cooling jacket requirements. A young engineer
argues that such a study is a waste of time and effort. Is he correct? Explain.

7.2 A gas phase reaction

 2A B

is conducted adiabatically in a constant volume batch reactor. Starting with the

statement of the first law of thermodynamics

dU = dQ + dW

where dU is the differential change in internal energy arising from the heat supplied,
dQ, and work done, dW, on the system.

a) show that the energy balance satisfies

2 dT rA PrA

i1 C i C vi dt H B [VB-2VA]
2 2
and identify the assumptions involved.

b) Further show that if A and B are ideal gases the above result reduces to

2 dT 1 r
i C i C vi rA H B A RT
1 dt 2 2

where,

C1 = CA, C2 = CB, Cvl CvA, Cv2 = CvB

T = Temperature
rA = rate of production of A
HB = heat of reaction per mole of B produced
VA,VB = pure component molar volumes of A and B
Cvi = specific heat at constant volume for pure component I
P = pressure

7.3 A first order liquid phase reaction is conducted adiabatically in a CSTR. The feed
temperature is 300K, the mean residence time is 1 hr, and the reactant concentration
in the feed is 2 moles/lit. It is experimentally observed that the system has two stable
operating temperatures of 302K and 379.2K for the above feed temperature.
Determine the temperature and conversion for the third, unstable steady state.

Data: Heat of reaction = -40,000 cal/gmole

Density of liquid = 1 gm/cm3
Specific heat = 1 cal/gm-C

7.4 Consider an adiabatic reaction A B in a tubular reactor and the data.

FAO = 20 kmol/hr To = 300 K

Cp = 0.5 kcal/kg.C xo = 0; x = 0.9

(-H) = 10,000 kcal/kmol ko = 3.27 106 kmol/[Link]

E = 9000 kcal/kmol m = 1000 kg/hr

a) Calculate the reactor volume and exit temperature when the reaction is of zeroth order.

b) Compare with the volume required when the reaction is carried out isothermally:

(i) at T = To
(ii) at T = (To + Te)/2

where Te is the exit temperature of the adiabatic reactor.

7.5 Consider a cracking reaction with rate

r 1014 e 24 ,000/ T C A gm / m 3 sec

where T is in K, and CA is in gm/m3. Suppose the reaction is conducted in an

adiabatic plug flow tubular reactor having a residence time of 0.3 sec. The crackable
component and its products have a heat capacity of 0.4 cal/gm-K, and the inerts
have a heat capacity of 0.5 cal/gm-K. The entering concentration of crackable
component is 132 gm/m3 and the concentration of inerts is 270 gm/m3. T = 525C at
the inlet; H R 203 cal / gm . Assuming constant properties calculate the outlet
concentration of A.

7.6 A perfectly mixed reactor is to be used for the hydrogenation of olefine, and will be
operated isothermally. The reactor is 10m3 in size, and the feed rate is 0.2 m3/s with
a reactant concentration CAo = 13 kmol/m3. For the conditions in the reactor, the rate
expression is
CA
rA kmol/m3 .sec
(1 C A
2

It is suspected that this nonlinear rate form, that has a maximum value, may cause
certain regions of unstable operation with multiple steady states.

a) From the reactor mass balance determine if this is the case, by plotting (-rA)
(C A - C A0 )
versus CA and versus CA on the same graph.

b) By considering (-rA) as the loss term and (CA CA0) as the generation term,
deduce the stability character of the steady states.
c) To what concentrations should the feed be changed to avoid this problem?
(Tutorial Sheet 7)

7.7 Ascertain whether the following exothermic reaction:

k1
A A P P k1 60 [Link] -1 k2 0.2 [Link] -1

k2

(k1 and k2 at 80C) could be carried out in the reactor arrangement shown below:
 Calculate the volume and heat removed from the CSTR and the PFTR. Do the
magnitudes of the heat being removed appear reasonable? Why or why not?

Data
CPA = 45 [Link]-1.K-1
CPP = 40 [Link]-1.K-1
HR = -7,500 [Link]-1 (per mole P produced)
CAo = 1.5 mole.L-1
FAo = 100 [Link]-1
Davis 9.8

7.8 A reaction is carried out in an adiabatic CSTR with a volume of 10,000 [Link] feed
solution with reactant A, at a concentration Davis 9.10

8. Heterogeneous Catalytic Reactions

8.1 Over a certain catalyst, the reaction AB C2 AC BC is known to occur with the
following mechanism:

AB X AB X
X AB X C 2 AC X BC X
AC X AC X
BC X BC X

Assuming that the surface reaction is rate controlling, determine an overall rate
expression.

8.2 A catalyst pellet has the following bimodal pore size distribution.

dv/dr
 cm3/gm- 0.01

0.004

20 50 80 200 300 400

r()

The crystal density of the nonporous support is 2.9 gm/cm3.

(a) What is the fractional porosity of the pellet?

(b) What is the specific surface area (i.e. surface area per unit mass)?
(c) Assuming Knudsen diffusion control estimate the effective diffusivity of
oxygen in the pellet. Take the tortuosity as 3.0 and T = 300 K.

8.3 A first order heterogeneous irreversible reaction is taking place within a spherical
catalyst pellet. The reactant concentration half way between the surface and centre
of the pellet (i.e. r = R/2) is equal to one-tenth the concentration at the external
surface, which is 0.001 gmole/lit. The pellet diameter is 2 x 10-3cm and the diffusion
coefficient is 0.1cm2/s.

(a) What is the concentration of reactant at a distance of 3 x 10-4cm from the external
pellet surface?
(b) To what diameter should the pellet be reduced if the effectiveness factor is to be
0.8?

8.4 A first order reaction A B is taking place in spheres of radius in. A is a gas
with partial pressure of about 1 atm and at room temperature outside the pellet. The
observed reaction rate is about 10-2 mole/sec per cm3 of packed reactor volume.
Would you consider diffusion to be an important limiting factor? De for a gas is
typically 0.1 to 1 cm2/sec.

8.5 A 2% hydrazine, 98% helium mixture is to be passed over a packed bed of spherical
catalyst particles 0.4 cm diameter at a gas phase velocity of 15 m/sec and temperature
of 750 K. Under these conditions the hydrazine decomposes at a rate controlled by
mass transfer. The kinematic viscosity of helium at 750 K is 4.5 x 10-4 m2/sec, and
the diffusion coefficient is 3.5 x 10-4 m2/sec. If the packed bed length is 0.05 m and
the bed voidage is 0.3 determine the conversion of hydrazine, assuming isothermal
operation. The following correlation is given
0.765 0.365
bJ D
Re0.82 Re0.386
Sh
where J D 1
Sc 3 Re
d pU
Re

dp = particle diameter
U = gas-phase velocity
= kinematic viscosity
 Sh = Sherwood number
Sc = Schmidt number

8.6 The reaction A B occurs catalytically with the following mechanism

A(g) + X A.X

A.X B.X

B.X B(g) + X

(a) derive an overall rate expression assuming that surface reaction controls.

(b) The above reaction is conducted isothermally in a radial flow reactor in which pure A
is fed into an inner pipe and flows radially outward over a packed bed of catalyst
particles, as shown below.

CATALYST
BED
PLAN

10m

CATALYST

PRODUCT
PRODUCT

FEED

It is known that the catalyst particles are small enough to provide an overall
effectiveness factor of unity. Assuming that the feed is uniformly distributed over
the length of the feed pipe determine the feed rate of A (in kg/hr) necessary to
achieve 80% conversion, given the following data:

Height of catalyst bed = 10 m

Inner radius of catalyst bed = 0.10 m

Outer radius of catalyst bed = 1 m

Reactor temperature = 600 K

Reactor pressure = 1 atm

Density of catalyst particles = 1,500 kg/m3

Surface area of catalyst = 100 m2/gm

 Bed porosity = 0.35

Surface reaction rate constant = 0.05 min-1

m3
Adsorption equilibrium constant for A = 0.05
mole
m3
Adsorption equilibrium constant for B = 0.025
mole

Maximum site concentration on catalyst surface = 2x10-6 moles/m2

Molecular weight of A = 100

(c) Would the result of (b) change if instead the feed flows radially inward.

(d) What is the advantage of such a reactor over a conventional axial flow fixed bed
reactor?

8.7 (a) In the synthesis of HNO3 from NH3 and air the 10% NH3-air mixture is passed over a
Pt-wire gauze (80 mesh) catalyst of 30 layers depth. Assuming the reaction to be
totally controlled by gas-phase mass transfer, compute the NH3 conversion. Use the
correlation
2
k m Sc 3
h 2
jD Pr 3 jH 106
. Re -0.7
u uC p
d p u
where Re

The contact time for n layers is

dp n

u

where = 0.5 is the void fraction, u is the velocity and dp is the wire diameter. Assume
isothermal operation at Re = 30 and 7 atm pressure. The reaction is
2 NH 3 5 2 02 2 NO 3H 2 O. Take the Schmidt number Sc as unity and perform the
computations for (i) plug flow and (ii) CSTR behaviour.

(b) For the bulk gas temperature of 800C calculate the surface temperature at the point of 50
per cent conversion. Assume Pr = Sc and Cp = 8 cal/gmole C, H = -216,000 cal/gmole
NH3.

9. Noncatalytic Gas-Solid Reactions

9.1 In the fabrication of solid state devices the growth of silicon dioxide on the silicon
wafer by oxidation is an important step. This is accomplished by exposing the flat
silicon wafer to oxygen for a fixed amount of time so that a suitably thick layer of
 oxide is formed. It is believed that the external mass transfer is rapid, and that the
process rate is governed by product layer diffusion of molecular oxygen and
interfacial reaction at the Si SiO 2 interface. Assume that the interfacial reaction is
first order in oxygen and the rate of consumption of oxygen per unit area at this
interface is ksC where, C is the local concentration of oxygen. It is given that the
product layer diffusion coefficient of oxygen is D, the surface concentration of
oxygen at the SiO2 oxygen interface is Co, and the molar density of silicon is .
Derive an expression for the thickness of the SiO2 layer as a function of time t.
Express your answer in terms of D, Co, t, , ks only. Assume that the thickness of the
product layer formed is the same as that of the silicon reacted.

9.2 Solid reactant particles are suspended in a bed type of arrangement using mild
fluidization. The particles are spherical and to begin with are of the same size Ro.
These are non-porous and the ash that forms flakes off and is carried away by the gas
stream. When the particles become 1/10th their original size they are removed from
the bed as fines in the gas stream. At this point, the bed has to be charged again with
fresh particles. The reaction on the particle surface (A(g) + B(s) Products) may be
considered instantaneous and rate controlled by the solid-gas mass transfer
coefficient, kSG. The operating conditions and properties are given below. Calculate
the batch time for this arrangement. Assume the gas concentration of A to be
uniform throughout the bed and constant at CAb.

Data:

k SG R
Sh 10, D A 1x10 3 cm2 / s,
DA
R o 2.5 mm, C Bo 0.04 mol/cm 3 , C Ab 4x10 5 mol/cm 3 .

What is the amount of gas adsorbed per particle?

9.3 Consider the reaction between solid (B) and gas (A): the solid is in the form of a
rectangular slab of thickness D; only one face perpendicular to the thickness
coordinate is exposed to the gas. If the reaction is instantaneous and gas phase
resistance is neglected, find the expression for solid conversion versus time. If D =
0.5cm, De=1 x 10-8 cm2/s, a (area of exposure) = 5cm2 find the time taken for the
whole slab to react.

9.4 Two small samples of solids are introduced into a constant environment oven and
kept there for one hour. Under these conditions the 4mm particles are 58% converted
and 2mm particles are 87.5% converted.

(a) Find the rate controlling mechanism for the conversion of solids.
(b) Find the time needed to completely convert 1mm particles in this
environment.

9.5 The noncatalytic gas-solid reaction

aA ( g) bB( s) products
 is conducted isothermally in a stirred bed reactor, in which gas A and spherical
particles of solid B, of radius R0, are fed continuously. The stirred bed of B may be
assumed well mixed, while the gas phase may be considered micromixed. The mean
residence time of the solid particles is , and it is known that under existing
conditions the reaction is controlled by external gas phase mass transfer. Given that
the external mass transfer coefficient is km, the molecular weight of B is MB and the
density of B is B,

(a) derive an expression for the mean exit conversion of solid B in terms of a, b,
km, Ro, MB, B, and CA, where CA is the gas phase concentration of A in the
reactor.
(b) Using the material balance for A derive a relationship that can be used to
calculate CA. You are given that A is fed at a volumetric flow rate of q and
inlet concentration C oA , and that the mass feed rate of B is m
.

9.6 The gas-solid reaction

A ( s) B( g) C( s) ( g)

is conducted isothermally in a vertical moving bed reactor. Solid spherical particles

of A of radius rp are fed at the top of the reactor at a constant molar flow rate MA, and
gas is fed at the bottom at a volumetric flow rate q with a concentration CBO of
reactant B. It is known that gas-solid mass transfer controls the progress of reaction,
and the mass-transfer coefficient is km. If the reactor radius is R, the bed voidage is
b and the reactor length is L, show that the outlet conversion of solid A is given by
qC BO
X A,out (1 e SL )
MA
3 2 k m (1 b )
where S =
rp q