1

CHEMICAL REACTION ENGINEERING

 KINETICS OF HOMOGENEOUS REACTIONS  MOLECULARITY AND ORDER OF REACTION

Rate of reaction - the number of units of mass of some participating The molecularity of an elementary reaction is the number of
reactants which is transformed into a product per molecules involved in the reaction, and this has been found to have
unit time and per unit volume. the values of one, two, or occasionally three.

d Ni
ri = 1
V dt
Suppose a single-phase reaction: aA + bB → rR

Rate of disapperance of A: - r A =
1 dNA =
V dt
Tetramolecular reactions are unlikely because the odds of
moles A disappearing mol having four molecules colliding at exactly the same place at the
,
( volume of fluid)( time) m3 − s same time are exceedingly very unlikely.

Rate of disapperance of B: - r B =
1 dNB = Consider a single reaction with stoichiometric equation:
V dt - rA = kCAaCBb a+b=n
moles B disappearing mol We call the powers to which the concentrations are raised the
, order of the reaction. Thus, the reaction is ath order with respect to
( volume of fluid)( time) m3 − s A, bth order with respect to B and nth order overall.

Rate of formation of R:
1 dNR =
rR = Note: If the molecularity and the overall order of reaction are the
V dt same, the reaction is elementary.
moles R forming mol
, 3  RATE CONSTANT, k
( volume of fluid)( time) m − s
Dimension of k for the nth-order reaction:
In addition, the rates of reaction of all materials are related by ( concentration )1 −n
time
−r A −r B r R
= =
a b r REACTION ORDER RATE CONSTANT EXAMPLE
Zeroth order (n = 0) concentration mol
 ELEMENTARY AND NON-ELEMENTARY REACTIONS time L− s
A. Elementary Reactions
- type of reactions which follows the law of mass action. First Order (n = 1) 1 1
time s
Law of mass action
- states that the rate of chemical reaction is at each instant Second Order (n = 2) ( concentration )−1 L
proportional to the concentration of the reactant with each
raised to a power equal to their coefficient or the actual number time mol − s
of molecules participating in the reaction.
Formulated over the period 1864–79 by the Norwegian Third Order (n = 3) ( concentration )−2
2
scientists Cato M. Guldberg and Peter Waage. time L
2
Consider a single reaction with stoichiometric equation:
mol − s
aA + bB → rR
 TEMPERATURE DEPENDENCE OF RATE EQUATION
a b a b a b
Rate expressions: - rA = kC CA B ; - rB = kC C
A B ; rR = kC C
A B
THEORY EXPRESSION AT TWO DIFFERENT T
B. Non-Elementary Reactions Arrhenius

( )
E
m=0 k=A −
RT
k2 E 1 1
- type of reactions which doesn’t follows the law of mass action. In e ln = −
other words, there’s no correspondence between the rate law k1 R T1 T 2
and stoichiometry.
Collision

( √ )
1
1 k= k2 T1 E
Consider a single reaction with stoichiometric equation: m= T 2A ln =
2 k1 T2 R

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aA + bB → rR

( 1 1
)
E
−
0.5 e RT −
k1 A B T1 T 2
Rate expression for formation of R: rR=
k 2 +(R /B) Transition State

( )
k = TA k2 T 1 E
m=1 E ln =
Note: The proposed reaction mechanism of a certain rate
e
−
RT k1 T 2 R
expression

here
is determined by trial and error which will not be included
( 1 1
−
T1 T 2 )
Non-elementary reactions are explained by assuming that what
we observe as a single reaction is in reality the overall effect of a k 2 r 2 t1
At the same concentration, = =
sequence of elementary reactions. The reason for observing only a k 1 r 1 t2
single reaction rather than two or more elementary reactions is
that the amount of intermediates formed is negligibly small and, where k = reaction rate constant r = reaction rate
therefore, escapes detection. E = activation energy, cal/gmol t = time
A = pre-exponential factor T = temperature, K
R = 1.987 cal/mol-K or 8.314 J/mol-K

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 INTERPRETATION OF BATCH REACTOR DATA HALF-LIFE

- time needed for the concentration of reactants to drop to one-half
 CONSTANT-VOLUME BATCH REACTOR
the original value
When we mention the constant-volume batch reactor we are
really referring to the volume of reaction mixture, and not the
volume of reactor. Thus, this term actually means a constant-density A. For nth order reaction: aA → R where a ≠ 1
reaction system. Most liquid-phase reactions as well as all gas-phase
reactions occurring in a constant-volume bomb fall in this class ( 2n − 1 ) − 1
General equation: t 1/ 2= n −1
k ( n− 1 ) C AO
ri =
1
V dt
=
N
d Ni d i
V ( ) =
d Ci
dt B. For 1st order reaction, where a = 1: t 1/ 2=
ln 2
dt k

or for ideal gases, where C =

P
: ri =
1 d Pi C. For the reactants which are present in their stoichiometric ratios:
RT RT dt aA + bB + cC + … → rR

For isothermal gas reaction: aA + bB → rR + sS ( 2n −1 ) −1

General equation: t 1/ 2= ' n −1
k ( n − 1 ) C AO
a
Reactant, A: P A =¿ P AO − ( P − P ¿)
Δn T
( )( )
b c
b c
where k’ = k … and n = a + b + c +
r a a
Product, R: P R=P RO +¿ ( P − P ¿)
Δn T  INTEGRATED RATE LAWS FOR COMPLEX CONST-VOL RXNS
A. Side/Simultaneous/Competing Reaction: A → R
where Δn = (r + s) – (a – b)
A→ S
− ( k 1+ k 2) t
FRACTIONAL CONVERSION, X i C A = C AO e
- fraction of reactant converted out of reactant fed
Relationships between A, R and S:
For any reactant, say A :
C A − C AO k 1 +k 2 C A − C AO k 1 +k 2
mol reacted N AO − N A NA ¿ ¿
XA = = =1– C R −C RO k1 C S −C SO 2
mol fed N AO N AO
For constant-volume processes:
C R −C RO k 1
¿
C S −C SO k 2
CA
XA =1– → C A = C AO ( 1 − X A )
C AO
B. Consecutive/Series Reaction: A → R → S

 INTEGRATED RATE LAWS FOR CONST-VOL IRREVERSIBLE RXNS

C A = C AO e− k t 1

th
A. For n order reaction: aA →R where a ≠ 1
k 1 C AO − k t − k t
General equation: CA
1 −n
−C AO
1 −n
= ( n −1 ) kt CR = ( e −e ) 1 2

k 2 −k 1

B. For 1st order reaction, where a = 1: A → R C AO

CS = ( k − k +k e −k t − k 2 e− k t )
k 2 −k 1 2 1 1
2 1

C AO
ln = kt
CA Other important equations:

( )
k2
ln ( k 2 /k 1) k1 k1
For the reactants which are present in their stoichiometric ratios: tC = C R , max = C AO k 2 −k 1
C R , eq =
R,max
k 2 −k 1 k2 k2
A. Second order : A + B → R
− k 1t
C AO e
1 C B C AO
ln = kt
( C BO − C AO ) C A C BO

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B. Third Order k1
i. 2A + B → R
C. Reversible Reaction: A→
←
R
( 2C BO −C AO ) ( C AO − C A ) C A C BO k2
+ ln =
C AO C A C B C AO
1 1 ( k 1+ k 2 ) C AO − k 2 C AO
2 t= ln
( C −C AO ) kt
2 BO k 1 +k 2 ( k 1 +k 2 ) C A −k 2 C AO

ii. A + B + C → R 1 C AO − C A ,eq
t= ln
k 1 +k 2 C A −C A , eq
ln ( C AO /C A ) ln ( C BO /C B )
+ +
( C AO −C BO ) ( C AO −C CO ) ( C BO − C AO ) ( C BO −C CO ) k 1 C R , eq
ln ( C CO /CC ) kc = =
k 2 C A ,eq
= kt
( CCO −C AO )( CCO − C BO )
D. Autocatalytic Reaction: A+R→R+R

C AO ( C O − C A ) C AO C R
ln = ln =C O kt =
C A ( C O −C AO ) C A C RO
( C AO +C RO ) kt

where C O = C A + C R + C AO + C RO = constant

 INTEGRATED RATE LAWS FOR VARIABLE VOLUME REACTIONS  IDEAL REACTORS FOR A SINGLE REACTION

VX =1 −V X =0
THREE TYPES OF IDEAL REACTORS
εA= V = V O ( 1+ε A X A ) CA =
A A

VX A. Batch reactor (BR)

=0
A
The reactants are initially charged into
C AO ( 1 − X A ) a container, are well mixed, and are left to
react for a certain period. The resultant
1+ ε A X A mixture is then discharged. This is an
unsteady-state operation where
C AO composition changes with time; however,
A. Zero Order ln ( 1+ε A X A )=kt at any instant the composition throughout
εA
the reactor is uniform.

B. 1st Order − ln ( 1 − X A ) = kt B. Plug flow reactor (PFR)

An ideal steady-state flow reactor
X A ( 1+ ε A ) characterized by the fact that the flow of
C. 2nd Order + ε A ln ( 1 − X A ) =¿ k fluid through the reactor is orderly with
( 1− X A ) no element of fluid overtaking or mixing
with any other element ahead or behind.
C AOt
Actually, there may be lateral mixing of fluid in a plug flow
reactor; however, there must be no mixing or diffusion along the
( 1+ε A ) ( 2 X A − X A 2 ) 2 X A ( ε A2 +ε A )
2
flow path. The necessary and sufficient condition for plug flow is
rd
D. 3 Order - - for the residence time in the reactor to be the same for all
2 ( 1− x A )2 1−xA elements of fluid.
2
ε A ln ( 1− x A )=¿ kC AO2t C. Continuously stirred tank reactor (CSTRS)
It is a reactor in which the contents
 SYMBOLS AND RELATIONSHIP BETWEEN CA AND XA are well stirred and uniform throughout.
There are two related measures of the extent of reaction, the Thus, the exit stream from this reactor
concentration CA and the conversion XA. However, the relationship has the same composition as the fluid
between CA and XA is often not obvious but depends on a number within the reactor. Also called the mixed
of factors. This leads to special cases, as follows. flow reactor (MFR) or backmix reactor
(BMR).
Special Case 1: Constant Density Batch and Flow Systems

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This includes most liquid reactions and also those gas reactions  IDEAL BATCH REACTOR
run at constant temperature and density. Here CA and XA are
XA
related as follows: d XA
General Equation: t = N AO ∫
CA VX −V X 0 ( −r A ) V
=1 =0
XA = 1 - εA= A A
=0
C AO VX =0
XA
dX
∫ −r A
A
If density is constant (ε A = 0): t = C AO or t =
Consider a single reaction with stoichiometric equation: 0 A

aA + bB → rR, with inerts CA

dCA
To relate the changes in B and R to A we have:
−∫
C AO
−r A
C AO −C A C BO − C B C R −C RO C AO X A C BO X B If density is not constant (ε A ≠ 0): t = C AO
= = or =
a b r a b XA
dX
∫ ( −r )( 1+Aε X )
Special Case 2: Batch and Flow Systems of Gases of Changing Density 0 A A A
but with T and P Constant
Here the density changes because of the change in number of Note: Integrated equations for both constant and varying volume for
moles during reaction. In addition, we require that the volume of a batch reactors are already shown previously.
fluid element changes linearly with conversion: V = V O ( 1+ε A X A )
SPACE-TIME AND SPACE-VELOCITY
Just as the reaction time t is the natural performance measure for
C AO −C A V X =1 −V X =0 a batch reactor, so are the space-time and space-velocity the proper
XA = εA = A A
≠0
C AO + ε A C A V X =0 A
performance measures of flow reactors.

Space-time, τ - time required to process one reactor volume of feed

Consider a single reaction with stoichiometric equation:
measured at specified conditions
aA + bB → rR, with inerts
Example: A space-time of 2 min means that every 2 min one
To follow changes in the other components we have: reactor volume of feed at specified conditions is being
treated by the reactor.
Between reactants: For products and inerts:

ε A X A =ε B X B Space-velocity, s - number of reactor volumes of feed at specified

CR conditions which can be treated in unit time
=
C AO C BO C AO Example: A space-velocity of 5 hr -1 means that five reactor
= volumes of feed at specified conditions are being fed
a ε A b εB into the reactor per hour.
C RO
( r /a ) X A +
C AO X A C BO X B C AO
=
a b 1+ε A X A

CA 1− XA CI 1
= =
C AO 1+ ε A X A C IO 1+ ε A X A

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RELATIONSHIP BETWEEN SPACE TIME (τ) AND SPACE-VELOCITY (s): HOLDING TIME FOR FLOW REACTORS
Holding time, ṫ - mean residence time of flowing material in the
1 C AO V V reactor
τ= = =
s F AO vO V
A. For constant density systems: τ=ṫ=
vO
where: C AO = molar concentration of A entering
F AO = molar feed rate of component A B. For fluids of changing density, e.g., nonisothermal gas reactions or
V = reactor volume gas reactions with changing number of moles, a distinction should
be made between space-time and holding time and the correct
v O = volumetric feed rate measure should be used in each situation.

 STEADY-STATE MIXED FLOW REACTOR XA

d XA
ṫ = C AO ∫
General Equation: τ =
C AO −C A C AO X A
=
0 ( −r A )( 1+ ε A X A )
−rA −r A For changing density systems τ ≠ ṫ, in which case it becomes
difficult to find how these terms are related.
n
For nth order reaction: nA → R with reaction rate: − r A = kC A
 DESIGN FOR SINGLE REACTIONS

A. If the density is constant, ε A = 0 Factors which are considered in designing a reactor system:
1. Reaction type
2. Planned scale of production
C AO −C A 3. Cost of equipment and operations
General Equation: kτ = n 4. Safety
CA 5. Stability and flexibility of operation
6. Equipment life expectancy
B. If the density is not constant, ε A ≠ 0 7. Length of time that the product is expected to be manufactured
8. Ease of convertibility of the equipment to modified operating
n conditions or to new and different processes
X A ( 1+ ε A X A )
General Equation: kτ = n−1 n With the wide choice of systems available and with the many
C AO (1 − X A) factors to be considered, no neat formula can be expected to give the
optimum setup. Experience, engineering judgment, and a sound
 STEADY-STATE PLUG FLOW REACTOR
knowledge of the characteristics of the various reactor systems are all
In a plug flow reactor the needed in selecting a reasonably good design and, needless to say,
composition of the fluid the choice in the last analysis will be dictated by the economics of the
varies from point to point overall process.
along a flow path;
consequently, the material Size Comparison of Single Reactors:
balance for a reaction
Batch Reactors
component must be made for
Advantage:
a differential element of
 Small instrumentation cost
volume dV.
 Flexibility of operation (may be shut down easily and quickly)
Disadvantage:
CA X Af  High labor and handling cost
dCA d XA  Considerable shutdown time to empty, clean out, and refill
General Equation: τ = -∫ = C AO ∫  Poorer quality control of the product
C A0
−rA 0
−r A
A. Batch versus Flow reactors
A. If density is constant ε A = 0: τ PFR = t batch Based on the advantages and disadvantages of batch rector
stated previously, we may generalize to state that the batch
Which means integrated rate equations of plug flow and batch reactor is well suited to produce small amounts of material and to
reactors for constant volume reactions are the same. produce many different products from one piece of equipment.
On the other hand, for the chemical treatment of materials in large
B. If density is not constant ε A ≠ 0: amounts the continuous process is nearly always found to be more
economical.
Zero order: kτ = C AO X A Relationship between batch reactor and PFR:
Regarding reactor sizes, for a given duty and for ε = 0 shows
First order: kτ = − ( 1+ ε A ) ln( 1 − X A ) - ε A X A that an element of fluid reacts for the same length of time in the
batch and in the plug flow reactor. Thus, the same volume of

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Second order: these reactors is needed to do a given job.

kτ C AO = 2ε A ( 1+ ε A )ln( 1 − X A ) + ε A
2 2
X A + ( 1+ ε A )

( XA
1− X A )

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B. MFR versus PFR  RECYCLE REACTOR

1. For any particular duty and for all positive reaction orders the Let the recycle ratio R be defined as
mixed reactor is always larger than the plug flow reactor. The
ratio of volumes increases with reaction order. R=
2. At low conversion the MFR is more suitable than PFR. At high
volume of fluid returned ¿ the reactor entrance ¿
conversion PFR is more suitable than MFR. volume leavin
This recycle ratio can be made to vary from zero to infinity.
The ratio of shaded Reflection suggests that as the recycle ratio is raised the behavior
and of hatched areas shifts from plug flow (R = 0) to mixed flow (R = infinity).
gives the ratio of
space-times needed XA
d XA
in these
reactors.
two
τ = CAO(R + 1) ∫ −rA
R
XA
R +1

Integrated recycle equations for ε = 0:

 MULTIPLE REACTOR SYSTEMS

[ ]
A. PLUG FLOW REACTORS IN SERIES AND/OR IN PARALLEL C AO + R C A
kτ
 N plug flow reactors in series with a total volume V gives the same  First order reaction: = ln
conversion as a single plug flow reactor of volume V.
R +1 ( R+1 ) C A

 For the optimum hook up of plug flow reactors connected in C AO ( C AO −C A )

parallel or in any parallel-series combination, we can treat the
k C AO τ
 Second order reaction: =
whole system as a single plug flow reactor of volume equal to the R+1 C A ( C AO + R C A )
total volume of the individual units if the feed is distributed in
such a manner that fluid streams that meet have the same
composition. Thus, for reactors in parallel V/F or τ must be the The expressions for ε ≠ 0 and for other reaction orders can be
same for each parallel line. evaluated, but are more cumbersome.

B. EQUAL-SIZE MIXED FLOW REACTORS IN SERIES

In plug flow, the concentration of reactant decreases
progressively through the system; in mixed flow, the concentration
drops immediately to a low value. Because of this fact, a plug flow
reactor is more efficient than a mixed flow reactor for reactions
whose rates increase with reactant concentration, such as nth-
order irreversible reactions, n > 0.

NOTE: The larger the number of units in series, the closer should
the behavior of the system approach plug flow

FOR N IDENTICAL MFRS IN SERIES:

C AO 1 N
First order reaction: = = ( 1+k τ i )
CA 1− X A

 DESIGN OF DIFFERENT TYPES OF REACTORS IN SERIES

a. If the rate concentration curve rises monotonously (n > 0) the
ordering of units should be plug flow followed by small CSTR and
large CSTR, respectively
b. For order of reaction (0<n<1), the reverse ordering namely large
CSTR to be followed by small CSTR and lastly by PFR can be
implemented.
c. For a negative order, or any other form where the rate has a
maximum or minimum, the best set up is a CSTR followed by a
PFR.

PROBLEMS

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1. A rocket engine burns a stoichiometric mixture of fuel (liquid 5. The reaction 2A → 2R + S takes place isothermally in a constant-
hydrogen) in oxidant (liquid oxygen). The combustion chamber is volume experimental reactor. Starting with a mixture of 80% A
cylindrical, 75 cm long and 60 cm in diameter, and the combustion and 20% inert, the initial pressure of 10 atm increases by 25% in 8
process produces 108 kg/s of exhaust gases. If combustion is minutes. What conversion is attained?
complete, find the rate of reaction of hydrogen and of oxygen. Solution:
Solution:
2A → 2R + S Δn = 3 – 2 = 1
Reaction: 2 H 2 (l) + O 2(l) → 2 H 2 O(g )
a
P A =¿ P AO − ( P − P¿ )
Mol H2O formed = 108
kg kmol
s 18 kg
= 6 kmol/s
( ) Δn T
2
¿ 0.8 ( 10 ) − [ 1.25 ( 10 ) −10 ]
π 1
Volume of chamber = ( 0.6 m )2 ( 0.75 ) = 0.212 m3 P A =¿ 3 atm
4
6 kmol /s P AO − P A 0.8 ( 10 ) − 3
rH O=
3
3 = 28.3 kmol/(m -s) At constant T and V: XA = = = 0.625
2
0.212 m P AO 0.8 (10)
`
a) Rate of reaction of hydrogen Follow-up Question:
− rH = r H 3 If the same feed in the preceding problem is introduced in an
O = 28.3 kmol/(m -s)
2 2
isothermal variable-volume batch reactor, what is the time
b) Rate of reaction of oxygen required for the same conversion?
1 1 Solution:
− rO 2
= (r
2 H 2 O )= 2 (28.3) = 14.15 kmol/(m -s) 3
At n = 2:
−1
C A −C AO
−1
= kt VX =1 −V X =0
εA= A A
=
−1
( 3) − ( 8) −1
= k (8 ) VX =0
2. Milk is pasteurized if it is heated to 63℃ for 30 min, but if it is
A

heated to 74℃ it only needs 15 s for the same result. Find the k =0.02604 14 −10
activation energy of this sterilization process 10
Solution:
ε A = 0.4
ln
k2 E
k1 R
=
( 1 1
−
T1 T 2 ) X A ( 1+ ε A )
+ ε A ln ( 1 − X A ) =¿ kC AOt
since
k 2 t1
=
k 1 t2
ln
t1
t2
=
E 1 1
− (
R T1 T 2 ) ( 1− X A )
(0.625) ( 1+ 0.4 )
+ 0.4ln ( 1 −0.625 )=¿ (0.02604)
ln
30(60)
15
=
E 1
−
1
8.314 336 347 ( ) (8)(t)
( 1− 0.625 )
E = 422 000 J/mol t = 9.32 min
3. The pyrolysis of ethane proceeds with an activation energy of
about 300 kJ/mol. How much faster is the decomposition at 650°C 6. The decomposition of NO2 to NO and O2 is studied in a batch inside
than at 500"C? a const-vol reactor from an initial pressure of 1 atm of pure NO2.
Solution: Time (min) 0 2 8 12 18

( )
r2 E 1 1 Total P (atm) 1 1.07 1.21 1.28 1.37
ln = − Determine the half-life of the reaction.
r1 R T 1 T 2 Solution:
2NO2 → 2NO + O2 Δn = 2 + 1 – 2 = 1
( )
r2 300 1 1
ln = −
r 1 8.314 x 10 −3
500+273 650+273 P AO = P¿
r2 a
r1
= 1970.71 P A =¿ P AO − ( P − P¿ )
Δn T
2
The decomposition at 650°C is 1971 times faster than at 500°C = 1−[ P −1 ]
1 T
4. For the reaction A + B → S, equal volumes of 1 molar A and 2
molar B are mixed and allowed to react for 1 h which half of A had = 1 − 2 PT – 2
been reacted. If the reaction is 1st-order with respect to A and B, P A =¿ 3 − 2 PT
how much time in hours is required for 75% of A to react?
Solution:

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( 3 −21 P )
1 2 P AO
Basis: Mixing 1 L of A and B: C AO = = 0.5 M ; CBO = = For 1st order reaction: ln = kt → ln = kt
1+ 1 1+ 1 PA T
1M
1
At XA = 0.5: CA = 0.5(1 - 0.5) = 0.25 CB = 1 – (0.5)(0.5) = 0.75 Using scical stat mode: t vs ln → k = 0.07338
3− 2 P T
At XA = 0.75: CA = 0.5(1 - 0.75) = 0.125 CB = 1 – (0.5)(0.75) = 0.625

Since k 1 = k 2, ln 2 ln2
For 1st order reaction: t 1/ 2 = = = 9.45 min
k 0.07338

[ 1 C B C AO
ln
t C A C BO ][
1
=
1 C B C AO
ln
t C A C BO ] 2
7. The rate constant of the second-order reaction of a gas mixture
containing 70% by of reactant A is 0.005/bar-s at 2 atm. What is the
half-life of the reaction?
1 (0.75)(0.5) 1 (0.625)(0.5) Solution:
ln = ln
1 (0.25)(1) t 2 (0.125)(1) P AO = 0.7(2 atm) = 1.4 atm or 1.382 bar
t 2 = 2.26 h
( 2n − 1) −1 ( 22 −1 ) −1
t 1/ 2=¿ n −1 ¿ 2−1
= 145
k ( n −1 ) P AO 0.005 ( 2− 1 ) (1.382)
s

8. The thermal decomposition of nitrous oxide (N2O) in the gas 11. In a rigid tank the first order reaction of the decomposition of
phase at 1030 K is studied in a constant volume vessel at various ozone to oxygen gas occurs. Supposing that a gas mixture initially
initial pressures of N2O. The half-life data so obtained are as charged contains 80% by volume ozone, and 20% inerts gas
follows: species at 1 atm and 40⁰C. If the pressure rises to 1.00067 after 5
Po (atm) 52.5 139 290 360 days, how long will the half of the ozone deplete at this
t1/2 (s) 860 470 255 212 temperature?
If reaction 2N2O → 2N2 + O2. Determine the order of reaction. Solution:
Solution: Reaction: 2O 3 → 3O 2 Δn = 3 - 2 = 1
(2 n− 1
) −1 P AO = 0.8(1 atm) = 0.8 atm
t 1/ 2=¿ n −1 = C P AO
1 −n

k ( n −1 ) P AO a
P A =¿ P AO −
Δn T
( P − P¿ )
Linearized form: ln( t 1/ 2 ) = (1 - n)ln( P AO ) + C 2
= 0.8 − [ 1.00067 −1 ]
1
Using scical stat mode: ln( P AO ) vs ln( t 1/ 2 ) → 1 - n = - 0.73
P A =¿ 0.79866 atm
n = 1.73

( 0.79866 )
9. The gas reaction, 3A → B occurs in a constant volume bomb such P AO 0.8
ln = kt → ln = k(5) → k = 3.353x10− 4
that 10% of A has been reacted in the first 50 seconds of PA
reaction. If the reaction is elementary, when will be the reaction
−1
90% complete? day
Solution:
ln 2 ln 2
General Equation: CA
1 −n
−C AO
1 −n
= ( n −1 ) kt t 1/ 2 = = − 4 = 2067 days or 5.66 days
k 3.353 x 10
−2 −2
For 3rd order reaction: C A−C AO = kt
12. For the following liquid-phase series reaction carried in a 500
For constant-volume processes: C A = C AO ( 1 − X A )
dm3 batch reactor.
−2 k 1=0.056/min B k 2=0.71/minC
[ C AO ( 1− X A ) ] −C AO
−2
= kt A
→ →
When is the time where B is a maximum?
C AO −2
[ ( 1− X A ) −1 ] = kt
−2
Solution:

( 1 − X A ) −1 = ( k /C AO )t
−2 −2
ln ( k 2 /k 1) ln ( 0.71/0.056 )
−2
tC = = = 3.88 min
( 1 − X A ) −1 = Ct
R,max
k 2 −k 1 0.71− 0.056

[ ][ ]
−2 −2
(1 − X A) =
(1 − X A) ( 1− 0.1 )−2 −1 = 13. The addition of hydrogen fluoride to propylene in
50 polyfluoropropylene production is competing reaction between
t 1 t 2
the 1-fluoro and 2-fluoro products. Supposing that the rate

craledesma
 11

( 1− 0.9 )−2 −1 constants for these reactions are k 1 = 0.046/min and k 2=

0.0134/min respectively. Determine the fraction of 2-fluoro
t2 formed in the product for 10 minutes time.
t 2 = 21 103 s or 5.86 h Solution:

10. The dimerization reaction of A to R is studied such that the initial C R −C RO k 1 C 2− fluro k 2 0.0134
¿ → ¿ ¿ = 0.2913
concentration is 0.2 mol/Li of A. The reaction is 25% complete is C S −C SO k 2 C1 − fluoro k 1 0.046
5 hours and 75% complete in 20 hours.
a) Determine the order of the reaction
b)Determine the half-life of the reaction
C 2 −fluro 0.2913
= = 0.2256 or 22.56 %
Solution: C1 − fluoro +C 2− fluro 1+ 0.2913
1 −n 1 −n
General Equation: −C AO = ( n −1 ) kt
CA
k1
For constant-volume processes: C A = C AO ( 1 − X A ) A→ B is conducted in
14. The first-order reversible liquid reaction ←
1− n
[ C AO ( 1− X A ) ] − C AO
1− n
= ( n −1 ) kt k2
a batch reactor. The initial concentrations are C A =0.5mol/li
C AO1− n [ ( 1− X A )1− n − 1 ] = ( n −1 ) kt O

and C B =0. After 8 minutes, the fractional conversion of A is

−1 = [ ( n − 1 ) k /C AO1 −n ]t
O
1 −n
(1 − X A) 1/3 and at equilibrium, the fractional conversion of A is 2/3. Find
1 −n the equilibrium constant.
(1 − X A) −1 = Ct Solution:

[ ][ ]
1−n 1−n
(1 − X A) (1 − X A) ( 1− 0.25 )1 −n −1 C A , eq = C AO ( 1 − X A , eq ) = 0.5 ( 1 −2/3 ) = 1/6
= =
t 1 t 2 5 C B , eq = 0.5 – 1/6 = 1/3
1 −n
( 1− 0.75 ) −1 C B , eq 1/3
20 kc = = =2
C A ,eq 1/6
n = 0.643
C AO 1− n
[ ( 1− X A )
1− n
− 1 ] = ( n −1 ) kt
(0.2)
1 −0.643
[ (1 − 0.25 )1 −0.643 − 1 ] = ( 0.643 −1 ) (k)(5)
( 2 n− 1 ) − 1
k = 0.0308 t 1/ 2=¿ n−1 ¿
k ( n −1 ) C AO
( 20.643 −1 ) −1
= 11.22 h
0.0308 ( 0.643 −1 ) (0.2)0.643 −1

15. Consider a feed CAO = 100, CBO = 200, CIO = 100 to a steady-flow 18. Ozone is converted to oxygen in the atmosphere catalyzed by
reactor. The isothermal gas-phase reaction is: A + 3B → 6R. If CA CFCs. The reaction is simulated in a movable piston such that
= 40 at the reactor exit, what is XA, XB, and CB? mixture contains 20% CFC at 1 atm. In 5 days, it is found that
Solution: the piston volume is 10% more than its initial volume. What is
the half-life of if reaction order is zero?
A + 3B + I → 6R Solution:
At XA = 0: V = 100 + 200 + 100 = 400 Reaction: 2O 3 → 3O 2
At XA = 1: V = 0 + (-100) + 100 + 600 = 600
At XA = 0: V = 1
VX =1 −V X =0 600 −400 At XA = 1: V = 0.8(3/2) + 0.2 = 1.4
εA= A A
= = 0.5
VX =0 400 VX =1 −V X =0 1.4 −1
A
εA= A A
= = 0.4
C AO C BO a ε A C BO (1)(0.5)(200) VX =0 1
→ εB =
A
= = =
a ε A b εB b C AO (3)( 100) % volume change = ε A X A = 0.1
1/3
P AO t εA 5(0.4 )
In 5 days, = = = 20.984
k ln ( 1+ε A X A ) ln ( 1+0.1 )

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 12

C AO −C A 100 − 40 Solving for half-life,

a) XA = = = 0.5
C AO + ε A C A 100+(0.5)(40) P AO ( 1 − X A ) P AO ( 1 − X A )
PA = → 0.5 P A 0 = →
ε A X A (0.5)(0.5) 1+ ε A X A 1+ 0.4 X A
b) ε A X A =ε B X B → X B=¿ = = 0.75
εB 1 /3 X A = 0.41667
C ( 1 − X B ) 200 (1 − 0.75 )
C B = BO = = 40 P AO t 1/ 2 ε A P AO ln ( 1+ ε A X A )
1+ε B X B 1+ ( 1/3 )( 0.75 ) = → t 1/ 2 =
k ln ( 1+ε A X A ) k εA
16. Consider a feed CAO = 100, CBO = 200 to a steady-flow reactor. The
isothermal gas-phase reaction is: A + B → R + S. If XA = 0.8 at the
P AO ln ( 1+ ε A X A )
t 1/ 2 =
reactor exit, what is XB, CA, and CB there? k εA
Solution:
20.984 ln [ 1+0.4 (0.41667) ]
C AO X A C BO X B C AO X A b =
a) = → XB= = 0.4
a b a C BO t 1/ 2 = 8.087 days
(100)(0.8)(1)
= 0.4 19. The first-order gas reaction 2A → 2B + C occurs occurs in a
(1)(200) piston reactor such that the reactor is initially charged with 70%
A, 10% B and inerts. In 2 hours, the vessel volume is 1.2 times
b) A + B → R + S
the initial volume. What is the mole fraction of A in 3 hours?
At XA = 0: V = 100 + 200 = 300 Solution:
At XA = 1: V = 0 + 100 + 100 + 100 = 300
Reaction: 2A → 2B + C
VX =1 −V X =0 300− 300
εA= A A
= = 0 (Density is At XA = 0: V = 1
VX A =0
300 At XA = 1: V = 0.7 + 0.7(1/2) + 0.1 + 0.2 = 1.35

constant) VX =1 −V X =0 1.35− 1
εA= A A
= = 0.35
C AO ( 1 − X A ) 100 (1 − 0.8 ) VX =0 1
CA= = = 20
A

1+ ε A X A 1+ ( 0 ) ( 0.8 ) After 2 hours,

% volume change
ε X (0)(0.8) % volume change = ε A X A → XA =
c) ε A X A =ε B X B → ε B= A A = =0 εA
XB 0.4
0.2
XA = = 0.5714
C BO ( 1 − X B ) 200 (1 − 0.4 ) 0.35
CB = = = 120
1+ε B X B 1+ ( 0 )( 0.4 )
For first order reaction: − ln ( 1 − X A ) = kt
17. A first-order gas phase reaction A → 2.5 R with k = 0.035/min is
carried out in a varying-volume batch reactor at 2 atm. The feed
contains pure A. what is the volume change after 30 minutes?
Solution:
[ − ln ( 1− X A )
t 1 t][
− ln ( 1− X A )
=
2
]
VX −V X 2.5− 1 −ln ( 1 −0.5714 ) −ln ( 1 − X A 2 )
=1 =0 =
εA= A A
= = 1.5 2 3
VX =0 1
A
X A 2 = 0.72
− ln ( 1 − X A ) = kt V = V O ( 1+ε A X A )
CB = 0.7(0.72) + 0.1 = 0.604 C C = 0.7(0.72)(0.5) = 0.252
− ln ( 1 − X A ) = 0.035(30) V
VO
= 1 + 1.5(0.65) CA = 0.7(1-0.7194) = 0.196 C i = 0.2
X A = 0.65
V 0.196
= 1.975 Mole fraction of A = = 0.157
VO 0.604+ 0.252+ 0.196+0.2

% volume change =
( V
VO
−1
) x 100

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 13

= ( 1.975 −1 ) x 100
% volume change = 0.975 or 97.5 % increase

20. Pure gaseous reactant A (CAO = 100 mmol/L) is fed at a steady rate Concentrations of A and B in mixture:
into a mixed flow reactor (V = 0.1 liter) where it dimerizes (2A → 2.8 1.6
R). For different gas feed rates the following data are obtained: CAO = = 1.4 mol/L CBO = = 0.8 mol/L
2 2
Reaction: A + 2B ↔ R
Since the density is constant, ε A = 0
CB = CBO(1 – XB) = 0.8(1 – 0.75) = 0.2 mol/L
Find a rate equation for this reaction.
Solution: (0.8)(0.75)
CA = 1.4 - = 1.1 mol/L
2A → R 2
− r A = kC A2 (0.8)(0.75)
CR = = 0.3 mol/L
log( − r A ) = 2log( C A ) + log k 2

VX =1 −V X =0 50− 100 −rA = 2

12.5 C A C B - 1.5 C R
εA= A A
= = - 0.5
VX A =0 100 = 12.5(1.1)(0.2)2 – 1.5(0.3)
− r A = 0.1 mol/L-min
Run CA vO τ XA −rA
1 85.7 10 0.01 0.25 2500 C AO −C A
2 66.7 3 0.033 0.5 1515.15 τ=
3 50 1.2 0.083 0.67 807.23 −rA
4 33.4 0.5 0.2 0.8 400 V 6 1.4 −1.1
since, τ = : =
Equations used:
v0 v0 0.1
V v O = 2 L/min or 1 L/min of each of the two feed streams
Column 4: τ =
vO Note: Solving in terms of B will yield the same answer
Run log log C AO −C A
Column 5: X A = 22. The third order reaction of 0.2 lbmol/ft 3 of A occurs in a CSTR
(C A) (− r A) C AO + ε A C A
reactor such that the conversion is 50% when the liquid pumped
1 1.933 3.398 C AO X A at 10 ft3/min. What rate should the pumping be so as to attain a
2 1.824 3.180 Column 6: − r A =
τ 90% conversion in an plant-scale CSTR with 50 times the volume
3 1.699 2.907 of the pilot reactor?
4 1.524 2.602 Using Caltech: Solution:
 slope = n = 1.96 or 2 C AO −C A
(check) For 3rd order reaction in CSTR (ε A = 0): kτ = 3
 y-int = log k = - 0.397 CA
k = 0.4
At X A = 0.5: C A = 0.2 ( 1− 0.5 ) = 0.1

Rate equation: − r A = 0.4C A

2 At X A = 0.9: C A = 0.2 ( 1− 0.1 ) = 0.02

Pilot reactor:
Note: If we ignore the density change in our analysis (or put ε A = 0
and use CA = CAO(1 – XA) ) we end up with an incorrect rate
equation (reaction order n = 1.6) which when used in design
k
( 10V ) =
0.2− 0.1
0.1
3 → kV = 1 000

would give wrong performance predictions. Plant scale:

( 50qV ) 0.2− 0.02

21. The elementary liquid-phase reaction: A + 2B ↔ R with the rate 50(1000)
equation k = 3 → = 22 500 → q=
0.02 q
( )
2
1 L 2
− r A = - r B = 12.5 C A CB - 20/9 ft3/min
2 2
mol − min
23. A plug-flow is hooked with an MFR of five times the volume where
a first order reaction occurs. If the conversion in the PFR is 20%,

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 14

mol what is the overall conversion?

( 1.5 min− 1 ) C R , Solution:
L− min
is to take place in a 6 L steady-state mixed flow reactor. Two feed Basis: C A 0(PFR) = 1 mol/L ; C A(PFR) = C A 0(MFR) = 1(1−0.2) = 0.8
streams, one containing 2.8 mol A/L and the other containing 1.6 mol/L
mol B/L, are to be introduced at equal volumetric flow rates into
the reactor, and 75% conversion of limiting component is desired.
CA CA
What should be the flow rate of each stream? Assume a constant dCA dC ln ( C A /C A 0 )
density throughout. PFR: τ = -∫ =- ∫ kCA =−
Solution: C A0
−rA C A0 A k
V ln ( 0.8 /1 ) kV
=− → = 0.223
q k q

C AO −C A C AO −C A
MFR: τ = =
−rA kCA
5V 0.8 −C A 0.8 −C A
= → 5(0.223) = → CA
q kC A CA
= 0.378

C A (MFR) 0.378
Overall Conversion = 1 − =1− = 0.62 or
C A 0 (PFR) 1
62 %

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 15

24. A solution containing 0.4 mol/Li of reactant that decomposes in 27. A homogeneous gas rxn A → 3R has a reported rate at 215 ℃
a second-order manner (half-life = 12 min) occurs in an MFR
− r A = 10− 2 C A0.5, [mol/L-s]
followed by a PFR in series at. The conversion in the MFR is 20%
and the overall is 80%. Determine the volume PFR/volume MFR. Find the space-time needed for 80% conversion of a 50% A-50%
Solution: inert feed to a plug flow reactor operating at 215 ℃ and 5 atm (
C AO = 0.0625 mol/L).
C A 0(MFR) = 0.4 mol Solution:
C A(MFR) = C AO(PFR) = 0.4(1−0.2) = 0.32 mol/L
VX =1 −V X =0 2− 1
C A (PFR ) εA= A A
= =1
Overall Conversion = 1 − VX =0 1
C A 0 (MFR) A

C A (PFR) C AO ( 1 − X A ) 0.0625 ( 1− 0.8 )

0.8 = 1 − → C A(PFR) = 0.08 CA= = = 0.00694 mol/L
0.4 1+ ε A X A 1+(1)(0.8)
CA
C AO −C A C AO −C A dCA
MFR: τ= = 2 τ = -∫
−rA kCA C A0
−rA
0.00694
V (MFR) 0.4 − 0.32 kV (MFR) dCA
=
k ( 0.32 )
2 → = =- ∫ −2
10 C A
0.5
q q 0.0625
0.781 (Eq. 1)
[
= -200 (0.00694)0.5 −(0.0625)0.5 ]
τ = 33.3 s
( )
CA CA
dCA d CA 1 1 1
PFR: τ = -∫
−rA
=- ∫ kC 2
= −
k C A C AO 28. The homogeneous gas decomposition of phosphine
C A0 C A0 A
4PH3(g) → P4(g) + 6H2
V (PFR)
q
=
1 1
(−
1
k 0.08 0.32
→
kV (PFR )
q ) =
proceeds at 649 ℃ with the first-order rate
− r PH = (10/h)C PH
3 3

What size of plug flow reactor operating at 649°C and 460 kPa
9.375 (Eq. 2) can produce 80% conversion of a feed consisting of 40 mol of
V (PFR) 9.375 pure phosphine per hour?
Dividing Eqs. 1 and 2: = = 12 Solution:
V (MFR) 0.781
Assuming the gas behaves ideally:
25. The second-order decomposition of aromatics to propane and nRT ( 40)(0.082057)(649+273)
ethane has an average rate constant of 6.0/atm-h. Suppose V= = = 666.6 L/h
that 100 kmol/h of vaporized aromatics at 200 oC and 3 atm is P 460/101325
to be processed in a system composed of an MFR followed by a
PFR twice the volume. What should be the volume of the MFR
VX =1 −V X =0 7 −4
εA= A A
= = 0.75
for an overall conversion of 90%? VX A =0 4
Solution:
P A (PFR) kτ = − ( 1+ ε A ) ln( 1 − X A ) − ε A X A
Overall Conversion = 1 −
P A 0 ( MFR)
0.9 = 1 −
P A (PFR )
→ P A (PFR) = 10
( 10 ) ( 666.6
V
) = − (1+ 0.75 )ln( 1 −0.8 ) – (0.75)(0.8)

100 V = 147.8 L

P AO − P A P AO − P A 29. For a gas reaction 2A → R + 2S taking isothermally in a constant

MFR: τ = = 2 volume reactor. Starting with 3 atm A and 1 atm inerts, the
−r A kCA pressure rises to 4.5 atm in 60 minutes. What space time and
space velocity is required to effect this conversion in a) plug
V (MFR) 100− P A flow b) back-mix reactor?
= 2 (Eq. 1)
q 6 PA Solution:
Constant-volume reactor:
a 2
( )
PA PA
d PA d PA 1 1 1 P A =¿ P AO − ( PT − P¿ ) ¿ 3 − ( 4.5 − 4 )=¿ 2
PFR: τ = -∫
−rA
=- ∫ kP 2
= −
k P A P AO
Δn 1
PA 0 PA 0 A 3− 2
XA = = 1/3
3

craledesma
 16

( )
−1 −1
2V ( MFR) 1 1 1 −1 −1
= kt →
2 −3
= − (Eq. 2) P A − P AO k= = 0.00278
q 6 10 P A 60
a) Plug Flow Reactor (PFR)

( )
2 ( 100 − P A ) 1 1 1 VX −V X
Substituting Eq. 1 to Eq. 2: = − =1 =0 5.5− 4
2 6 10 P εA= A A
= = 0.375
6 PA A VX =0 4
A

P A (MFR) = 40
kτ C AO = 2ε A ( 1+ ε A )ln( 1 − X A ) + ε A
2 2
X A + ( 1+ ε A )
nRT 100 000(0.08206)(473)
Using IGE: q =

377 L/h
P
=
3
= 129 XA
(
1− X A )
(0.00278)(τ)(3) =
V(MFR) =
( 100 − P A
6PA
2
) [
(q) =
100 − 40
6 (40)
2
](129 377) = 808.6 L (0.375) ( 1+ 0.375 ) ln ( 1− 1/3 ) + ( 0.375 )2 ( 1/3 ) + ( 1+0.375 )2
τ = 68.83 minutes
( 1−1/31/3
26. How many 210 Li –reactors connected in series are required for
a 98% conversion of a first order conversion of lactose to 1 1
galactose and glucose (half-life = 35 minutes) at a rate of 10 Space velocity = = = 0.0145 min-1 or 0.87 hr-1
τ 68.83
Li/min?
Solution:
ln 2 ln 2 210
t 1/ 2= → k= = 0.0198 ; τ i = = 21 min
k 35 10
1 N 1 N
= ( 1+k τ i ) → = [ 1+(0.0198)(21) ]
1− X A 1− 0.98
→ N ≈ 11

craledesma
 17

b) Back-Mix Reactor (BMR) 32. One hundred liters/hr of radioactive fluid having a half-life of 20
n hr is to be treated by passing it through two ideal stirred tanks
X A ( 1+ ε A X A ) in series, V = 40 000 liters each. In passing through this system,
General Equation: n−1 n
= kτ how much will the activity decay?
C AO (1 − X A) Solution:

[ ( )( )]
2
X A ( 1+ ε A X A )
2 1 N 1 ln 2 40 000
1− X A (
= 1+k τ i ) → = 1+
For 2nd order reaction: 2
= kτ 1− X A 20 100
C AO ( 1− X A )
(1/3) [ 1+ ( 0.375 ) (1 /3 ) ]
2 X A = 99.5 %
=
2
( 3 ) ( 1 −1/3 )
(0.00278)(τ)
τ = 113.82 minutes

1 1
Space velocity = = = 0.0088 min− 1 or 0.53 hr − 1
τ 113.82
30. The reactor setup shown in below consists of three plug flow
reactors in two parallel branches. Branch D has a reactor of
volume 50 liters followed by a reactor of volume 30 liters.
Branch E has a reactor of volume 40 liters. What fraction of the
feed should go to branch D?

Solution:
Note: Branch D consists of two reactors in series; hence, it may
be considered to be a single reactor of volume. Also, for
reactors in parallel V/F must be identical if the
conversion is to be the same in each branch.

( VF ) ( VF )
D
=
E

80 40
=
FD FE
F D = 2F E
FD
Fraction of feed should go to branch D =
F D+ FE
2 FE
=
2 FE+ F E
Fraction of feed should go to branch D = 2/3
31. At present we have 90% conversion of a liquid feed (n = 1, C A0 =
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
increase/ decrease the processing rate of our feed to the same
90% conversion?
Solution:

C A = 10(1−0.9) = 1 mol/L

kτ
R +1
= ln
[
C AO + R C Af
( R+1 ) C Af ] →
kτ
2+ 1
= ln
[
10+(2)(1)
( 2+1 ) (1) ]
→ k τ 1 = 4.16

craledesma
 18

→
kτ
0+1
= ln

2.303
[
10+(0)(1)
( 0+1 ) (1) ]
→ k τ2 =

k τ 1 q2 4.16
= = = 1.806
k τ 2 q1 2.303

q2
% increase/decrease = − 1 = 1.806 − 1 = 0.806 or 80.6 %
q1
Thus, without recycle, processing rate is 80.6 % higher.

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