CHEMICAL PROCESS MODELLING AND SIMULATION

ASSIGNMENT

DETAILED SOLUTIONS OF
CHAPTER - 2 AND 3 OF LUYBEN BOOK,
CHAPTER - 5 OF COKER BOOK

Submitted by
KUNDRAPU CHAITANYA
BT18CME023

DEPARTMENT OF CHEMICAL ENGINEERING

VISVESVARAYA NATIONAL INSTITIUTE OF TECHNOLOGY
NAGPUR
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 INDEX
S.No. TITLE Pg. No.
1 Chapter 2 Luyben 04
Problem 2.1 05
Problem 2.2 07
Problem 2.3 08
Problem 2.4 10
Problem 2.5 12
Problem 2.6 14
Problem 2.7 16
2 Chapter 3 Luyben 18
Problem 3.1 19
Problem 3.2 20
Problem 3.3 22
Problem 3.4 23
Problem 3.5 26
Problem 3.6 27
Problem 3.7 29
Problem 3.8 30
Problem 3.9 33
Problem 3.10 33
Problem 3.11 35
Problem 3.12 36
Problem 3.13 37
Problem 3.14 39
Problem 3.15 41
Problem 3.16 45
Problem 3.17 48
Problem 3.18 52
Problem 3.19 53
Problem 3.20 54
Problem 3.21 59
3 Chapter 5 Coker 62
Problem 5.1 63
Problem 5.2 65
Problem 5.3 68
Problem 5.4 70
Problem 5.5 75
Problem 5.6 81

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Problem 5.7 86
Problem 5.8 92
Problem 5.9 93
Problem 5.10 95
Problem 5.11 100
Problem 5.12 102
Problem 5.13 104
Problem 5.14 105
Problem 5.15 107
Problem 5.16 108
Problem 5.17 121
Problem 5.18 123

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CHAPTER 2

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Problem 2.1
Consider the tank of perfectly mixed liquid and a chemical reaction takes place in the liquid
in the tank. The system is now a CSTR (continuous stirred-tank reactor) as shown in Fig. 1
Component A reacts irreversibly and at a specific reaction rate k to form product, component
B. Write the component continuity equations for the given CSTR at
(a) Simultaneous Reaction (First Order, Isothermal)
k1 k2
A→ B A→ C
(b) Reversible (First Order, Isothermal)
k1
A↔ B

Solution :
Assumption:
➢ The fluid is assumed to be of constant density.
➢ The Temperature in reactor is constant.
➢ The reaction is assumed to be a first order reaction.
➢ There is perfect mixing in CSTR.
➢ Rate constants are assumed to be constant and does not change with temperature.
Notation :
➢ V = Volume of CSTR reactor
➢ CA0 = Initial concentration of A
➢ CB0 = Initial concentration of B
➢ CC0 = Initial concentration of C
➢ CA = Final concentration of A
➢ CB = Final concentration of B
➢ CC = Final concentration of C
➢ F0 = Feed stream flowrate
➢ F = Product Stream flowrate
➢ k1 , k2 = Rate constant of reaction.
Component Continuity Equation :
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction

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 Time rate of change of moles
= [ ]
of jth component inside system

For part A of simultaneous reaction, we have ;

Flow of all three components A,B and C into the system: FoCAo , FoCBo , FoCCo
Flow of all three components A,B and C out of systems: FCA , FCB , FCC
ⅆVCA ⅆVCB ⅆVCC
Accumulation term for three components : , ,
ⅆt ⅆt ⅆt

The generation terms for the three component is given by :

For A : - k1VCA – k2VCA
For B : k1VCA
For C : k2VCA
Now substituting the values in Component Continuity Equation, we get
For A:
dVCA
= F0 CA0 − k1 VCA − k 2 VCA − FCA
dt
For B:
dVCB
= F0 CB0 + k1 VCA − FCB
dt
For C:
dVCC
= F0 CC0 + k 2 VCA − FCC
dt

For part B of Reversible reaction, we have ;

Flow of all two components A and B into the system: FoCAo , FoCBo
Flow of all two components A and B out of systems: FCA , FCB
ⅆVCA ⅆVCB
Accumulation term for A and B components : ,
ⅆt ⅆt

The generation terms for A and B components is given by :

For A : - k1VCA + k2VCB
For B : + k1VCA – k2VCB
Now substituting the values in Component Continuity Equation, we get
For A:
dVCA
= F0 CA0 − k1 VCA + k 2 VCB − FCA
dt

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For B:
dVCB
= F0 CB0 + k1 VCA − k 2 VCB − FCB
dt

Thus, we have the component continuity equation for Simultaneous and Reversible reaction
for the given components A, B and C.

Problem 2.2
Write the component continuity equations for a tubular reactor for the given reaction
k1 k2
A→ B → C

Solution :
Assumption:
➢ D is diffusion coefficient due to both diffusion and turbulence.
➢ Assuming plug flow conditions.
➢ Density ,velocity and concentration can vary with time.
➢ Isothermal Condition.
Notations:
➢ ν is the flowrate
➢ AT is the area cross sectional area of reactor.
➢ CA , CB , CC are the concentrations of A ,B ,C.
➢ k1 and k2 are rate constants.
Component Continuity Equation :
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system

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Molar flow of components entering into boundary at z (bulk flow and diffusion):
dCj
= AT vCj − AT Dj
dz
Molar flow of components leaving the system at boundary z + dz
dCj
∂( AT vCj ) dCj ∂ ( AT Dj )
dz
= AT vCj + [ ] dz − AT Dj − [ ] dz
∂x dz ∂x

Time rate of change of components inside the system:

∂(AT Cj dz)
=
∂t
Rate of generation for terms for the reaction:
For A: - AT dz k1 CA
For B: AT dz k1 CA – AT dz k2 CB
For C: At dz k2 CB
Now substituting the values in Component Continuity Equation, we get
For A:

∂CA
∂CA ∂(vCA ) ∂(DA ∂t )
=− + − k1 CA
∂t ∂z ∂z
For B:

∂CB
∂CB ∂(vCB ) ∂(DB ∂t )
=− + + k1 CA − k 2 CB
∂t ∂z ∂z
For C:

∂CC
∂CC ∂(vCC ) ∂(DC ∂t )
=− + + k 2 CB
∂t ∂z ∂z

Thus, we have the component continuity equation for the given reaction in tubular reactor for
the given components A, B and C.
Problem 2.3
Write the component continuity equations for a perfectly mixed batch reactor (no inflow or
outflow) with first-order isothermal reactions:
(a) Consecutive
(b) Simultaneous

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(c) Reversible
Solution :
Assumption:
➢ Simple first order reaction.
➢ Assuming constant volume of reactor.
➢ Isothermal Conditions.
Notations :
➢ k1 and k2 are the rate constant of the reactions.
➢ CA = Concentration of A
➢ CB = Concentration of B
➢ CC = Concentration of C
➢ V is the volume of reactor.
Component Continuity Equation :
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system

1) For Consecutive Reaction :

k1 k2
A→ B → C
For A :
dVCA
= −k1 VCA
dt
dCA
= −k1 CA
dt
For B :
dVCB
= k1 VCA − k 2 VCB
dt
dCB
= k1 CA − k 2 CB
dt
For C :
dVCC
= k 2 VCB
dt
dCC
= k 2 CB
dt
2) For Simultaneous Reactions :
k1
A→ B

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 k2
A→ C
For A :
dVCA
= − k1 VCA − k 2 VCA
dt
dCA
= − k1 CA − k 2 CA
dt
For B :
dVCB
= k1 VCA
dt
dCB
= k1 CA
dt
For C :
dVCC
= k 2 VCA
dt
dCC
= k 2 CA
dt
3) For Reversible Reaction :
k1
A↔ B
For A :
dVCA
= − k1 VCA + k 2 VCB
dt
dCA
= − k1 CA + k 2 CB
dt
For B :
dVCB
= + k1 VCA − k 2 VCB
dt
dCB
= + k1 CA − k 2 CB
dt

Hence, we get the component continuity equations for all the three conditions.
Problem 2.4
Write the energy equation for the CSTR with a cooling coil that can remove the exothermic
heat of reaction λ1 and λ2. Here we have consecutive first order reactions occur with
exothermic heats of reaction λ1 and λ2
k1 k2
A → B→ C

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Solution :
Assumption :
➢ Exothermic reaction
➢ Potential and Kinetic energy is assumed negligible.
➢ Work done is zero.
➢ Negligible heat loss across the CSTR surface.
➢ Perfect mixing occurring in reactor.
➢ Density and specific heat are constant.
➢ Heat capacities are assumed to be constant
Notations :
➢ CpA and CpB heat capacities of A and B respectively
➢ k1 and k2 are the rate constants
➢ CA and CB are the concentrations of A and B
➢ ρA and ρB are the densities.
➢ h is the enthalpy of liquid and H is the enthalpy of gas
➢ T0 and T are initial and final temperatures
➢ F0 and F are the initial and final flowrates
Energy Balance Equation :
Flow of internal, kinetic and Flow of internal, kinetic and
[ potential energy into the ] − [ potential energy out ofthe ]
system by convection or diffusion system by convection or diffusion

Heat added to the system Work done by system

+ [by conduction, radiation and] − [on surrounding (Shaft ]
reaction. or PV work)
Time rate of change of
= [Internal, Kinetic and Potential]
inside system

Flow of internal energy into the system :

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 = F0 ( CA0 hA0 + CB0 hB0 )
= F0 T0 ( CA0 CpA + CB0 CpB )
Flow of internal energy out of the system :
= F ( CA hA + CB hB )
= F T( CA CpA + CB CpB )
Rate of heat generation :
= −λ1 vCA k1 − λ2 vCB k 2

Time rate of change of internal energy inside the system :

d [V( hA ρA + hB ρB )]
=
dt
d [VT ( CpA ρA + CpB ρB )]
=
dt
Now substituting all this values in energy balance equation
We get,
d [VT ( CpA ρA + CpB ρB )]
dt
= F0 T0 ( CA0 CpA + CB0 CpB ) − F T( CA CpA + CB CpB ) − (λ1 vCA k1
+ λ2 vCB k 2 )

So, we got the energy balance equation for the given condition.

Problem 2.5
Charlie Brown and Snoopy are sledding down a hill that is inclined θ degrees from
horizontal. The total weight of Charlie, Snoopy, and the sled is M. The sled is essentially
frictionless but the air resistance of the sledders is proportional to the square of their velocity.
Write the equations describing their position x, relative to the top of the hill (x=0). Charlie
likes to ”belly flop”, so their initial velocity at the top of the hill is v0. What would happen if
Snoopy jumped off the sled halfway down the hill without changing the air resistance?
Solution :
Assumption :
➢ There is no frictional force between sled and hill.
➢ Force due to air resistance is Fair = kV2 N
➢ Assuming the inclination of the hill is constant.
➢ Assuming no other external force is acting on sled other than gravitational pull and
force due to air resistance
Notations :
➢ V0 = Initial velocity at the top of the hill

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 ➢ X = Inclined distance covered by sled from the initial point.
➢ V = Velocity after some time interval.
➢ M = Total weight of Charlie, Snoopy, and the sled.
➢ θ = Hill inclination in degrees
➢ k = Proportionality constant
➢ Fg = Force acting due to weight .
➢ Fr = resistance force due to air
➢ g = Acceleration due to gravity = 9.81 m/s2

Mgsin θ

Mg
Ɵ θ
-
Force Balance Equation: hbjbi
Total force actiing in Total force actiing in rate of change of
[ ]− [ ]= [ ]
direction of motion opposite direction of motion momentum of body
So,
dMV
Fg − Fr =
dt
As M is constant and we have values of Fg and Fr
dV
Mgsinθ − kV 2 = M
dt
But,
dx
V=
dt
So,
dx 2 d2 x
Mgsinθ − k [ ] = M 2
dt dt
With the initial conditions at t=0
dx
X=0 , = V0
dt
Assuming that half way the sled already reached his terminal velocity (the velocity at which
total forces acting on body becomes zero), after Snoopy jumps, Charlie Brown will
decelerate, because of reduction in mass M , Fg is momentarily smaller that Fr. In any case,
the final velocity reached by Charlie Brown alone will be smaller than the velocity that would
have been reached if Snoopy remained in the sled.

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Now, we have 1 unknown (V) and one equation (eq. 1). Hence, our system is satisfied.

Problem 2.6
An automatic bale tosser on the back of a farmer’s hay baler must throw a 60-pound bale of
hay 20 feet back into a wagon. If the bale leaves the tosser with a velocity vr in a direction θ
= 45O above the horizontal, what must vr be? If the tosser must accelerate the bale from a
dead start to vr in 6 feet, how much force must be exerted ?
What value of θ would minimize the acceleration force ?

Solution :
Assumption:
➢ The wagon is considered to be not moving .
➢ Friction force between bale and tosser is neglected.
➢ Friction between bale and air is also neglected.
➢ Assuming that the y coordinate at the exit of the tosser and at the wagon are equal.
➢ Motion of bale is assumed to be 2D, it have no movement in Z direction.
Notation:
➢ L = Length between tosser and wagon.
➢ vr = Velocity of bale at exist of tosser.
➢ M = Mass of bale.
➢ g = Acceleration due to gravity.
➢ tf = Time of flight.
➢ a = Acceleration.

Equation of Motion :
Ma
F=
gc

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As we know that the half time of flight is equal to the time required for reaching the
maximum altitude.
It can be calculated by dividing the Y component of velocity at exit of tosser by acceleration
due to gravity.
So, the Y component of velocity is given by = vr sin θ
1 vr sin θ
tf =
2 g
The distance L must be covered in tf
L
= vr cos θ
tf
Using above two equations we get

Lg
vr = √
2 cos θ sin θ

vr = 25.4 ft/sec
As,
1
l = ut + at 2
2
But u = 0 at start of motion of bale
Here l is the length of the tosser or the length for which the force is applied
1
l = at 2
2
And,
vr = at
Here t is time duration for which the force is applied
So, from the above two equation we get:
vr 2 Lg
a= =
2l 4l cos θ sin θ
Now from the Newton Second Law of motion and force balance we get,
Mgsin θ Ma
Ft − =
gc gc
So substituting the value of a from the above equation,
Mg L
Ft = [sin θ + ]
gc 4l cos θ sin θ
Substituting the values, we get forces as Ft = 142 lbr

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And minimum acceleration force will be required at θ = 0o

Problem 2.7
A mixture of two immiscible liquids is fed into a decanter. The heavier liquid a settle to the
bottom of the tank. The lighter liquid β form a layer on the top. The two interfaces are
detected by floats and are controlled by manipulating the two flows Fα and Fβ

Fα = Kαhα
Fβ = Kβ(hα + hβ)
The controller increases or decreases the flow as the level rises or fall.
The total feed rate is Fo . The weight fraction of liquid a in the feed is x. The two
densities ρα and ρβ are constant.
Write the equations describing the dynamic behaviour of this system.

Soluiton :
Assumption :
➢ The two liquids are assumed to be completely immiscible.
➢ Distant boundary is formed between two liquids.
➢ Density of two liquids is constant.
➢ Fo , Fα and Fβ are considered to be volumetric flow rates.
Notations :
➢ Fo = Total feed volumetric flow rate.
➢ Fα = Liquid α volumetirc flow rate.

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 ➢ Fβ = Liquid β volumetric flow rate.
➢ hα = Liquid level of liquid α
➢ hβ = Liquid level of liquid β
➢ xα = Weight fraction of α in feed
➢ xα,v = Volumetric fraction of α in feed
➢ ρα = Density of liquid α
➢ ρβ = Density of liquid β
➢ A = Cross section Area of Decanter

First of all we need to calculate the volumetric flow rate of α

Volumetric flow rate of α =
xα
ρα
=
xα (1 − x α )
ρα + ρβ
The Total Continuity equation :
Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system

For α:
dhα
F0 xα,v = Fα + A
dt
dhα
F0 xα,v = K α hα + A
dt
So,
dhα 1
= [F0 xα,v − K α hα ]
dt A
For β :
dhβ
F0 (1 − xα,v ) = Fβ + A
dt
dhβ
F0 (1 − xα,v ) = K β ( hα + hβ ) + A
dt
So,
dhβ 1
= [F0 (1 − xα,v ) − K β ( hα + hβ ) ]
dt A

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CHAPTER 3

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Problem 3.1
A fluid of constant density p is pumped into a cone-shaped tank of total volume Hπr 2 /3. The
flow out of the bottom of the tank is proportional to the square root of the height h of liquid in
the tank. Derive the equations describing the system?
Sol:

Assumptions:
➢ Fluid of constant density ρ
➢ Total volume of cone V=HπR2 /3
➢ Flow out of the bottom of the tank F=k√h
Let the liquid be present in the cone at height h.
Total volume of cone = HπR2 /3
Volume of the liquid present in the cone: VL = hπr 2 /3
By similarity of triangles: (If two objects have the same shape, they are called "similar"
When two figures are similar, the ratios of the lengths of their corresponding sides are equal.)

r h
=
R H
Rh
⸫r= H
hπ πR2 h3
⸫VL = (Rh/H)2 =
3 3H2

Total continuity equation for system:

Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
d(ρv)
F0 ρ − Fρ =
d(t)

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 dv
ρ(F0 − F) = ρ
dt
dv
F0 − F =
dt
πR2 h3
d( )
F0 − F = 3H 2
dt
πR2 d(h3 )
F0 − F =
3H 2 dt
πR2 dh
F0 − k√h = 2
(3h2 )
3H dt
πR2 h2 dh
F0 − k√h =
H 2 dt
H2 H2 dh
F0 2 2 − k√h ( 2 2 ) =
πR h πR h dt
dh H 2 k 1 F0 H 2
+ 2 3=
dt πR h2 πR2 h2

Problem 3.2
A perfect gas with molecular weight M flows at a mass flow rate W0 into a cylinder through
a restriction. The flow rate is proportional to the square root of the pressure drop over the
restriction:

Wo = k o √Po − P
where P is the pressure in the cylinder and P0 is the constant upstream pressure. The system
is isothermal. Inside the cylinder, a piston is forced to the right as the pressure P builds up. A
spring resists the movement of the piston with a force that is proportional to the axial
displacement x of the piston.
Fs = kx
The piston is initially at x = 0 when the pressure in the cylinder is zero. The crosssectional
area of the cylinder is A. Assume the piston has negligible mass and friction. (a) Derive the
equations describing the system. (b) What will the steady state piston displacement be?

Solution:

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Assumption:
➢ Piston has negligible mass and friction.
➢ Initially at x = 0, pressure on the cylinder is zero.
➢ Cross-sectional area of cylinder is A.
Total continuity equation for region outside the piston:
Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
d(ρV)
Wo − 0 =
dt
ⅆ(ρAx)
Wo − 0 = ⅆt

PM
d( RT Ax)
K o √Po − P =
dt
MA d(Px)
K o √Po − P =
RT dt
d(Px) RTK o
= √Po − P
dt MA
Force balance for piston:
Sum of forces acting on piston = Mass x acceleration
Pressure force
Pressure forces excerted Force excerted dMv
excerted on piston
[ by piston by presssure ] − [ ] − [ on piston ] =
by atmosphere dt
in cylinder by spring
on spring side
dv
PA − Patm A − Fs = M
dt
But mass of piston is negligible (i.e M=0)
(P − Patm )A = K s x
PA = K s x + Patm A
Ksx
P= + Patm
A

d(Px) RTK o √Po − P

=
dt MA

dx dP RTK o √Po − P
P +x =
dt dt MA
At steady state x and p are constant so their derivative will be zero.

RTK o √Po − P
=0
MA

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 P = P0
Ksx
P= + Patm
A
(P0 − Patm )A = K s x
(P0 − Patm )A
∴x=
Ks

Problem 3.3
A perfectly mixed, isothermal CSTR has an outlet weir. The flow rate over the weir is
proportional to the height of liquid over the weir, how to the 1.5 power. The weir height is hw.
The cross-sectional area of the tank is A. Assume constant density. A first-order reaction
takes place in the tank:
k
A→ B
Derive the equations describing the system.

Ans:
Assumptions:
➢ Perfectly mixed CSTR
➢ Density of fluid is constant
➢ First order reaction is taking place
➢ Total height(H)= how+hw
Total continuity equation:
Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
d(Vρ)
F0 ρ0 − Fρ =
dt
But density(ρ)=constant
d(V)
Ρ(F0 − F) = ρ
dt

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 d(A ∗ H)
F0 − F =
dt
Put F = K f h1.5
ow

d(A ∗ H)
F0 − K f h1.5
ow =
dt
dH
F0 − K f h1.5
ow = A
dt
d(how + hw )
F0 − K f h1.5
ow = A
dt
Component continuity equation
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
d(VCA )
F0 CA0 − FCA + (−kCA0 V) =
dt
d(AHCA )
F0 CA0 − FCA + (−kCA0 V) =
dt
d(HCA )
F0 CA0 − FCA + (−kCA V) = A
dt
Put F = K f h1.5
ow , H = how + hw , V = A(how + hw )

d((how + hw ) CA )
F0 CA0 − K f h1.5
ow CA + (−kCA A(how + hw ) ) = A
dt
From Arrhenius equation,
−EA
K = k 0 e RT

Problem 3.4
In order to ensure an adequate supply for the upcoming set-to with the Hatfields, Grandpa
McCoy has begun to process a new batch of his famous Liquid Lightning moonshine. He
begins by pumping the mash at a constant rate F, into an empty tank. In this tank the ethanol
undergoes a first-order reaction to form a product that is the source of the high potency of
McCoy’s Liquid Lightning. Assuming that the concentration of ethanol in the feed, C, is
constant and that the operation is isothermal, derive the equations that describe how the
concentration C of ethanol in the tank and the volume V of liquid in the tank vary with time.
Assume perfect mixing and constant density.

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Ans. Given that ethanol present in the feed mash undergoes a first order reaction in a batch
reactor, to form a product that is the source of the high potency of McCoy’s Liquid
Lightning.
Assumptions
➢ The tank is under isothermal conditions
➢ There is perfect mixing throughout the tank
➢ The density of the mixture is constant throughout.
➢ The concentration of reactant (ethanol) in the feed stream is constant.
Total continuity equation
Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
ρdV
F0 ρ − 0 =
dt
dV
Fo =
dt

∫ Fo dt = ∫ dV

Fo t = V + m
Substituting the boundary conditions, at t=0, V=0 we get m=0
V = Fo t (1)

Component continuity equation

Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
d(VC)
F0 C0 − 0 − kVC =
dt
dC dV
F0 C0 − kVC = V +C
dt dt
Substituting the equation (1) here we get
dC d(F0 t)
F0 C0 − kF0 tC = F0 t +C
dt dt
dC
C0 − ktC = t +C
dt
dC 1
C0 = t + C( k + )t
dt t
C0 dC 1
= + C( k + )
t dt t

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Using integration factor method to solve the above differential equation.
1
Integration factor, I.F = e∫(k+ t )ⅆt
1
I.F = e∫(kⅆt+ t ⅆt)
I.F = ekt+lnt
I.F = ekt . eloge t
I.F = tekt
Multiplying the differential equation on both the sides with I.F, we get
C0 dC 1
tekt = tekt + Ctekt ( k + )
t dt t
dC d(tekt )
ekt C0 = (tekt )( ) + (C)( )
dt dt

kt
d (tekt C)
e C0 =
dt
ekt C0 dt = d (tekt C)

∫ ekt C0 dt = ∫ d (tekt C)

C0 ∫ ekt dt = tekt C

ekt
C0 = tekt C + m
k

Substituting the boundary conditions, t = 0, C = C0 we get

C0
=m
k
Substituting the m value, we get,
ekt C0
C0 = tekt C +
k k
ekt 1
C0 ( − ) = tekt C
k k
C0 ekt 1
C = kt ( − )
te k k
C0
C= (1 − e−kt )
kt

25 | P a g e
Problem 3.5
A rotating-metal-drum heat exchanger is half submerged in a cool stream, with its other half
in a hot stream. The drum rotates at a constant angular velocity ω (radians per minute).
Assume TH and T, are constant along their respective sections of the circumference. The
drum length is L, thickness d, and radius R. Heat transfer coefficients in the heating and
cooling zones are constant (UH and UC). Heat capacity Cp and density of the metal drum are
constant. Neglect radial temperature gradients and assume steady state operation.
(a) Write the equations describing the system.
(b) What are the appropriate boundary conditions?

Ans. Given, A rotating metal drum heat exchanger half submerged in a cool stream, with its
other half in a hot stream.
Assumptions
➢ TH and TC are constant along their respective sections.
➢ Heat transfer coefficient in the heating and cooling zones are constant (UH and UC)
➢ Heat capacity Cp and density of metal drum ρ are constant
➢ Neglect radial temperature gradients.
➢ Steady state operation
Energy balance equation
Consider a small volume of size dΔθRL,
Flow of internal, kinetic and Flow of internal, kinetic and
[ potential energy into the ] − [ potential energy out ofthe ]
system by convection or diffusion system by convection or diffusion

Heat added to the system Work done by system

+ [by conduction, radiation and] − [on surrounding (Shaft ]
reaction. or PV work)
Time rate of change of
= [Internal, Kinetic and Potential]
inside system
At steady state condition the time rate of change energy will be zero, so
For the heating zone (θ: [0, π]) the steady state energy balance equation will be,

26 | P a g e
 ∂T
RdLρωCp Tθ − RdLρωCp (Tθ + dθ) − 2RLUH (Th − TH )dθ = 0
∂θ
∂T
RdLρωCp Tθ − RdLρωCp Tθ − RdLρωCp dθ − 2RLUH (Th − TH )dθ = 0
∂θ
∂T
RdLρωCp dθ = − 2RLUH (Th − TH )dθ
∂θ
∂T
dρωCp dθ = − 2UH (Th − TH )dθ
∂θ
dT
dρωCp = − 2UH (Th − TH )
dθ
dT 2UH (Th − TH )
=−
dθ dρωCp

For the cooling zone (θ: [π, 2π]) the steady state energy balance equation will be,
∂T
RdLρωCp Tθ − RdLρωCp (Tθ + dθ) − 2RLUC (Tc − TC )dθ = 0
∂θ
∂T
RdLρωCp Tθ − RdLρωCp Tθ − RdLρωCp dθ − 2RLUC (Tc − TC )dθ = 0
∂θ
∂T
RdLρωCp dθ = − 2RLUC (Tc − TC )dθ
∂θ
∂T
dρωCp dθ = − 2UC (Tc − TC )dθ
∂θ
dT
dρωCp = − 2UC (Tc − TC )
dθ
dT 2UC (Tc − TC )
=−
dθ dρωCp

The boundary conditions for the system are

Th (0) = Tc (2π)
Th (π) = Tc (π)

Problem 3.6
Consider the system that has two stirred chemical reactors separated by a plug-flow deadtime
of D seconds. Assume constant holdups (V1 and V2), constant throughput (F), constant
density, isothermal operation at temperatures T1 and T2, and first order kinetics with
simultaneous reactions:
k1 k2
A→ B A→ C

27 | P a g e
No reaction occurs in the plug-flow section. Write the equations describing the system.

Ans. Given a system consisting of two stirred chemical reactors separated by a plug flow
dead time of D seconds
Assumptions
➢ Constant holdups V1 and V2
➢ Constant throughput F
➢ Constant density
➢ Isothermal operation on both tanks at T1 and T2 respectively.
Component continuity equation,
For reactor 1
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system

dCA1,t
V1 = FCA0 − FCA1,t − k1,T1 V1 CA1,t − k 2,T1 V1 CA1,t
dt
dCB1,t
V1 = −FCB1,t + k1,T1 V1 CA1,t
dt
dCC1,t
V1 = −FCC1,t + k 2,T1 V1 CA1,t
dt
For reactor 2
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system

dCA2,t
V2 = FCA1,t−D − FCA2,t − k1,T2 V2 CA2,t − k 2,T2 V2 CA2,t
dt

28 | P a g e
 dCB2,t
V2 = FCB1,t−D − FCA2,t + k1,T2 V2 CA2,t
dt
dCC2,t
V2 = FCC1,t−D − FCC2,t + k 2,T2 V2 CA2,t
dt
The expressions for rate constants are
−E1
k1,T1 = k10 eRT1

−E2
k 2,T1 = k 20 eRT1

−E1
k1,T2 = k10 eRT2

−E2
k 2,T2 = k 20 eRT2

Problem 3.7
Consider the isothermal hydraulic system sketched below. A slightly compressible polymer
liquid is pumped by a constant-speed, positive displacement pump so that the mass flow rate
W1 is constant. Liquid density is given by
ρ = Po + β (P – Po)
where ρo, β, and Po are constants, ρ is the density, and P is the pressure.
Liquid is pumped through three resistances where the pressure drop is proportional to the
square of the mass flow:
ΔP = RW2.
A surge tank of volume V is located between R1 and R2, and is liquid full. The pressure
downstream of R3 is atmospheric.
(a) Derive the differential equation that gives the pressure P in the tank as a function of time
and W1.
(b) Find the steady state value of tank pressure P.

Ans.
Given

29 | P a g e
 ΔP = RW 2
Patm + P − Patm = (R 2 + R 3 )W22

P
W2 = √
(R 2 + R 3 )

Total continuity equation

Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
d(ρV)
W1 − W2 =
dt
dρ
W1 − W2 = V
dt
d(P0 + β (P – P0 ))
W1 − W2 = V
dt
dP
W1 − W2 = V(0 + β − 0)
dt
dP
W1 − W2 = Vβ
dt

P dP
W1 − √ = Vβ
(R 2 + R 3 ) dt

At steady state,

P
W1 − √ =0
(R 2 + R 3 )

P = (R 2 + R 3 )W12

Problem 3.8
Develop the equations describing an “inverted” batch distillation column. This system has a
large reflux drum into which the feed is charged. This material is fed to the top of the
distillation column (which acts like a stripper). Vapor is generated in a reboiler in the base.
Heavy material is withdrawn from the bottom of the column. Derive a mathematical model of
this batch distillation system for the case where the tray holdups cannot be neglected.
Solution:
Assumptions:
➢ Trays are ideal.
➢ Holdup in trays consist of liquid only.

30 | P a g e
 ➢ Binary distillation takes place, and component balances shall be written for the more
volatile component.
➢ αAB is the relative volatility of more volatile component A w.r.t. less volatile
component B, which is a constant and known.

➢ Any liquid accumulation anywhere is perfectly mixed.

➢ Equimolar counter diffusion takes place between trays.
Notation:
➢ Tray related: bottommost tray is tray 1, topmost is N; Lj=liquid outflow rate from tray
j, Vj=vapour flow rate from tray j, Hj= specific molar enthalpy of vapour outflow
from tray j, hj= specific molar enthalpy of liquid outflow from tray j. Mj=molar
accumulation of liquid in tray j
➢ x=mole fraction of more volatile component in liquid.
➢ y=mole fraction of more volatile component in vapour.
➢ MR=moles of liquid accumulated in reflux drum.
➢ ‘o’ refers to the reboiler.
Balance on ith tray
Total molar balance.
dMi
= Li+1 + Vi−1 − Vi − Li
dt

31 | P a g e
Component balance.
dMi xi
= Li+1 xi+1 + Vi−1 yi−1 − Vi yi − Li xi
dt
Energy balance:
d(Mi hi )
= Li+1 hi+1 + Vi−1 Hi−1 − Vi Hi − Li xi
dt
i varies from 1 to N.
for tray 1, input liquid is R.
Balance on reboiler.
Total molar balance.
dMo
= L1 − Vo − W
dt
Component balance.
dMo xo
= L1 x1 − Vo yo − Wxo
dt
Energy balance
dMo ho
= L1 h1 − Vo Ho − Who + Q
dt
Balances on reflux drum.
Total molar balance.
dMR
= F + VN − R
dt
Component balance.
dMR xR
= Fx + VN yN − RxR
dt
Energy balance
dMR hR
= Fh + VN HN − RhR
dt
Equilibrium relationship.
αxi
yi =
1 + (α − 1)xi
i varies from 1 to n.
Equimolar counter diffusion:
L1 = L2 = L3 … … … . LN
V1 = V2 = V3 … … … … VN

32 | P a g e
Unknowns are xi, yi, Mi, Li, Vi, hi, MR, hR, W
i ϵ [0.N].

Problem 3.9
An ice cube is dropped into a hot, perfectly mixed, insulated cup of coffee. Develop the
equations describing the dynamics of the system. List all assumptions and define all terms
Solution:
Assumptions:
➢ Ice is at its fusion temperature Tm.
➢ The coffee container is perfectly insulated.
➢ Coffee is perfectly mixed, with temperature Tc throughout.
➢ Specific heat of coffee and water = Cp.
➢ Area of ice cube at any instant=A
➢ Latent heat of fusion of water = λ
Let Mi=mass of ice; Mc=mass of coffee
Overall mass balance.
dMi dMc
+ =0
dt dt
Mass balance on ice.
dMi UA(Tc − Tm )
=
dt λ
Energy balance on coffee.
dMc Tc Mi
Cp = C T − UA(Tm − Tc )
dt dt p m

Unknowns=Mi, Mc, Tc.

Problem 3.10
An isothermal irreversible reaction A→B takes place in the liquid phase in a constant-
volume reactor. The mixing is not perfect. Observation of flow patterns indicates that a two-
tank system with back mixing, as shown in the sketch below, should approximate the
imperfect mixing. Assuming and are constant, write the equations describing the system.

33 | P a g e
Solution:
Assumptions
➢ Isothermal system
➢ Constant volume reactors
➢ Perfectly mixed reactors
➢ Incompressible flows
For tank 1
Total Continuity equation
V1 dρ1
= Fρo − (F + FR )ρ1 + FR ρ2
dt
Divide by V1 and define τ1 = V1/F
dρ1 ρo FR ρ2 1 FR
= + − ( + ) ρ1
dt τ1 V1 τ1 V1

Component balance on A.
dCA1 CAo FR CA2 1 FR
= + −( + + k) CA1
dt τ1 V1 τ1 V1
−EA
k = αe RT
For Tank 2
Total Continuity
dρ2 1 FR
= (ρ1 − ρ2 ) ( + + k)
dt τ2 V2
Component balance on A
dCA2 1 FR 1 FR
= ( + ) CA1 − ( + + k)
dt τ2 V2 τ2 V2

Equations=5
Unknowns=CA1, CA2, FR, V1, V2

34 | P a g e
Problem 3.11
The liquid in a jacketed, non-isothermal CSTR is stirred by an agitator whose mass is
significant as compared with the reaction mass. The mass of the reactor wall and the mass of
the jacket wall are also significant. Write the energy equations for the system. Neglect radial
temperature gradients in the agitator, reactor wall, and jacket wall.

Solution.
Assumptions:
➢ Reactor and agitator are perfectly mixed and of constant volume.
➢ Physical properties are temperature invariant.
➢ Work done due to agitation is negligible.
➢ Input and output flow rates are equal and constant in both, reactor and agitator.
➢ No heat losses
➢ Radial temperature gradients neglected.
Notations:
➢ Agitator: Ma=mass, Ta=temperature, cp=specific heat, Aa=surface area.
➢ Reactant liquid: V=volume, T=temperature, ρ=density, cr=specific heat.
➢ Reactor wall: Mr=mass, Tr=temperature, A1=inner surface area, A2=outer surface
area, U1=inner heat transfer coefficient, U2=outer heat transfer coefficient
➢ Jacket liquid: Vj=volume, ρw =density, cw=specific heat, Tj=temperature
➢ Jacket wall: Mw=mass, Tw=temp., U3=inner side h.t.c., A3=inner surface area.
➢ Other parameters given in figure.
Energy balance on reactor.
dT
ρVCr = ρF(To − T) − U1 A1 (T − Tr ) − Ua Aa (T − Ta )
dt
Energy balance on agitator.
dTa
Ma cp = Ua Aa (T − Ta )
dT
Energy balance on reactor wall
dTr
Mr cp = U1 A1 (T − Tr ) − U2 A2 (Tr − Tj )
dt

35 | P a g e
Energy balance on jacket liquid
dTj
ρw Vj cw = Fj (Tjo − Tj ) + U2 A2 (Tr − Tj ) − U3 A3 (Tj − Tw )
dt
Energy balance on jacket wall.
dTw
Mw Cp = U3 A3 (Tj − Tw )
dt
Equations=5
Unknowns=T, Tj, Ta, Tr, Tw.

Problem 3.12
The reaction 3A → 2B + C is carried out in an isothermal semi batch reactor. B is the desired
product. Product C is a very volatile by-product that must be vented off to prevent a pressure
build-up in the reactor. Gaseous C is vented off through a condenser to force any A and B
back into the reactor to prevent loss of reactant and product. Assume Fv is pure C. The
reaction is first-order in CA. The relative volatilities of A and C to B are 1.2 and 10
respectively. Assume perfect gases and constant pressure. Write the equations describing the
system. List all assumptions.

Solution:
Assumption.
➢ Gas consist of C only.
➢ Perfectly mixed reactor
➢ Constant overall volume
➢ Isothermal
➢ Reaction is 1st order in A.
Component balance on A.

36 | P a g e
 dCA
VL = −3kCA
dt
Component balance on B.
dCB
VL = 2kCA
dt
Component balance on C.
Let the constant pressure in the reactor be P and Temperature be T.
P dVG FV P
= kVL CA −
RT dt RT
Conservation of volume.
VL + VG = VR
1 equation is remaining.
Unknowns: CA, CB, VL, FV, VG.

Problem 3.13
Write the equations describing a simple version of the petroleum industry’s catalytic cracking
operation. There are two vessels as shown in Fig. Component A is fed to the reactor where it
reacts to form product B while depositing component C on the solid fluidized catalyst.
A→B+0.1C
Spent catalyst is circulated to the regenerator where air is added to burn off C.
C+O→P
Combustion products are vented overhead, and regenerated catalyst is returned to the reactor.
Heat is added to or removed from the regenerator at a rate Q.
Your dynamic mathematical model should be based on the following assumptions :
1. The perfect-gas law is obeyed in both vessels.
2. Constant pressure is maintained in both vessels.
3. Catalyst holdups in the reactor and in the regenerator are constant.
4. Heat capacities of reactants and products are equal and constant in each vessel.
Catalyst heat capacity is also constant.
5. Complete mixing occurs in each vessel.
Solution:
Notations:
➢ C represent concentration,
➢ c represent specific heat.
➢ A1=area to volume ratio of catalyst in reactor, A2=area to volume ratio of catalyst in
regenerator
➢ a means air
➢ ρ=density of catalyst.

37 | P a g e
 ➢ ρj=density of stream j

Balances on the reactor.

Component balance on A:
dCA M1 A_1K1 CA
V1 = Fo CAo − − F1 CA
dt ρ
Component balance on B:
dCB M1 A1 K1 CA
V1 = − F1 CB
dt ρ
Component balance on catalyst.
dx1 M1 A1 K1 CA
M1 = W(x2 − x1 ) −
dt ρ
Energy balance.
dT1 M1 A1 K1 λ1
(M1 cpc + V1 ρ1 cp1 ) = Fo ρo cp1 To − F1 ρ1 cp1 T1 + Wcpc (T2 − T1 } −
dt ρ
Balances on the regenerator.

38 | P a g e
Balance on component O.
dCO M2 A2 K 2 CO x2
V2 = Fa COa − F2 CO −
dt ρ
Balance on component P.
dCP M2 K 2 CO x2
V2 = − F2 CP
dt ρ
Mass balance on catalyst.
dx2 M2 A2 K 2 CO x2
M2 = W{x1 − x2 ) −
dt ρ
Energy balance
dT2 M2 A2 K 2 CO x2 λ2
(M2 cpc + V2 ρ2 cp2 ) = Fa ρa cp2 Ta − F2 ρ2 cp2 T2 + Wcpc (T1 − T2 ) − +Q
dt ρ

Problem 3.14
Flooded condensers and flooded reboilers are sometimes used on distillation columns. In
Figure, a liquid level is held in the condenser, covering some of the tubes. Thus, a variable
amount of heat transfer area is available to condense the vapor. Column pressure can be
controlled by changing the distillate (or reflux) draw-off rate.
Write the equations describing the dynamics of the condenser.

Solution:
Assumptions:
➢ The dynamic of the fluid in the shell side is negligible.
➢ The heat transferred to the cooling water is due to heat of condensation alone.
➢ The area available for heat transfer is proportional to the volume of the tubes not
occupied by the condensed fluid.
➢ Density is constant.
➢ Plug Flow of cooling water.
Notations:

39 | P a g e
 ➢ VT = Total Volume of tubes.
➢ V = Volume of the tubes occupied by the condensed fluid.
➢ AT = Total surface area of the tubes.
➢ FW = Volumetric flowrate of cooling water.
➢ F = Flowrate of the process fluid to be condensed.
➢ λ = Latent heat of condensations.
Total continuity equation:
Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
dVρ lb
Fρ − R − D = ,( )
dt s

Energy Balance for the tubes unoccupied by the fluid:

Flow of internal, kinetic and Flow of internal, kinetic and
[ potential energy into the ] − [ potential energy out ofthe ]
system by convection or diffusion system by convection or diffusion

Heat added to the system Work done by system

+ [by conduction, radiation and] − [ surrounding (Shaft ]
on
reaction. or PV work)
Time rate of change of
= [Internal, Kinetic and Potential]
inside system
Tw,in + Tw,out
(FρCp T + Fρλ) − FρCp T − UA (T − )=0
2
Tw,in + Tw,out
UA (T − ) = Fρλ
2

Since, we are assuming that only latent heat is involved, there will not be any accumulation
term.
As we have assumed that the area available for heat transfer is proportional to the volume of
the tubes not occupied by the condensed fluid we can write,
Tw,in + Tw,out
A = AT (T − )
2

Therefore, the equation becomes,

VT − V Tw,in + Tw,out Btu
U( ) AT (T − ) = Fρλ , ( )
VT 2 s

Energy balance for cooling water:

Flow of internal, kinetic and Flow of internal, kinetic and
[ potential energy into the ] − [ potential energy out ofthe ]
system by convection or diffusion system by convection or diffusion

40 | P a g e
 Heat added to the system Work done by system
+ [by conduction, radiation and] − [on surrounding (Shaft ]
reaction. or PV work)
Time rate of change of
= [Internal, Kinetic and Potential]
inside system
Btu
Fw ρw Cpw Tw,in − Fw ρw Cpw Tw,out + Fρλ = 0 , ( )
s

Since, we are assuming that the dynamics of shell side fluid (water) to be negligible, the
accumulation term will not be there.
From the figure it is seen that the flowrate of stream D is a function of pressure(P) inside the
condenser. Therefore, we can write,
D = f (P)

Problem 3.15
When cooling jackets and internal cooling coils do not give enough heat transfer area, a
circulating cooling system is sometimes used. Process fluid from the reactor is pumped
through an external heat exchanger and back into the reactor. Cooling water is added to the
shell side of the heat exchanger at a rate Fw as set by the temperature controller. The
circulation rate through the heat exchanger is constant. Assume that the shell side of the
exchanger can be represented by two perfectly mixed lumps in series and that the process
fluid flows counter-current to the water flow, also through two perfectly mixed stages. The
reaction is irreversible and first order in reactant A:
k
A →B
The contents of the tank are perfectly mixed. Neglect reactor and heat exchanger metal.
Derive a dynamic mathematical model of this system.

Solution:
Assumptions:
➢ The shell and tube side of the heat exchanger may be considered as two perfectly
mixed lumps in series.

41 | P a g e
 ➢ The volume contained in the both shell and tube lumps of the heat exchanger is
constant.
➢ Density and specific heat are constant.
➢ Density and specific heat are independent of the concentration of A and B.
➢ The reactor is perfectly mixed.

Notations:
➢ T1 , T2 = Temperature of the fluid in tube 1 and 2 respectively.
➢ TW1 , TW2 = Temperature of the water in shell 1 and 2 respectively.
➢ λ = Exothermic Heat of Reaction.
➢ EA = Activation energy
➢ U = Overall Heat Transfer Coefficient
➢ VW , VT = Volume of shell and tube lump respectively.
➢ T = Temperature inside the reactor.
➢ Subscript “w” represents the shell side fluid i.e., cooling water.

Total continuity equation for the system:

Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
ρdV
F0 ρ − Fρ =
dt
dV ft 3
F0 − F = ,( )
dt s
Component continuity for A:
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
d(VCA ) mol
F0 CA0 − FCA − kVCA = ,( )
dt s
Component continuity for B:
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction

42 | P a g e
 Time rate of change of moles
= [ ]
of jth component inside system
d(VCB ) mol
−FCB + kVCA = ,( )
dt s
Energy balance for reactor:
Flow of internal, kinetic and Flow of internal, kinetic and
[ potential energy into the ] − [ potential energy out ofthe ]
system by convection or diffusion system by convection or diffusion

Heat added to the system Work done by system

+ [by conduction, radiation and] − [on surrounding (Shaft ]
reaction. or PV work)
Time rate of change of
= [Internal, Kinetic and Potential]
inside system
d(ρVCp T)
F0 ρCp T0 + Fc ρCp T2 − FρCp T − FC ρCp T − kVCA λ =
dt
kVCA λ d(VT) Btu
F0 T0 + Fc (T2 − T) − FT − = ,( )
Cp ρ dt s
Energy balance for shell 1:
Flow of internal, kinetic and Flow of internal, kinetic and
[ potential energy into the ] − [ potential energy out ofthe ]
system by convection or diffusion system by convection or diffusion

Heat added to the system Work done by system

+ [by conduction, radiation and] − [on surrounding (Shaft ]
reaction. or PV work)
Time rate of change of
= [Internal, Kinetic and Potential]
inside system
d(ρw Vw Cpw Tw1 )
Fw ρw Cpw Tw0 − Fw ρw Cpw Tw1 + UA(T2 − Tw1 ) =
dt
UA(T2 − Tw1 ) dTw1 Btu
Fw Tw0 − Fw Tw1 + = Vw ,( )
ρw Cpw dt s
Energy balance for shell 2:
Flow of internal, kinetic and Flow of internal, kinetic and
[ potential energy into the ] − [ potential energy out ofthe ]
system by convection or diffusion system by convection or diffusion

Heat added to the system Work done by system

+ [by conduction, radiation and] − [on surrounding (Shaft ]
reaction. or PV work)
Time rate of change of
= [Internal, Kinetic and Potential]
inside system

43 | P a g e
 d(ρw Vw Cpw Tw2 )
Fw ρw Cpw Tw1 − Fw ρw Cpw Tw2 + UA(T1 − Tw2 ) =
dt
UA(T1 − Tw2 ) dTw2 Btu
Fw Tw1 − Fw Tw2 + = Vw ,( )
ρw Cpw dt s
Energy balance for tube 1:
Flow of internal, kinetic and Flow of internal, kinetic and
[ potential energy into the ] − [ potential energy out ofthe ]
system by convection or diffusion system by convection or diffusion

Heat added to the system Work done by system

+ [by conduction, radiation and] − [on surrounding (Shaft ]
reaction. or PV work)
Time rate of change of
= [Internal, Kinetic and Potential]
inside system
d(ρVT Cp T1 )
FC ρCp T − FC ρCp T1 − UA(T1 − Tw2 ) =
dt
UA(T1 − Tw2 ) dT1 Btu
FC T − FC T1 + = VT ,( )
ρCp dt s
Energy balance for tube 2:
Flow of internal, kinetic and Flow of internal, kinetic and
[ potential energy into the ] − [ potential energy out ofthe ]
system by convection or diffusion system by convection or diffusion

Heat added to the system Work done by system

+ [by conduction, radiation and] − [ surrounding (Shaft ]
on
reaction. or PV work)
Time rate of change of
= [Internal, Kinetic and Potential]
inside system
UA(T2 − Tw1 ) dT2 Btu
FC T1 − FC T2 + = VT ,( )
ρCp dt s
Arrhenius equation:
EA
k = k 0 exp (− )
RT
Also, from the figure it can be seen that the flowrate F is the function of the volume of the
contents inside the reactor. Thus, we can write,
F = f(V)
Also, the figure shows that the flowrate of cooling water is a function of temperature inside
the reactor.Hence, we can write,
Fw = f(T)

44 | P a g e
Problem 3.16
A semi-batch reactor is run at constant temperature by varying the rate of addition of one of
the reactants, A. The irreversible, exothermic reaction is first order in reactants A and B.
k
A+B→ C
The tank is initially filled to its 40 percent level with pure reactant B at a concentration CB0.
Maximum cooling water flow is begun, and reactant A is slowly added to the perfectly
stirred vessel.
Write the equations describing the system. Without solving the equations, try to sketch the
profiles of FA, CA, and CB with time during the batch cycle.

Solution:
Assumptions:
➢ Irreversible exothermic reaction.
➢ Tank is initially filled at 40% level.
➢ Vessel is perfectly mixed.
➢ Density and specific heat are constant.
➢ Steady state plug flow of cooling water at constant flowrate, FW.
Notations:
➢ h0 = Initial height of the reactants in the reactor.
➢ hmax= Maximum reactor height.
➢ h = Height at any given time t.
➢ λ = Exothermic heat of reaction.
Total continuity equation for the system:
Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
ρdV
FA ρA =
dt
ρAdh
FA ρA =
dt
On integrating the above equation, we get,
FA ρA t
h = h0 +
Aρ

45 | P a g e
But it is given that h0 = 0.4 hmax. Hence, the equation becomes,
FA ρA t
h = 0.4hmax + , (ft)
Aρ
Component balance for A:
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
d(VCA )
F0 CA0 − kVCA CB =
dt
d(hCA )
F0 CA0 − kVCA CB = A
dt
dCA dh
F0 CA0 − kCA CB Ah = A [h + CA ]
dt dt
On substituting for h from eq. (1), we get,
FA ρA t
F0 CA0 − kCA CB A [0.4hmax + ]
Aρ
FA ρA t dCA FA ρA A mol
= A [0.4hmax + ] + CA ,( )
Aρ dt Aρ s
Component Balance for B:
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
d(VCB )
−kVCA CB =
dt
d(hCB )
−kCA CB Ah = A
dt
dCB dh
−kCA CB Ah = A [h + CB ]
dt dt
On substituting for h from eq. (1), we get,
FA ρA t FA ρA t dCB FA ρA A mol
−kCA CB A [0.4hmax + ] = A [0.4hmax + ] + CB ,( )
Aρ Aρ dt Aρ s
Component Balance for C:
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
d(VCC )
kVCA CB =
dt
d(hCC )
kCA CB Ah = A
dt

46 | P a g e
 dCC dh
kCA CB Ah = A [h + CC ]
dt dt
On substituting for h from eq. (1), we get,
FA ρA t FA ρA t dCC FA ρA A mol
kCA CB A [0.4hmax + ] = A [0.4hmax + ] + CC ,( )
Aρ Aρ dt Aρ s
Energy balance for reactor:
Flow of internal, kinetic and Flow of internal, kinetic and
[ potential energy into the ] − [ potential energy out ofthe ]
system by convection or diffusion system by convection or diffusion

Heat added to the system Work done by system

+ [by conduction, radiation and] − [ surrounding (Shaft ]
on
reaction. or PV work)
Time rate of change of
= [Internal, Kinetic and Potential]
inside system
Tw,in + Tw,out d(ρAhCp T)
FA ρA CpA TA − kλCA CB Ah − UA (T − ) =
2 dt
Tw,in + Tw,out dT Btu
FA ρA CpA TA − kλCA CB Ah − UA (T − ) = ρAhCp ,( )
2 dt s
Energy balance for cooling water:
Flow of internal, kinetic and Flow of internal, kinetic and
[ potential energy into the ] − [ potential energy out ofthe ]
system by convection or diffusion system by convection or diffusion

Heat added to the system Work done by system

+ [by conduction, radiation and] − [ surrounding (Shaft ]
on
reaction. or PV work)
Time rate of change of
= [Internal, Kinetic and Potential]
inside system
Tw,in + Tw,out Btu
Fw ρw Cpw Tw,in − Fw ρw Cpw Tw,out + UA (T − ) = 0 ,( )
2 s
Also, from the figure it can be seen that the flowrate of inlet stream is a function of
temperature inside the reactor. Hence, we can write,
FA = f(T)
Now, we have 7 unknowns (FA , h , CA , CB , CC , T , Tw,out) and 7 equations (eq. 1 to 7).
Hence, our system is satisfied.
Initially, the reactor is only filled with B and hence, its concentrations is very high at the start.
Therefore, as soon as any A will enter the reactor, it will rapidly react with B and get
consumed. Hence, the concentration of A will remain negligible when the process starts.
Now, as the time proceeds the reactant B will get consumed and its concentration inside the
reactor will drop. So, in order to maintain good rate of reaction the, the concentration of A
will need to be increased and this can be done by increasing the flowrate of stream A. Hence,
the flowrate of A and the concentration of A will start increasing.

47 | P a g e
Problem 3.17
Develop a mathematical model of the three-column train of distillation columns sketched in
Figure 17. The feed to the first column is 400 kg*mol/h and contains four components (1, 2,
3, and 4) each at 25 mol %. Most of the lightest component is removed in the distillate of the
first column, most of the next lightest in the second column distillate and the final column
separates the final two heavy components. Assume constant relative volatilities throughout
the system: α1, α2, and α3. The condensers are total condensers and the reboilers are partial.
Trays, column bases, and reflux drums are perfectly mixed. Distillate flow rates are set by
reflux drum level controllers. Reflux flows are fixed. Steam flows to the reboilers are set by
temperature controllers. Assume equimolal overflow, negligible vapor holdup, and negligible
condenser and reboiler dynamics. Use a linear liquid hydraulic relationship:
Mn − Mn
Ln = Ln +
β
where Ln and Mn are the initial steady state liquid rate and holdup and β is a constant with
unit of seconds.

Solution:
Assumptions:
➢ Liquid phase is perfectly mixed.
➢ The composition of the vapour and liquid leaving the plates will be in equilibrium.
➢ Negligible vapour holdup. Hence, the molar flowrate of vapour through each plate is
equal.

48 | P a g e
 ➢ Equimolal overflow.
➢ Negligible heat losses and sensible heat effects.
➢ Negligible dynamics of reboiler and condenser.
➢ Constant reflux rate.

Notations:
➢ F= Feed rate(mol/min)
➢ V= Vapour rate(mol/min)
➢ Ln= Liquid rate from nth plate(mol/min)
➢ Mn= Liquid holdup on nth plate(mol)
➢ MD= Reflux drum holdup(mol)
➢ MB= Bottom holdup(mol)
➢ FW= Flowrate of steam(mol/min)
➢ λW= Latent heat of condensation of steam.
➢ Subscript i represents the ith distillation column (i = 1, 2, 3).

As all the three distillation column are identical, the modelling equations for all three
distillation columns will be the same.

Total continuity equation for condenser and reflux drum:

Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
dMD
[V − R − D = ]
dt i
Total continuity equation for condenser and reflux drum for the more volatile component:
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
dMD xD
[VyNT − RxD − DxD = ]
dt i
Total continuity equation for top tray (n = NT):
Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
dMNT
[R − LNT = ]
dt i
Total continuity equation for top tray for the more volatile component:
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
dMNT xNT
[RxD − LNT xNT + VyNT−1 − VyNT − DxD = ]
dt i
Total continuity equation for next to top top tray (n = NT - 1):

49 | P a g e
 Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
dMNT−1
[LNT − LNT−1 = ]
dt i
Total continuity equation for next to top tray for the more volatile component:
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
dMNT−1 xNT−1
[ LNT xNT − LNT−1 xNT−1 + VyNT−2 − VyNT−1 = ]
dt i
Total continuity equation for nth tray:
Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
dMn
[Ln+1 − Ln = ]
dt i
Total continuity equation for nth tray for the more volatile component:
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
dMn xn
[ Ln+1 xn+1 − Ln xn + Vyn−1 − Vyn = ]
dt i
Total continuity equation for feed tray:
Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
dMNF
[LNF+1 − LNF + F = ]
dt i
Total continuity equation for feed tray for the more volatile component:
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
dMn xn
[ LNF+1 xNF+1 − LNF xNF + VyNF−1 − VyNF + Fz = ]
dt i
Total continuity equation for first tray:
Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
dM1
[L2 − L1 = ]
dt i
Total continuity equation for feed tray for the more volatile component:

50 | P a g e
 Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
dM1 x1
[ L2 x2 − L1 x1 + VyB − Vy1 = ]
dt i
Total continuity equation for reboiler and column base:
Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
dMB
[L1 − V − B = ]
dt i
Total continuity equation reboiler for the more volatile component:
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
dMB xB
[ L1 x1 − VyB − BxB = ]
dt i
Energy balance for the reboiler:
Flow of internal, kinetic and Flow of internal, kinetic and
[ potential energy into the ] − [ potential energy out ofthe ]
system by convection or diffusion system by convection or diffusion

Heat added to the system Work done by system

+ [by conduction, radiation and] − [on surrounding (Shaft ]
reaction. or PV work)
Time rate of change of
= [Internal, Kinetic and Potential]
inside system
[ L1 CP T − V(CP T + λ) − BCP T + FW λW = 0]i
The inlet and outlet temperature from the reboiler will be the same as we are neglecting the
sensible heat effects.
From the figure it can be seen that D is the function of MD , B is the function of MB and FW
is the function of temperature inside the column. Also, Ln is the function of Mn. Therefore,
[ D = f(MD )]i
[ B = f(MB )]i
[ FW = f(T)]i
[ Ln = f(Mn )]i
The composition of the vapour will be the function of liquid composition and temperature
as they are in equilibrium. Therefore,
[ y = f(x, T)]i

Unknowns Equations
Tray Composition(xn and yn) 2NT Tray continuity NT
Tray Total Continuity NT Tray component continuity NT
Tray liquid holdup(Mn) NT Equilibrium relation(Tray + Base) NT + 1

51 | P a g e
 Reflux drum Composition(xD) 1 Hydraulic for Ln NT
Reflux Drum flow(D) 1 Level controller for D and B 2
Reflux Drum holdup(MD) 1 Reflux component continuity 1
Base Composition(xB , yB) 2 Reflux total continuity 1
Base flows(V, B) 2 Base component continuity 1
Base Holdup(MB) 1 Base total continuity 1
Steam Flowrate(FW) 1 Steam Flowrate control 1
Total 4NT + 1 Energy equation of reboiler 1
Total 4NT + 1
Therefore, we have (4NT + 1) equations and (4NT + 1) unknowns.

Problem 3.18
The rate of pulp lay down F on a paper machine is controlled by controlling both the pressure
P and the height of slurry h in a feeder drum with cross sectional area A. F is proportional to
the square root of the pressure at the exit slit. The air vent rate G is proportional to the square
root of the air pressure in the box P. Feedback controllers set the inflow rates of air G0 and
slurry F0 to hold P and h. The system is isothermal. Derive a dynamic mathematical model
describing the system.

Solution:
Assumptions:
➢ F is proportional to the square root of pressure at the exit slit.
➢ Air vent rate G is proportional to the square root of the air pressure in the box.
➢ Isothermal system.
➢ Constant density of slurry.
Notations:
➢ H = Total height of the vessel.
➢ ρ0 = Density of inlet air.
➢ ρ = Density of air inside the vessel.
➢ P = Pressure of air inside the vessel.
➢ ρS = Density of slurry.
➢ VT = Total volume of the vessel.
➢ V = Volume occupied by the slurry.

Total continuity equation for the slurry:

Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system

52 | P a g e
 ρs dV
F0 ρs − Fρs =
dt
dh
F0 − F = A
dt
Total pressure at the bottom of the vessel = ρs gh + P. Hence, as per our assumption,

F = K F √ρs gh + P
dh ft 3
F0 − K F √ρs gh + P = A ,( )
dt s
Total continuity equation for the air:
Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
d[ρ(VT − V)]
G0 ρ0 − Gρ =
dt
As per our assumption,
G = K G √P.

d[ρ(H − h)] lb
G0 ρ0 − ρK G √P = A ,( )
dt s
According to the ideal gas equation,

ρ = PM⁄RT , (Psia)
Also, from the figure given in the question it can be seen that the gas flowrate G0 is the
function of the pressure, P and the liquid flowrate F0 is the function of height, h. Hence, we
can write,
G0 = f(P)
F0 = f(h)
Therefore, we have 5 unknowns (F0 , G0 , P , h , ρ) and 5 equations (eq. 1 to 5).

Problem 3.19
A wax filtration plant has six filters that operate in parallel, feeding from one common feed
tank. Each filter can handle 1000 GPM when running, but the filters must be taken off line
every six hours for a cleaning procedure that takes ten minutes. The operating schedule calls
for one filter to be cleaned every hour.
How many gallons a day can the plant handle? If the flow rate into the feed tank is held
constant at this average flow rate, sketch how the liquid level in the feed tank varies over a
typical three-hour period.

Solution:
Assumptions:
➢ Constant and equal feed rate to each filter.
➢ Cleaning procedure takes 10 minutes.
➢ Every hour one tank is cleaned.

53 | P a g e
We have been given that after every one hour, one of the six filters is cleaned and it takes
10 minutes to clean it. Therefore, if we consider the basis of 1 hour, then five out of the six
tanks will be working for complete one hour while the remaining one tank will only work
for 50 minutes as 10 minutes will be consumed in cleaning it.
Therefore, the capacity of the filters is,
5(tanks) ∗ 1000(GPM) ∗ 60(min⁄hr) + 1(tank) ∗ 1000(GPM) ∗ 50(min⁄hr)
C=
60(min⁄hr)
= 5833.333 GPM
Therefore, a plant can handle,
5833.333(GPM) ∗ 60(min⁄hr) ∗ 24 (hr⁄day) = 8400000 gallons per day.

Now, for every one hour, suppose that one of the tanks is being cleaned for the first 10
minutes. Therefore, only 5 filters will be running during this time interval of 10 minutes.
Hence, by

Total continuity equation for the feed tank:

Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
5833.333 − 5 ∗ 1000 = Accumation rate
Accumulation rate = 833.333 GPM
This accumulation will be taking place only for the first 10 minutes during which one of the
tanks is being cleaned.
Therefore, total accumulation during the first 10 minutes = 833.333*10 = 8333.33 gallons.
Now, once the tank is cleaned after 10 minutes and it also comes into working, this
accumulated amount will slowly start decreasing and finally the net accumulation at the end
of one hour will become zero. Hence, the profile will look like as follows.

Problem 3.20
Alkylation is used in many petroleum refineries to react unsaturated butylene with
isobutane to form high octane iso octane (alkylate). The reaction is carried out in a two
liquid phase system: sulfuric acid/hydrocarbon.
The butylene feed stream is split and fed into each of a series of perfectly mixed tanks
(usually in one large vessel). This stepwise addition of butylene and the large excess of
isobutane that is used both help to prevent undesirable reaction of butylene molecules with
each other to form high boiling, low octane polymers. Low temperature (40 ◦F) also favours

54 | P a g e
the desired reaction. The reaction is exothermic. One method of heat removal that is
often used is auto-refrigeration: the heat of vaporization of the boiling hydrocarbon liquid
soaks up the heat of reaction.
The two liquid phases are completely mixed in the agitated sections, but in the last section
the two phases are allowed to separate so that the acid can be recycled and the hydrocarbon
phase sent off to a distillation column for separation.
Derive a dynamic mathematical model of the reactor.

k1
iC4 + C4= → iC8
k2
C4= → Polymer
Solution:
Assumptions:
➢ Perfectly mixed vessels.
➢ Constant density.
➢ Exothermic reaction.
➢ Heat removal is due to boiling of hydrocarbons.
➢ Vapour phase does not contain any polymer and acid.
➢ Two phases are completely separated in the last section.
Notations:
➢ Subscript iC4 represents isobutane.
➢ Subscript C4 represents butylene.
➢ Subscript iC8 represents iso-octane.
➢ Subscript Poly represents Polymer.
➢ Subscript n represents nth reactor.
➢ Subscript Vn represents vapour from nth reactor.
➢ Subscript AC represents Acid.
➢ λ1 and λ2 represents the heat of reaction with rate constant k1 and k2.
➢ λ is the latent heat of vaporisation of hydrocarbon solution.
➢ VT is the total volume occupied by the acid and hydrocarbon in the last separating
section
➢ VAC is the volume occupied by the acid alone in the last separating section.

55 | P a g e
 ➢ FHC is the flowrate of the hydrocarbon stream from the separating section.
Total continuity equation for the 1st reactor:
Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
ρ1 dV1 lb
FiC4 ρiC4 + FC4 ρC4 + FAC ρAC − F1 ρ1 − FV1 ρV = ,( )
dt s
Component balance for iC4 in 1st reactor:
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
d(VCiC4 )1 mol
FiC4 CiC4 − (FCiC4 )1 − (FCiC4 )V1 − (k1 VCiC4 CC4 )1 = ,( )
dt s
Component balance for C4 in 1st reactor:
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
d(VCC4 )1 mol
FC4 CC4 − (FCC4 )1 − (FCC4 )V1 − (k1 VCiC4 CC4 )1 − (k 2 VCC4 )1 = ,( )
dt s

Component balance for iC8 in 1st reactor:

Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
d(VCiC8 )1 mol
− (FCiC8 )1 − (FCiC8 )V1 + (k1 VCiC4 CC4 )1 = ,( )
dt s
Component balance for Polymer in 1st reactor:
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system

d(VCPoly ) mol
1
−(FCPoly ) + (k 2 VCC4 )1 = ,( )
1 dt s
Component balance for Acid in 1st reactor:
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction

56 | P a g e
 Time rate of change of moles
= [ ]
of jth component inside system
d(VCAC )1 mol
FAC − (FCAC )1 = ,( )
dt s
Energy Balance for 1st reactor:
Flow of internal, kinetic and Flow of internal, kinetic and
[ potential energy into the ] − [ potential energy out ofthe ]
system by convection or diffusion system by convection or diffusion

Heat added to the system Work done by system

+ [by conduction, radiation and] − [ surrounding (Shaft ]
on
reaction. or PV work)
Time rate of change of
= [Internal, Kinetic and Potential]
inside system

(FρCp T) + (FρCp T) − (FρCp T) − [Fρ(Cp T + λ)]V1 − (k1 λ1 VCiC4 CC4 )1 − (k 2 λ2 VCC4 )1

iC4 C4 1
d [(VρCp T) ] Btu
1
= ,( )
dt s
th
Total continuity equation for n reactor (n = 2, 3, 4):
Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
ρn dVn
F(n−1) ρ(n−1) − Fn ρn − FVn ρV =
dt
Component balance for iC4 in nth reactor (n = 2, 3, 4):
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
d(VCiC4 )n mol
(FCiC4)n−1 − (FCiC4 )n − (FCiC4 )Vn − (k1 VCiC4 CC4 )n = ,( )
dt s

Component balance for C4 in nth reactor (n = 2, 3, 4):

Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
d(VCC4 )n mol
(FCC4 )n−1 − (FCC4 )n − (FCC4 )Vn − (k1 VCiC4 CC4 )n − (k 2 VCC4 )n = ,( )
dt s

Component balance for iC8 in nth reactor (n = 2, 3, 4):

57 | P a g e
 Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
d(VCiC8 )n mol
(FCiC8 )n−1 − (FCiC8 )n − (FCiC8 )Vn + (k1 VCiC4 CC4 )n = ,( )
dt s
Component balance for Polymer in nth reactor (n = 2, 3, 4):
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system

d(VCPoly ) mol
n
(FCPoly ) − (FCPoly ) + (k 2 VCC4 )n = ,( )
n−1 n dt s
Component balance for Acid in nth reactor (n = 2, 3, 4):
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system
d(VCAC )n mol
(FCAC )n−1 − (FCAC )n = ,( )
dt s
Energy Balance for 1st reactor:
Flow of internal, kinetic and Flow of internal, kinetic and
[ potential energy into the ] − [ potential energy out ofthe ]
system by convection or diffusion system by convection or diffusion

Heat added to the system Work done by system

+ [by conduction, radiation and] − [on surrounding (Shaft ]
reaction. or PV work)
Time rate of change of
= [Internal, Kinetic and Potential]
inside system

(FρCp T) − (FρCp T) − [Fρ(Cp T + λ)]Vn − (k1 λ1 VCiC4 CC4 )n − (k 2 λ2 VCC4 )n

n−1 n
d [(VρCp T) ]
Btu n
= ,( )
dt s
Component balance for Hydrocarbon in the separating section:
Flow of moles of jth Flow of moles of jth Rate of formation of moles
[ ]− [ ] + [ th ]
component into system component out of system of j component by reaction
Time rate of change of moles
= [ ]
of jth component inside system

[F( CiC4 + CC4 + CiC8 + CPoly )]4 − FHC =

d[( CiC4 + CC4 + CiC8 + CPoly )(VT − VAC )] mol
= ,( )
dt s

58 | P a g e
Total continuity equation for the vapours:
Mass Flow into Mass flow out Time rate of change
[ ]− [ ]= [ ]
the system of the system mass inside the system
d(ρV VV ) lb
(FV1 + FV2 + FV3 + FV4 − FV )ρV = ,( )
dt s
Assuming the vapours to be ideal gas, we can write,
PM
ρV =
RT
Molar mass of the vapour(M) will be the function of vapour composition (CV). Therefore,
M = f(CV )
The density(ρn) of the of the reaction mixture inside the nth reactor will be the function of the
composition (Cn) of the nth reactor. Therefore,
ρn = f(Cn )
The specific heat (Cpn) of the of the reaction mixture inside the nth reactor will be the function
of the composition (Cn) of the nth reactor. Therefore,
Cpn = g(Cn )
The outlet vapour flowrate is the function of pressure(P) inside the vessel. Therefore,
FV = f(P)
The Hydrocarbon flowrate (FHC) is the function of volume (VT) inside the separating section.
Hence,
FHC = f(VT )
The rate constant(k) is related to the temperature by Arrhenius equation. Therefore,
k = k 0 exp (−EA ⁄RT)
Now, we have 23 unknowns [F1 , FV1 , ρn , V1 , ρV , (CiC4)1 , (CiC4)V1 , (CiC8)1 , (CPoly)1 ,
(CAC)1 , T1 , CPn , Fn , FVn , Vn , (CiC4)n , (CiC4)Vn , (CiC8)n , (CPoly)n , (CAC)n , Tn , k0 , M] and
23 equations (eq. 1 to 23).

Problem 3.21
Benzene is nitrated in an isothermal CSTR in three sequential irreversible reactions
k1
Benzene + HNO3 → Nitrobenzene + H2 O
k2
Nitrobenzene + HNO3 → dinitrobenzene + H2 O
k3
Di − nitrobenzene + HNO3 → tri − nitrobenzene + H2 O
Assuming each reaction is linearly dependent on the concentrations of each reactant, derive a
mathematical model of the system. There are two feed streams, one pure benzene and one
concentrated nitric acid (98 wt %). Assume constant densities and complete miscibility.
Solution:
Assumptions:

59 | P a g e
 ➢ Each reaction is linearly dependent on the concentrations of each reactant, i.e
−rB = k1 CB CHNO3
−rHNO3 = k1 CB CHNO3 + k 2 Cnitro CHNO3 + k 3 Cⅆi−nitro CHNO3
−rnitro = − k1 CB CHNO3 + k 2 Cnitro CHNO3
−rⅆi−nitro = − k 2 Cnitro CHNO3 + k 3 Cⅆi−nitro CHNO3
−rtri−nitro = − k 3 Cⅆi−nitro CHNO3
➢ Two feed streams of pure benzene and concentrated nitric acid (98 wt %).
➢ Density is constant throughout the reactions
➢ Complete miscibility
Notations:
➢ V = Volume of the CSTR
➢ FHNO3 = Flow rate of concentrated nitric acid stream
➢ FB = Flow rate of benzene
➢ F = Flow rate of the outlet stream
Total continuity equation:
[Mass flow intothe system] − [Mass flow out of the system]
= [Time rate of change of mass inside the system]
ⅆ(Vρ)
FHNO3 ρ1 − FB ρ2 − Fρ = ⅆt

Since density is constant, the above equation changes to

ⅆ(V)
FHNO3 − FB − F = ⅆt

Component Continuity Equation:

[Inflow of component j]
= [Outflow of component j] + [Rate of consumption of component j ]
+ [Rate of change of component j inside system ]
Benzene:
d(VCB )
= FB CBo − FCB − Vk1 CB CHNO3
dt
HNO3:
d(VCHNO3 )
= FHNO3 CHNO3,i − FCHNO3 − V(k1 CB CHNO3 + k 2 Cnitro CHNO3 + k 3 Cⅆi−nitro CHNO3 )
dt
Nitrobenzene:
d(VCnitro )
= FCnitro − V(− k1 CB CHNO3 + k 2 Cnitro CHNO3 )
dt
Di-nitrobenzene:

60 | P a g e
 d(VCⅆi−nitro )
= FCⅆi−nitro − V(− k 2 Cnitro CHNO3 + k 3 Cⅆi−nitro CHNO3 )
dt
Tri-nitrobenzene:
d(VCtri−nitro )
= FCtri−nitro − V(− k 3 Cⅆi−nitro CHNO3 )
dt
Now, we have 6 unknowns (F, CB , CHNO3 , Cnitro, Cdi-nitro, Ctri-nitro) and 6 equations from (1) to
(6). Therefore, the system is sufficiently specified.

61 | P a g e
CHAPTER 5

62 | P a g e
Problem 5.1
Consider an isothermal batch reactor for a given conversion of the reactant
aA + bB → cC + dD ….. (1)
where component A is the limiting reactant. The stoichiometric coefficients are: a = 1; b = 2,
c = 1 and d = 0. The initial moles of components A, B, C and D are NA = 0.001 gmol, NB =
0.003 gmol, NC = 0.0 gmol, ND = 0.0 gmol, respectively. A mixture of A and B is charged
into a 1-litre reactor. Determine the holding time to achieve 90% fractional conversion of A
(XA = 0.9). The rate constant is k = 1.0 * 105 [(liter)2/(gmol2.min)] and the reaction is first
order in A, second order in B and third order overall.
Solution:
Assuming a constant volume batch system, and substituting the values of stoichiometric
coefficients in (1), we get
k
A + 2B → C
where A is the limiting reactant.
The material balance of component A in the batch reactor is
1 dNA
−rA = −
V dt
where the concentration CA = NA/VR
ⅆCA
−rA = − = kCA CB 2 ….. (2)
ⅆt

The concentrations of A and B can be expressed in terms of the fractional conversion and the
stoichiometry of the reaction as:
Component A B
At time t = 0 CAo CBo
At time t = t CA CB
Amount reacted (CAo - CA) (CBo – CB)

From the stoichiometry,

2(CAo − CA ) = (CBo − CB )
The concentration of B is expressed as
CB = CBo − 2 (CAo − CA ) ….. (3)
CAo −CA
Using the fractional conversion XA at constant volume, XA = CAo

Therefore, the amount reacted, CAo − CA = CAo X A …... (4)

Or CA = CAo (1 − XA ) …… (5)
Differentiating equation (4), −dCA = CAo dXA …… (6)
Substituting equations (3),(5),(6) in (2), we get

63 | P a g e
 dXA
CAo = kCAo (1 − XA ){CBo − 2(CAo − CA )}2
dt
= kCAo (1 − XA )(CBo − 2CAo XA )2
dXA CBo
CAo = kCAo (1 − XA ) {CAo ∗ [ − 2XA ]}2
dt CAo
ⅆXA
= kCAo 2 (1 − XA ) (M − 2XA )2 …… (7)
ⅆt
C
where M = CBo.
Ao

Rearranging equation (7) and integrating between the limits t = 0, XA = 0 and t = t holding time,
XA = 0.9, gives
0.9 ⅆXA t=t
∫0 = kCAo 2 ∫t=0 holding time dt …… (8)
(1−XA )(M−2XA )2

The integral on the left side of equation 8 can be expressed by partial fraction to give
1 A B C
≡ + + …… (9)
(1−XA )(M−2XA )2 1−XA M−2XA (M−2XA )2

Rearranging Eq (9) gives

1 ≡ A(M − 2XA )2 + B(1 − XA )(M − 2XA ) + C(1 − XA ) …… (10)
Putting XA = 1 into equation (10),
1
A = (M−2)2 …… (11)

Putting XA = 0 into equation (10),

1 = AM 2 + BM + C …… (12)
Putting XA = M/2 into equation (10)
M 2
1 = C (1 − 2 ) ⇒ C = 2−M …… (13)

Substituting equations (11), (13) in equation (12)

M2 2 −2
1 = (M−2)2 + BM + 2−M ⇒ B = (M−2)2

The integral of equation (9) between the limits becomes

0.9 ⅆXA
I = ∫0 (1−XA )(M−2XA )2

1 X ⅆX 2 X ⅆX 2 X ⅆX
= (M−2)2 ∫0 A 1−XA − (M−2)2 ∫0 A M−2X
A
+ 2−M ∫0 A (M−2XA 2
…… (14)
A A A)

1 XA 1 XA 1 1 X
I=− 2
[ln(1 − X A )] 0 + 2
[ln(M − 2X A )] 0 + [ ]0 A
(M − 2) (M − 2) 2 − M M − 2XA
Or
1 (M − 2XA ) 2XA (M − 2)
I= 2
[ln { } − ] = kCAo 2 t holⅆing time
(M − 2) M(1 − XA ) M(M − 2XA )

64 | P a g e
The holding time, t holⅆing time is given by the expression
1 (M−2X ) 2XA (M−2)
t holⅆing time = 2 [ln {M(1−XA )} − ] …… (15)
kCAo (M−2)2 A M(M−2XA )

Given V = 1 litre,
NAo gmol NBo gmol C
CAo = = 0.001 , CBo = = 0.003 , M = CBo = 3 , XA = 0.9,
V L V L Ao

k = 1.0*105 [(L)2/(gmol2.min)]
Substituting the above values in equation (15), we get
1 (3 − 2 ∗ 0.9) 2 ∗ 0.9 ∗ (3 − 2)
t holⅆing time = [ln { }− ]
105 2
∗ (0.001) (3 − 2) 2 3(1 − 0.9) 3(3 − 2 ∗ 0.9)
= 8.86 min.
Therefore, it would take approximately 8.86 minutes to convert 90% of reactant A charged to
the 1L reactor.

Problem 5.2
Determine the conversion for a reaction taking place in an isothermal batch reactor,
aA + bB → cC + dD ….. (1)
where component A is the limiting reactant. The stoichiometric coefficients are: a = 1; b = 2,
c = 1 and d = 0. The initial moles of components A, B, C and D are NA = 0.001 gmol, NB =
0.003 gmol, NC = 0.0 gmol, ND = 0.0 gmol, respectively. A mixture of A and B is charged
into a 1-litre reactor operating 4 minutes. The rate constant is k = 1.0 * 105
[(liter)2/(gmol2.min)] and the reaction is first order in A, second order in B and third order
overall.
Solution:
Assuming a constant volume batch system, and substituting the values of stoichiometric
coefficients in (1), we get
k
A + 2B → C
where A is the limiting reactant.
The material balance of component A in the batch reactor is
1 dNA
−rA = −
V dt
where the concentration CA = NA/VR
ⅆCA
−rA = − = kCA CB 2 ….. (2)
ⅆt

The concentrations of A and B can be expressed in terms of the fractional conversion and the
stoichiometry of the reaction as:

65 | P a g e
 Component A B
At time t = 0 CAo CBo
At time t = t CA CB
Amount reacted (CAo - CA) (CBo – CB)

From the stoichiometry,

2(CAo − CA ) = (CBo − CB )
The concentration of B is expressed as
CB = CBo − 2 (CAo − CA ) ….. (3)
CAo −CA
Using the fractional conversion XA at constant volume, XA = CAo

Therefore, the amount reacted, CAo − CA = CAo X A …... (4)

Or CA = CAo (1 − XA ) …… (5)
Differentiating equation (4), −dCA = CAo dXA …… (6)
Substituting equations (3), (5), (6) in (2), we get
dXA
CAo = kCAo (1 − XA ){CBo − 2(CAo − CA )}2
dt
= kCAo (1 − XA )(CBo − 2CAo XA )2
dXA CBo
CAo = kCAo (1 − XA ) {CAo ∗ [ − 2XA ]}2
dt CAo
ⅆXA
= kCAo 2 (1 − XA ) (M − 2XA )2 …… (7)
ⅆt
C
where M = CBo.
Ao

Rearranging equation (7) and integrating between the limits t = 0, XA = 0 and t = t holding time,
XA = 0.9, gives
0.9 ⅆXA t=t
∫0 = kCAo 2 ∫t=0 holding time dt …… (8)
(1−XA )(M−2XA )2

The integral on the left side of equation 8 can be expressed by partial fraction to give
1 A B C
≡ + + …… (9)
(1−XA )(M−2XA )2 1−XA M−2XA (M−2XA )2

Rearranging Eq (9) gives

1 ≡ A(M − 2XA )2 + B(1 − XA )(M − 2XA ) + C(1 − XA ) …… (10)
Putting XA = 1 into equation (10),
1
A = (M−2)2 …… (11)

Putting XA = 0 into equation (10),

1 = AM 2 + BM + C …… (12)

66 | P a g e
Putting XA = M/2 into equation (10)
M 2
1 = C (1 − 2 ) ⇒ C = 2−M …… (13)

Substituting equations (11), (13) in equation (12)

M2 2 −2
1 = (M−2)2 + BM + 2−M ⇒ B = (M−2)2

The integral of equation (9) between the limits becomes

0.9 ⅆXA
I = ∫0 (1−XA )(M−2XA )2

1 X ⅆX 2 X ⅆX 2 X ⅆX
= (M−2)2 ∫0 A 1−XA − (M−2)2 ∫0 A M−2X
A
+ 2−M ∫0 A (M−2XA 2
…… (14)
A A A)

1 1 1 1
I=− [ln(1 − XA )]X0 A + [ln(M − 2XA )]X0 A + [
X
] A
(M − 2) 2 (M − 2) 2 2 − M M − 2XA 0
Or
1 (M − 2XA ) 2XA (M − 2)
I= 2
[ln { } − ] = kCAo 2 t holⅆing time
(M − 2) M(1 − XA ) M(M − 2XA )
The holding time, t holⅆing time is given by the expression
1 (M−2X ) 2XA (M−2)
t holⅆing time = 2 [ln {M(1−XA )} − ] …… (15)
kCAo (M−2)2 A M(M−2XA )

Taking an initial guess for the fractional conversion XA, guess 1 = 0.8 and substituting in
equation (15),
1 (3 − 2 ∗ 0.8) 2 ∗ 0.8 ∗ (3 − 2)
t holⅆing time = 5 2 2
[ln { }− ]
10 ∗ (0.001) (3 − 2) 3(1 − 0.8) 3(3 − 2 ∗ 0.8)
we get t holⅆing time = 4.663 minutes , which is greater than the required holding time,
t holⅆing time = 4 minutes.
Taking a second guess for the fractional conversion XA, guess 2 = 0.7 and substituting in
equation (15),
1 (3 − 2 ∗ 0.7) 2 ∗ 0.7 ∗ (3 − 2)
t holⅆing time = 5 2 2
[ln { }− ]
10 ∗ (0.001) (3 − 2) 3(1 − 0.7) 3(3 − 2 ∗ 0.7)
we get t holⅆing time = 2.837 minutes , which is less than the required holding time,
t holⅆing time = 4 minutes.
Taking a third guess for the fractional conversion XA, guess 3 = 0.75 and substituting in equation
(15),
1 (3 − 2 ∗ 0.75) 2 ∗ 0.75 ∗ (3 − 2)
t holⅆing time = [ln { } − ]
105 ∗ (0.001)2 (3 − 2)2 3(1 − 0.75) 3(3 − 2 ∗ 0.75)
we get t holⅆing time = 3.598 minutes , which is less than the required holding time,
t holⅆing time = 4 minutes.

67 | P a g e
Taking a fourth guess for the fractional conversion XA, guess 4 = 0.775 and substituting in
1 (3−2∗0.775) 2∗0.775∗(3−2)
equation (15), t holⅆing time = 105 ∗(0.001)2(3−2)2 [ln { 3(1−0.775) } − 3(3−2∗0.775) ]

we get t holⅆing time = 4.083 minutes , which is greater than the required holding time,
t holⅆing time = 4 minutes.
Taking a fifth guess for the fractional conversion XA, guess 5 = 0.771 and substituting in
1 (3−2∗0.771) 2∗0.771∗(3−2)
equation (15), t holⅆing time = 105 ∗(0.001)2(3−2)2 [ln { 3(1−0.771) } − 3(3−2∗0.771) ]

we get t holⅆing time = 3.9995 minutes , which is approximately equal to the required
holding time, t holⅆing time = 4 minutes.
Therefore, the fractional conversion XA for the 4-min isothermal batch operation is 77.1%,
and this answer is obtained by trial-and-error method.

Problem 5.3
k
Gas A decomposes irreversibly to form gas B according to the reaction A → 2B,
−rA = kCA 2
The reaction is second order and is performed in an isothermal constant pressure batch
reactor. Determine the conversion with time for the reaction assuming that A and B are ideal
gases, and starting with pure A at NAo. Derive a general expression for time t in terms of the
k
fractional conversion XA for an nth order reaction expressed by A → bB
Solution:
Since the volume depends on conversion or time in a constant pressure batch reactor,
consider the mole balance in relation to the fractional conversion XA. From the stoichiometry,
Component A B
At time t = 0 NAo 0
At time t = t NA NB
Amount reacted NAo − NA NB

From the stoichiometry,

2(NAo − NA ) = NB
NAo −NA
The fractional conversion, XA = NAo

Therefore, the amount reacted, NAo − NA = NAo X A …... (1)

Or NA = NAo (1 − XA ) …… (2)
Differentiating equation (4), dNA = −NAo dXA …… (3)
Therefore, the amount of component B is
NB = 2NAo XA …… (4)

68 | P a g e
ꜪA is the fractional change in volume of the system between no conversion and complete
conversion of reactant A, and is given by
VXA =1 − VXA =0
∈A =
VXA =0
k 2 −1
For the gas phase reaction A → 2B, ∈A = =1
1

We know that V = Vo (1 +∈A XA ) …… (5)

Since two moles of B are formed for every mole of A that disappears, then the mole balance
table becomes
Component Mole initially at time t = 0 Moles at t = t
A NAo NA = NAo (1 − XA )
B 0 2NAo XA
Total moles NAo NAo (1 + XA )
Volume V0 Vo (1 + XA )

The batch reactor design equation for component A is

1 ⅆNA
−rA = − V = kCA 2 …… (6)
ⅆt

Substituting equations (2), (3), (5) in equation (6), we get

NAo dXA NAo (1 − XA ) 2
−rA = = k{ }
Vo (1 +∈A XA ) dt Vo (1 +∈A XA )
Put ∈A = 1 in the above equation,
NAo ⅆXA NAo (1−XA )
−rA = V = k{ }2 …… (7)
o (1+XA ) ⅆt Vo (1+XA )

Re-arranging equation (7),

(1+XA ) ⅆXA NAo
=k dt …… (8)
(1−XA )2 VO

Integrating equation (8) between the limits of fractional conversion t = 0, XA = 0 and t = t, XA

= XA gives,
XA (1+XA ) ⅆXA NAo t
∫0 =k ∫0 dt …… (9)
(1−XA )2 VO

Expressing the left side of the equation (9) into partial fraction give
1+ XA A B
I= ≡ + (1−X …… (10)
(1−XA )2 1−XA A)
2

1 + XA = A(1 − XA ) + B …… (11)
Put XA = 1 into equation (11) gives B = 2
Put XA = 0 into equation (11), gives A + B = 1 ⇒ A = - 1.
Substituting the values of A and B into the right side of equation (10) and integrating between
the limits results in

69 | P a g e
 XA XA
dXA 2 dXA
I= ∫ − + ∫
(1 − XA ) (1 − XA )2
0 0

X 2 X
I = [ln (1 − XA )]0 A + [ ]0 A = kCAo t
1 − XA
2X A
{ln(1 − XA ) + } = kCAo t
1 − XA
1 2XA
t = kC {ln(1 − XA ) + } …… (12)
Ao 1−XA

Equation (12) gives an expression for the reaction time and fractional conversion for an
isothermal constant pressure batch reactor.
k
Considering an nth order irreversible reaction represented by A → bB with −rA = kCAn ,
the design equation is
1 dNA
−rA = − = kCAn
V dt
Or in terms of the fractional conversion XA ,
dXA n−1
= kCAo (1 − XA )n {1 + (b − 1)XA }1−n
dt
Integrating the above equation,
1 XA ⅆXA
t= ∫0 …… (13)
kCn−1
Ao (1−XA )n {1+(b−1)XA }1−n

Equation (13) is the generalized equation, which can be used to determine the reaction time
of an nth order reaction with b, the stoichiometric coefficient of the product component B.

Problem 5.4
Consider the reaction scheme
k1
A→ B
k2
B ⟺ C
k3

k4
B→ D
in a constant volume batch reactor under isothermal conditions. The rate constants are k1 = 5
hr-1, k2 = 4 hr-1, k3 = k4 = 3 hr-1. The initial concentrations are CAo = 16mol/L and CBo = CCo
= CDo = 0 mol/L. Determine the concentrations of A,B,C, and D wth time for a period of 2
hours.
Solution:
Assuming that the reactions are first order in a constant volume batch reactor, the rate
equations for components A, B, C and D, respectively, are:

70 | P a g e
 ⅆCA
−rA = − = k1 CA …… (1)
ⅆt
ⅆCB
−rB = − = (k 2 + k 4 )CB − k1 CA − k 3 CC …… (2)
ⅆt
ⅆCC
−rC = − = k 3 CC − k 2 CB …… (3)
ⅆt
ⅆCD
rD = = k 4 CB …… (4)
ⅆt

Rearranging equations (1), (2), (3), we get

ⅆCA
= −k1 CA …… (5)
ⅆt
ⅆCB
= k1 CA + k 3 CC − (k 2 + k 4 )CB …… (6)
ⅆt
ⅆCC
= k 2 CB − k 3 CC …… (7)
ⅆt

Equation (4), (5), (6), (7) are first order differential equations. The differential equations can
be solved using Runge Kutta fourth order (RK4) method with time increment = ∆t = 0.2 hr.
The formulae involved to solve the equations using RK4 method are:
1
CA,j+1 = CA,j + (p1 + 2p2 + 2p3 + p4 )
6
p1 = (∆t)f(t j , CA,j )
∆t p1
p2 = (∆t)f(t j + , CA,j + )
2 2
∆t p2
p3 = (∆t)f(t j + , CA,j + )
2 2
p4 = (∆t)f(t j + ∆t, CA,j + p3 )
Concentration of A:
t p1 p2 p3 p4 p CA
0 16
0.2 -16 -8 -12 -4 -10 6
0.4 -6 -3 -4.5 -1.5 -3.75 2.25
0.6 -2.25 -1.125 -1.6875 -0.5625 -1.40625 0.844
0.8 -0.84375 -0.42188 -0.63281 -0.21094 -0.52734 0.316
1 -0.31641 -0.1582 -0.2373 -0.0791 -0.19775 0.119
1.2 -0.11865 -0.05933 -0.08899 -0.02966 -0.07416 0.044
1.4 -0.04449 -0.02225 -0.03337 -0.01112 -0.02781 0.017
1.6 -0.01669 -0.00834 -0.01251 -0.00417 -0.01043 0.006
1.8 -0.00626 -0.00313 -0.00469 -0.00156 -0.00391 0.002
2 -0.00235 -0.00117 -0.00176 -0.00059 -0.00147 0.001

For t = 0.2 hours,

ⅆCA
Taking f(t j , CA,j ) = = −k1 CA
ⅆt

71 | P a g e
 1
CA,j+1 = CA,j + (p1 + 2p2 + 2p3 + p4 )
6
Take j = 0, we get
p1 = (∆t)f(t 0 , CA0 ) = 0.2 ∗ (−5 ∗ CA,0 ) = −16
∆t p1 p1
p2 = (∆t)f (t 0 + , CA,0 + ) = 0.2 ∗ (−5 ∗ (CA,0 + )) = −8
2 2 2
∆t p2 p2
p3 = (∆t)f (t 0 + , CA,0 + ) = 0.2 ∗ (−5 ∗ (CA,0 + )) = −12
2 2 2

p4 = (∆t)f(t 0 + ∆t, CA,0 + p3 ) = 0.2 ∗ (−5 ∗ (CA,0 + p3 )) = −4

1 −16 − 2 ∗ 8 − 2 ∗ 12 − 4
p = (p1 + 2p2 + 2p3 + p4 ) = = −10
6 6
Therefore,
CA1 = CA0 + p = 16 – 10 = 6 mol/L
The concentration of A at t = 0.2 hours is 6 mol/L.
Concentration of B:
t q1 q2 q3 q4 q CB
0 0
0.2 16 -3.2 16.16 -20.544 3.562667 3.562667
0.4 3.137067 -1.84128 3.454731 -6.52352 -0.02659 3.536074
0.6 0.122661 -1.08649 0.336622 -2.303 -0.61335 2.922727
0.8 -0.4485 -0.69484 -0.32376 -0.98122 -0.57782 2.344908
1 -0.46795 -0.48536 -0.3942 -0.53128 -0.45973 1.885181
1.2 -0.39092 -0.36306 -0.34387 -0.35209 -0.35948 1.525703
1.4 -0.31442 -0.28353 -0.28167 -0.26264 -0.28458 1.241127
1.6 -0.25287 -0.22674 -0.22844 -0.20698 -0.22837 1.012758
1.8 -0.20462 -0.18355 -0.18558 -0.16689 -0.18496 0.827796
2 -0.16643 -0.14947 -0.15122 -0.1358 -0.1506 0.677194

For t = 0.2 hours,

ⅆCB
Taking f(t j , CB,j ) = = k1 CA + k 3 CC − (k 2 + k 4 )CB
ⅆt

1
CB,j+1 = CB,j + (q1 + 2q 2 + 2q 3 + q 4 )
6
Take j = 0, we get
q1 = (∆t)f(t 0 , CB0 ) = 0.2 ∗ (5CAo + 3CCo − 7CB0 ) = 16
∆t q1 p1 r1 q1
q 2 = (∆t)f (t 0 + , CB,0 + ) = 0.2 ∗ (5(CAo + ) + 3(CCo + ) − 7(CB0 + ))
2 2 2 2 2
= −3.2

72 | P a g e
 ∆t q2 p2 r2 q2
q 3 = (∆t)f (t 0 + , CB,0 + ) = 0.2 ∗ (5(CAo + ) + 3(CCo + ) − 7(CB0 + ))
2 2 2 2 2
= 16.16
q 4 = (∆t)f(t 0 + ∆t, CB,0 + q 3 ) = 0.2 ∗ (5(CAo + p3 ) + 3(CCo + r3 ) − 7(CB0 + q 3 ))
= −20.544
1 16 − (2 ∗ 3.2) − (2 ∗ 16.16) − 20.544
q = (q1 + 2q 2 + 2q 3 + q 4 ) = = 3.562667
6 6
Therefore,
CB1 = CB0 + q = 0 + 3.562667 = 3.562667 mol/L
The concentration of B at t = 0.2 hours is 3.562667 mol/L.

Concentration of C:
t r1 r2 r3 r4 r CC
0 0
0.2 0 6.4 -3.2 14.848 3.541333 3.541333
0.4 0.725333 1.76256 -0.53995 3.813086 1.163941 4.705274
0.6 0.005695 0.053051 -0.44482 0.541883 -0.03933 4.665948
0.8 -0.46139 -0.50237 -0.58861 -0.36723 -0.50176 4.164185
1 -0.62258 -0.62299 -0.62983 -0.56004 -0.61471 3.549472
1.2 -0.62154 -0.59144 -0.58933 -0.54304 -0.58769 2.961785
1.4 -0.55651 -0.51532 -0.51532 -0.47265 -0.51508 2.44671
1.6 -0.47512 -0.43373 -0.4357 -0.39646 -0.43507 2.011635
1.8 -0.39677 -0.35959 -0.36232 -0.32785 -0.36141 1.650228
2 -0.3279 -0.2961 -0.29886 -0.26956 -0.2979 1.352331

For t = 0.2 hours,

ⅆCC
Taking f(t j , CC,j ) = = k 2 CB − k 3 CC
ⅆt

1
CC,j+1 = CC,j + (r1 + 2r2 + 2r3 + r4 )
6
Take j = 0, we get
r1 = (∆t)f(t 0 , CC0 ) = 0.2 ∗ (4CBo − 3CC0 ) = 0
∆t r1 q1 r1
r2 = (∆t)f (t 0 + , CC,0 + ) = 0.2 ∗ (4(CBo + ) − 3(CC0 + )) = 6.4
2 2 2 2
∆t r2 q2 r2
r3 = (∆t)f (t 0 + , CC,0 + ) = 0.2 ∗ (4(CBo + ) − 3(CC0 + )) = −3.2
2 2 2 2
r4 = (∆t)f(t 0 + ∆t, CC,0 + r3 ) = 0.2 ∗ (4(CBo + q 3 ) − 3(CC0 + r3 )) = 14.848
1 0 + 2 ∗ 6.4 − (2 ∗ 3.2) + 14.848
r = (r1 + 2r2 + 2r3 + r4 ) = = 3.541333
6 6

73 | P a g e
Therefore,
CC1 = CC0 + r = 0 + 3.541333 = 3.541333 mol/L
The concentration of C at t = 0.2 hours is 3.541333 mol/L.
Concentration of D:
t s1 s2 s3 s4 s CD
0 0
0.2 0 4.8 -0.96 9.696 2.896 2.896
0.4 2.1376 3.07872 1.585216 4.210438 2.612652 5.508652
0.6 2.121644 2.158443 1.795696 2.323617 2.058923 7.567575
0.8 1.753636 1.619086 1.545184 1.559381 1.606926 9.174501
1 1.406945 1.266559 1.261335 1.170426 1.272193 10.44669
1.2 1.131109 1.013833 1.02219 0.924787 1.021324 11.46802
1.4 0.915422 0.821096 0.830364 0.746419 0.82746 12.29548
1.6 0.744676 0.668816 0.676654 0.607612 0.673872 12.96935
1.8 0.607655 0.546268 0.552591 0.496306 0.55028 13.51963
2 0.496678 0.446748 0.451836 0.405947 0.449965 13.96959
For t = 0.2 hours,
ⅆCD
Taking f(t j , CD,j ) = = k 4 CB
ⅆt

1
CD,j+1 = CD,j + (s1 + 2s2 + 2s3 + s4 )
6
Take j = 0, we get
s1 = (∆t)f(t 0 , CD0 ) = 0.2 ∗ 3CB0 = 0
∆t s1 q1
s2 = (∆t)f (t 0 + , CD,0 + ) = 0.2 ∗ 3 ∗ (CBo + ) = 4.8
2 2 2
∆t s2 q2
s3 = (∆t)f (t 0 + , CD,0 + ) = 0.2 ∗ 3 ∗ (CBo + ) = −0.96
2 2 2
s4 = (∆t)f(t 0 + ∆t, CD,0 + s3 ) = 0.2 ∗ 3 ∗ (CBo + q 3 ) = 9.696
1 0 + 2 ∗ 4.8 − (2 ∗ 0.96) + 9.696
s = (s1 + 2s2 + 2s3 + s4 ) = = 2.896
6 6
Therefore,
CD1 = CD0 + s = 0 + 2.896 = 2.896 mol/L
The concentration of D at t = 0.2 hours is 2.896 mol/L.
Therefore,
t CA CB CC CD
0 16 0 0 0
0.2 6 3.562667 3.541333 2.896
0.4 2.25 3.536074 4.705274 5.508652
0.6 0.844 2.922727 4.665948 7.567575
0.8 0.316 2.344908 4.164185 9.174501
1 0.119 1.885181 3.549472 10.44669

74 | P a g e
 1.2 0.044 1.525703 2.961785 11.46802
1.4 0.017 1.241127 2.44671 12.29548
1.6 0.006 1.012758 2.011635 12.96935
1.8 0.002 0.827796 1.650228 13.51963
2 0.001 0.677194 1.352331 13.96959

Problem 5.5
Consider the simulation of a constant volume batch reaction of the form
k1
A + D→ B
k2
B + D→ C
k3
D + D→ E
The reactor initially contains 0.12 mol/m3 of A and 0.4 mol/m3 of D with the rate constants k1
= 0.4, k2 = 0.2, and k3 = 0.05 m3/mol.min. What are the compositions of A, B, C, and D after
5 minutes?

Solution:
Assume the rates to be second order in a constant volume batch system and determine the rate
equations as follows.
The reaction rate for various components is expressed by
ⅆCA
−rA = − = k1 CA CD …… (1)
ⅆt
ⅆCB
−rB = − = − k1 CA CD + k 2 CB CD …… (2)
ⅆt
ⅆCC
+rC = = k 2 CB CD …… (3)
ⅆt
ⅆCD
−rD = − = k1 CA CD + k 2 CB CD + k 3 CD2 …… (4)
ⅆt

75 | P a g e
Re-arranging (1), (2) and (4), we get
ⅆCA
= − k1 CA CD …… (5)
ⅆt
ⅆCB
= k1 CA CD − k 2 CB CD …… (6)
ⅆt
ⅆCD
= − ( k1 CA CD + k 2 CB CD + k 3 CD2 ) …… (7)
ⅆt

Equation (3), (5), (6), (7) are first order differential equations. The differential equations can
be solved using Runge-Kutta fourth order (RK4) method with time increment = ∆t = 0.5
minutes.
The formulae involved to solve the equations using RK4 method are:
1
CA,j+1 = CA,j + (p1 + 2p2 + 2p3 + p4 )
6
p1 = (∆t)f(t j , CA,j )
∆t p1
p2 = (∆t)f(t j + , CA,j + )
2 2
∆t p2
p3 = (∆t)f(t j + , CA,j + )
2 2
p4 = (∆t)f(t j + ∆t, CA,j + p3 )
Concentration of A:
t p1 p2 p3 p4 p CA
0 0.2
0.5 -0.0160 -0.0150 -0.0150 -0.0141 -0.0150 0.1850
1 -0.0141 -0.0132 -0.0133 -0.0125 -0.0133 0.1717
1.5 -0.0125 -0.0117 -0.0118 -0.0111 -0.0118 0.1599
2 -0.0111 -0.0105 -0.0105 -0.0099 -0.0105 0.1494
2.5 -0.0099 -0.0094 -0.0094 -0.0089 -0.0094 0.1400
3 -0.0089 -0.0085 -0.0085 -0.0080 -0.0085 0.1315
3.5 -0.0081 -0.0076 -0.0077 -0.0073 -0.0077 0.1239
4 -0.0073 -0.0069 -0.0070 -0.0066 -0.0069 0.1169
4.5 -0.0066 -0.0063 -0.0063 -0.0060 -0.0063 0.1106
5 -0.0060 -0.0058 -0.0058 -0.0055 -0.0058 0.1048
5.5 -0.0055 -0.0053 -0.0053 -0.0051 -0.0053 0.0996
6 -0.0051 -0.0048 -0.0049 -0.0047 -0.0049 0.0947
6.5 -0.0047 -0.0045 -0.0045 -0.0043 -0.0045 0.0902
7 -0.0043 -0.0041 -0.0041 -0.0040 -0.0041 0.0861
7.5 -0.0040 -0.0038 -0.0038 -0.0037 -0.0038 0.0823
8 -0.0037 -0.0035 -0.0035 -0.0034 -0.0035 0.0788
8.5 -0.0034 -0.0033 -0.0033 -0.0032 -0.0033 0.0755
9 -0.0032 -0.0031 -0.0031 -0.0029 -0.0031 0.0724
9.5 -0.0029 -0.0028 -0.0028 -0.0028 -0.0028 0.0696
10 -0.0028 -0.0027 -0.0027 -0.0026 -0.0027 0.0669

76 | P a g e
For t = 0.5 minutes
ⅆCA
Taking f(t j , CA,j ) = = − k1 CA CD
ⅆt

1
CA,j+1 = CA,j + (p1 + 2p2 + 2p3 + p4 )
6
Take j = 0, we get
p1 = (∆t)f(t 0 , CA0 ) = 0.5 ∗ (−0.4 ∗ 0.2 ∗ 0.4) = −0.016
∆t p1 p1 s1
p2 = (∆t)f (t 0 + , CA,0 + ) = 0.5 ∗ (−0.4 ∗ (CAo + ) ∗ (CDo + )) = −0.015
2 2 2 2
∆t p2 p2 s2
p3 = (∆t)f (t 0 + , CA,0 + ) = 0.5 ∗ (−0.4 ∗ (CAo + ) ∗ (CDo + )) = −0.015
2 2 2 2

p4 = (∆t)f(t 0 + ∆t, CA,0 + p3 ) = 0.5 ∗ (−0.4 ∗ (CAo + p3 ) ∗ (CDo + s3 )) = −0.0141

1
p= (p + 2p2 + 2p3 + p4 ) = −0.015
6 1
Therefore,
CA1 = CA0 + p = 0.2 – 0.015 = 0.185 mol/L
The concentration of A at t = 0.5 minutes is 0.185 mol/L.

Concentration of B:
t q1 q2 q3 q4 q CB
0 0
0.5 0.0160 0.0147 0.0147 0.0135 0.0147 0.0147
1 0.0135 0.0124 0.0125 0.0115 0.0125 0.0272
1.5 0.0115 0.0106 0.0106 0.0098 0.0106 0.0378
2 0.0098 0.0090 0.0091 0.0084 0.0091 0.0469
2.5 0.0084 0.0077 0.0078 0.0072 0.0078 0.0547
3 0.0072 0.0066 0.0067 0.0062 0.0067 0.0613
3.5 0.0062 0.0057 0.0057 0.0053 0.0057 0.0670
4 0.0053 0.0049 0.0049 0.0046 0.0049 0.0720
4.5 0.0046 0.0042 0.0043 0.0040 0.0043 0.0762
5 0.0040 0.0037 0.0037 0.0034 0.0037 0.0799
5.5 0.0034 0.0032 0.0032 0.0029 0.0032 0.0831
6 0.0029 0.0027 0.0027 0.0025 0.0027 0.0858
6.5 0.0025 0.0024 0.0024 0.0022 0.0024 0.0882
7 0.0022 0.0020 0.0020 0.0019 0.0020 0.0902
7.5 0.0019 0.0017 0.0018 0.0016 0.0017 0.0920
8 0.0016 0.0015 0.0015 0.0014 0.0015 0.0935
8.5 0.0014 0.0013 0.0013 0.0012 0.0013 0.0948
9 0.0012 0.0011 0.0011 0.0010 0.0011 0.0959
9.5 0.0010 0.0009 0.0009 0.0008 0.0009 0.0968
10 0.0008 0.0008 0.0008 0.0007 0.0008 0.0975

77 | P a g e
For t = 0.5 minutes,
ⅆCB
Taking f(t j , CB,j ) = = k1 CA CD − k 2 CB CD
ⅆt

1
CB,j+1 = CB,j + (q1 + 2q 2 + 2q 3 + q 4 )
6
Take j = 0, we get
q1 = (∆t)f(t 0 , CB0 ) = 0.5 ∗ (0.4 ∗ CAo CDo − 0.2CBo CDo ) = 0.016
∆t q1
q 2 = (∆t)f (t 0 + , CB,0 + )
2 2
p1 s1 q1 s1
= 0.5 ∗ [(0.4 ∗ (CAo + )(CDo + )) − (0.2(CBo + )(CDo + ))]
2 2 2 2
= 0.0147
∆t q2
q 3 = (∆t)f (t 0 + , CB,0 + ) =
2 2
p2 s2 q2 s2
= 0.5 ∗ [(0.4 ∗ (CAo + )(CDo + )) − (0.2(CBo + )(CDo + ))]
2 2 2 2
= 0.0147
q 4 = (∆t)f(t 0 + ∆t, CB,0 + q 3 ) =
= 0.5 ∗ [(0.4 ∗ (CAo + p3 )(CDo + s3 )) − (0.2(CBo + q 3 )(CDo + s3 ))]
= 0.0135
1 0.016 + (2 ∗ 0.0147) + (2 ∗ 0.0147) + 0.0135
q = (q1 + 2q 2 + 2q 3 + q 4 ) = = 0.0147
6 6
Therefore, CB1 = CB0 + q = 0 + 0.0147 = 0.0147 mol/L
The concentration of B at t = 0.5 minutes is 0.0147 mol/L.
Concentration of C:
t r1 r2 r3 r4 r CC
0 0
0.5 0.0000 0.0003 0.0003 0.0006 0.0003 0.0003
1 0.0006 0.0008 0.0008 0.0010 0.0008 0.0011
1.5 0.0010 0.0012 0.0012 0.0013 0.0012 0.0022
2 0.0013 0.0015 0.0014 0.0016 0.0014 0.0037
2.5 0.0016 0.0017 0.0017 0.0017 0.0017 0.0053
3 0.0017 0.0018 0.0018 0.0019 0.0018 0.0071
3.5 0.0019 0.0019 0.0019 0.0020 0.0019 0.0091
4 0.0020 0.0020 0.0020 0.0020 0.0020 0.0111
4.5 0.0020 0.0021 0.0021 0.0021 0.0021 0.0131
5 0.0021 0.0021 0.0021 0.0021 0.0021 0.0152
5.5 0.0021 0.0021 0.0021 0.0021 0.0021 0.0173
6 0.0021 0.0021 0.0021 0.0021 0.0021 0.0195
6.5 0.0021 0.0021 0.0021 0.0021 0.0021 0.0216
7 0.0021 0.0021 0.0021 0.0021 0.0021 0.0236
7.5 0.0021 0.0021 0.0021 0.0020 0.0021 0.0257
8 0.0020 0.0020 0.0020 0.0020 0.0020 0.0277
8.5 0.0020 0.0020 0.0020 0.0020 0.0020 0.0297

78 | P a g e
 9 0.0020 0.0020 0.0020 0.0020 0.0020 0.0317
9.5 0.0020 0.0019 0.0019 0.0019 0.0019 0.0336
10 0.0019 0.0019 0.0019 0.0019 0.0019 0.0355

For t = 0.5 minutes,

ⅆCC
Taking f(t j , CC,j ) = = k 2 CB CD
ⅆt

1
CC,j+1 = CC,j + (r1 + 2r2 + 2r3 + r4 )
6
Take j = 0, we get
r1 = (∆t)f(t 0 , CC0 ) = 0.5 ∗ (0.2 ∗ CBo ∗ CDo ) = 0
∆t r1 q1 s1
r2 = (∆t)f (t 0 + , CC,0 + ) = 0.5 ∗ (0.2 ∗ (CBo + ) ∗ (CDo + )) = 0.0003
2 2 2 2
∆t r2 q2 s2
r3 = (∆t)f (t 0 + , CC,0 + ) = 0.5 ∗ (0.2 ∗ (CBo + ) ∗ (CDo + )) = 0.0003
2 2 2 2
r4 = (∆t)f(t 0 + ∆t, CC,0 + r3 ) = 0.5 ∗ (0.2 ∗ (CBo + q 3 ) ∗ (CDo + s3 )) = 0.0006
1 0 + 2 ∗ 0.0003 + (2 ∗ 0.0003) + 0.0006
r= (r1 + 2r2 + 2r3 + r4 ) = = 0.0003
6 6
Therefore,
CC1 = CC0 + r = 0 + 0.0003 = 0.0003 mol/L
The concentration of C at t = 0.5 minutes is 0.0003 mol/L.
Concentration of D:
t s1 s2 s3 s4 s CD
0 0.4
0.5 -0.0200 -0.0191 -0.0191 -0.0183 -0.0191 0.3809
1 -0.0183 -0.0175 -0.0175 -0.0168 -0.0175 0.3634
1.5 -0.0168 -0.0161 -0.0161 -0.0154 -0.0161 0.3473
2 -0.0154 -0.0148 -0.0148 -0.0143 -0.0148 0.3324
2.5 -0.0143 -0.0137 -0.0137 -0.0132 -0.0137 0.3187
3 -0.0132 -0.0127 -0.0127 -0.0123 -0.0127 0.3060
3.5 -0.0123 -0.0118 -0.0118 -0.0114 -0.0118 0.2942
4 -0.0114 -0.0110 -0.0110 -0.0107 -0.0110 0.2831
4.5 -0.0107 -0.0103 -0.0103 -0.0100 -0.0103 0.2728
5 -0.0100 -0.0097 -0.0097 -0.0094 -0.0097 0.2631
5.5 -0.0094 -0.0091 -0.0091 -0.0088 -0.0091 0.2541
6 -0.0088 -0.0085 -0.0085 -0.0083 -0.0085 0.2456
6.5 -0.0083 -0.0080 -0.0080 -0.0078 -0.0080 0.2375
7 -0.0078 -0.0076 -0.0076 -0.0074 -0.0076 0.2300
7.5 -0.0074 -0.0072 -0.0072 -0.0070 -0.0072 0.2228
8 -0.0070 -0.0068 -0.0068 -0.0066 -0.0068 0.2160
8.5 -0.0066 -0.0064 -0.0064 -0.0062 -0.0064 0.2096
9 -0.0062 -0.0061 -0.0061 -0.0059 -0.0061 0.2035

79 | P a g e
 9.5 -0.0059 -0.0058 -0.0058 -0.0056 -0.0058 0.1977
10 -0.0056 -0.0055 -0.0055 -0.0054 -0.0055 0.1922

For t = 0.5 minutes,

ⅆCD
Taking f(t j , CD,j ) = = − ( k1 CA CD + k 2 CB CD + k 3 CD2 )
ⅆt

1
CD,j+1 = CD,j + (s1 + 2s2 + 2s3 + s4 )
6
Take j = 0, we get
2 ))
s1 = (∆t)f(t 0 , CD0 ) = 0.5 ∗ (− (0.4CAo CDo + 0.2CBo CDo + 0.05CDo = −0.02

∆t s1
s2 = (∆t)f (t 0 + , CD,0 + ) =
2 2
= 0.5
p1 s1 q1 s1
∗ (− (0.4 (CAo + ) (CDo + ) + 0.2(CBo + )(CDo + )
2 2 2 2
s1
+ 0.05(CDo + )2 )) = −0.0191
2
∆t s2
s3 = (∆t)f (t 0 + , CD,0 + )
2 2
= 0.5 ∗
p2 s2 q2 s2
∗ (− (0.4 (CAo + ) (CDo + ) + 0.2(CBo + )(CDo + )
2 2 2 2
s2 2
+ 0.05(CDo + ) )) = −0.0191
2

s4 = (∆t)f(t 0 + ∆t, CD,0 + s3 )

= 0.5 ∗
∗ (− (0.4(CAo + p3 )(CDo + s3 ) + 0.2(CBo + q 3 )(CDo + s3 )
+ 0.05(CDo + s3 )2 )) = −0.0183
1 −0.02 − 2 ∗ 0.0191 − (2 ∗ 0.0191) − 0.0183
s= (s1 + 2s2 + 2s3 + s4 ) = = −0.0191
6 6
Therefore,
CD1 = CD0 + s = 0.4 − 0.0191 = 0.3809 mol/L
The concentration of D at t = 0.5 minutes is 0.3809 mol/L.
Therefore,
t CA CB CC CD
0 0.2 0 0 0.4
0.5 0.1850 0.0147 0.0003 0.3809
1 0.1717 0.0272 0.0011 0.3634
1.5 0.1599 0.0378 0.0022 0.3473
2 0.1494 0.0469 0.0037 0.3324

80 | P a g e
 2.5 0.1400 0.0547 0.0053 0.3187
3 0.1315 0.0613 0.0071 0.3060
3.5 0.1239 0.0670 0.0091 0.2942
4 0.1169 0.0720 0.0111 0.2831
4.5 0.1106 0.0762 0.0131 0.2728
5 0.1048 0.0799 0.0152 0.2631
5.5 0.0996 0.0831 0.0173 0.2541
6 0.0947 0.0858 0.0195 0.2456
6.5 0.0902 0.0882 0.0216 0.2375
7 0.0861 0.0902 0.0236 0.2300
7.5 0.0823 0.0920 0.0257 0.2228
8 0.0788 0.0935 0.0277 0.2160
8.5 0.0755 0.0948 0.0297 0.2096
9 0.0724 0.0959 0.0317 0.2035
9.5 0.0696 0.0968 0.0336 0.1977
10 0.0669 0.0975 0.0355 0.1922

Problem 5.6
Consider the following reaction scheme:
k1 k3
A↔ B→ C
k2

k5 ↕ k4
in a constant volume batch reactor under isothermal conditions, and with rate constants
k1 = 0.4 hr-1, k2 = 0.1 hr-1, k3 = 0.16 hr-1, k4 = 0.08 hr-1 and k5 = 0.13 hr-1. The original
compositions in the batch are: CA = 7 gmol/L, CB = 2.0 gmol/L, CC = 0 gmol/L, CD = 0.5
gmol/L.
Determine the concentrations of each component as a function of time for 2 hours.

81 | P a g e
Solution:
From the reaction scheme, it can be assumed that the rate equations are first order.
The rate of disappearance of component A is:
ⅆCA
−rA = − = k1 CA − k 2 CB …… (1)
ⅆt

The rate of disappearance of component B is:

ⅆCB
−rB = − = (k 2 + k 3 + k 4 )CB − k1 CA − k 5 CD …… (2)
ⅆt

The rate of formation of component C is:

ⅆCC
+rC = = k 3 CB …… (3)
ⅆt

The rate of disappearance of component D is:

ⅆCD
−rD = − = k 5 CD − k 4 CB …… (4)
ⅆt

Re-arranging (1), (2) and (4), we get

ⅆCA
= k 2 CB − k1 CA …… (5)
ⅆt
ⅆCB
= k1 CA + k 5 CD − (k 2 + k 3 + k 4 )CB …… (6)
ⅆt
ⅆCD
= k 4 CB − k 5 CD …… (7)
ⅆt

Equation (3), (5), (6), (7) are first order differential equations. The differential equations can
be solved using Runge-Kutta fourth order (RK4) method with time increment = ∆t = 0.5
minutes.
The formulae involved to solve the equations using RK4 method are:
1
CA,j+1 = CA,j + (p1 + 2p2 + 2p3 + p4 )
6
p1 = (∆t)f(t j , CA,j )
∆t p1
p2 = (∆t)f(t j + , CA,j + )
2 2
∆t p2
p3 = (∆t)f(t j + , CA,j + )
2 2
p4 = (∆t)f(t j + ∆t, CA,j + p3 )
Concentration of A:
t p1 p2 p3 p4 p CA
0 7.0000
0.2 -0.5200 -0.4948 -0.4962 -0.4722 -0.4957 6.5043
0.4 -0.4723 -0.4497 -0.4509 -0.4294 -0.4505 6.0538
0.6 -0.4294 -0.4091 -0.4102 -0.3909 -0.4098 5.6440

82 | P a g e
 0.8 -0.3909 -0.3727 -0.3737 -0.3563 -0.3733 5.2707
1 -0.3563 -0.3399 -0.3408 -0.3251 -0.3405 4.9302
1.2 -0.3252 -0.3104 -0.3112 -0.2971 -0.3109 4.6193
1.4 -0.2971 -0.2838 -0.2845 -0.2718 -0.2843 4.3350
1.6 -0.2719 -0.2599 -0.2605 -0.2491 -0.2603 4.0747
1.8 -0.2491 -0.2383 -0.2388 -0.2285 -0.2386 3.8361
2 -0.2285 -0.2188 -0.2193 -0.2100 -0.2191 3.6170

For t = 0.2 hours,

ⅆCA
Taking f(t j , CA,j ) = = k 2 CB − k1 CA
ⅆt

1
CA,j+1 = CA,j + (p1 + 2p2 + 2p3 + p4 )
6
Take j = 0, we get
p1 = (∆t)f(t 0 , CA0 ) = 0.2 ∗ (0.1CB − 0.4CA ) = −0.52
∆t p1 q1 p1
p2 = (∆t)f (t 0 + , CA,0 + ) = 0.2 ∗ ((0.1 ∗ (CBo + )) − (0.4(CAo + )))
2 2 2 2
= −0.4948
∆t p2 q2 p2
p3 = (∆t)f (t 0 + , CA,0 + ) = 0.2 ∗ ((0.1 ∗ (CBo + )) − (0.4(CAo + )))
2 2 2 2
= −0.4962
p4 = (∆t)f(t 0 + ∆t, CA,0 + p3 ) = 0.2 ∗ ((0.1 ∗ (CBo + q 3 )) − (0.4(CAo + p3 ))) = −0.4722
1
p = (p1 + 2p2 + 2p3 + p4 ) = −0.4957
6
Therefore,
CA1 = CA0 + p = 7 – 0.4957 = 6.5043 mol/L
The concentration of A at t = 0.2 hours is 6.5043 mol/L.
Concentration of B:
t q1 q2 q3 q4 q CB
0 2.0000
0.2 0.4370 0.4016 0.4038 0.3704 0.4030 2.4030
0.4 0.3705 0.3393 0.3413 0.3119 0.3406 2.7437
0.6 0.3120 0.2846 0.2864 0.2605 0.2858 3.0294
0.8 0.2606 0.2366 0.2381 0.2154 0.2376 3.2670
1 0.2155 0.1944 0.1958 0.1759 0.1953 3.4623
1.2 0.1760 0.1575 0.1587 0.1413 0.1583 3.6206
1.4 0.1413 0.1252 0.1263 0.1110 0.1259 3.7465
1.6 0.1111 0.0970 0.0979 0.0847 0.0976 3.8441
1.8 0.0847 0.0724 0.0733 0.0617 0.0730 3.9170
2 0.0617 0.0510 0.0518 0.0417 0.0515 3.9685

For t = 0.2 hours,

83 | P a g e
 ⅆCB
Taking f(t j , CB,j ) = = k1 CA + k 5 CD − (k 2 + k 3 + k 4 )CB
ⅆt

1
CB,j+1 = CB,j + (q1 + 2q 2 + 2q 3 + q 4 )
6
Take j = 0, we get
q1 = (∆t)f(t 0 , CB0 ) = 0.2 ∗ (0.4CAo + 0.13CDo − 0.34CB0 ) = 0.4370
∆t q1
q 2 = (∆t)f (t 0 + , CB,0 + )
2 2
p1 s1 q1
= 0.2 ∗ (0.4(CAo + ) + 0.13(CDo + ) − 0.34(CB0 + )) = 0.4016
2 2 2
∆t q2
q 3 = (∆t)f (t 0 + , CB,0 + )
2 2
p2 s2 q2
= 0.2 ∗ (0.4(CAo + ) + 0.13(CDo + ) − 0.34(CB0 + )) = 0.4038
2 2 2
q 4 = (∆t)f(t 0 + ∆t, CB,0 + q 3 )
= 0.2 ∗ (0.4(CAo + p3 ) + 0.13(CDo + s3 ) − 0.34(CB0 + q 3 )) = 0.3704
1
q = (q1 + 2q 2 + 2q 3 + q 4 ) = 0.4030
6
Therefore,
CB1 = CB0 + q = 2 + 0.4030 = 2.4030 mol/L
The concentration of B at t = 0.2 hours is 2.4030 mol/L.
Concentration of C:
t r1 r2 r3 r4 r CC
0 0.0000
0.2 0.0640 0.0710 0.0704 0.0769 0.0706 0.0706
0.4 0.0769 0.0828 0.0823 0.0878 0.0825 0.1531
0.6 0.0878 0.0928 0.0924 0.0970 0.0925 0.2456
0.8 0.0969 0.1011 0.1007 0.1046 0.1009 0.3465
1 0.1045 0.1080 0.1077 0.1108 0.1078 0.4543
1.2 0.1108 0.1136 0.1133 0.1159 0.1134 0.5677
1.4 0.1159 0.1181 0.1179 0.1199 0.1180 0.6856
1.6 0.1199 0.1217 0.1214 0.1230 0.1215 0.8072
1.8 0.1230 0.1244 0.1242 0.1254 0.1242 0.9314
2 0.1253 0.1263 0.1262 0.1270 0.1262 1.0576

For t = 0.2 hours,

ⅆCC
Taking f(t j , CC,j ) = = k 3 CB
ⅆt

1
CC,j+1 = CC,j + (r1 + 2r2 + 2r3 + r4 )
6
Take j = 0, we get
r1 = (∆t)f(t 0 , CC0 ) = 0.2 ∗ (0.16CBo ) = 0.064

84 | P a g e
 ∆t r1 q1
r2 = (∆t)f (t 0 + , CC,0 + ) = 0.2 ∗ 0.16(CBo + ) = 0.0710
2 2 2
∆t r2 q2
r3 = (∆t)f (t 0 + , CC,0 + ) = 0.2 ∗ 0.16(CBo + ) = 0.0704
2 2 2
r4 = (∆t)f(t 0 + ∆t, CC,0 + r3 ) = 0.2 ∗ 0.16(CBo + q 3 ) = 0.0769
1
r= (r + 2r2 + 2r3 + r4 ) = 0.0706
6 1
Therefore, CC1 = CC0 + r = 0 + 0.0706 = 0.0706 mol/L
The concentration of C at t = 0.2 hours is 0.0706 mol/L.
Concentration of D:
t s1 s2 s3 s4 s CD
0 0.5000
0.2 0.0190 0.0222 0.0219 0.0249 0.0220 0.5220
0.4 0.0249 0.0275 0.0272 0.0296 0.0273 0.5494
0.6 0.0296 0.0317 0.0315 0.0334 0.0316 0.5809
0.8 0.0334 0.0350 0.0348 0.0363 0.0349 0.6158
1 0.0363 0.0375 0.0373 0.0384 0.0374 0.6532
1.2 0.0384 0.0393 0.0392 0.0399 0.0392 0.6924
1.4 0.0399 0.0405 0.0404 0.0409 0.0404 0.7329
1.6 0.0409 0.0412 0.0411 0.0414 0.0412 0.7741
1.8 0.0414 0.0415 0.0414 0.0415 0.0415 0.8155
2 0.0415 0.0414 0.0413 0.0412 0.0414 0.8569

For t = 0.2 hours,

ⅆCD
Taking f(t j , CD,j ) = = k 4 CB − k 5 CD
ⅆt

1
CD,j+1 = CD,j + (s1 + 2s2 + 2s3 + s4 )
6
Take j = 0, we get
s1 = (∆t)f(t 0 , CD0 ) = 0.2 ∗ (0.08CBo − 0.13CDo ) = 0.0190
∆t s1 q1 s1
s2 = (∆t)f (t 0 + , CD,0 + ) = 0.2 ∗ (0.08(CBo + ) − 0.13(CDo + )) = 0.0222
2 2 2 2
∆t s2 q2 s2
s3 = (∆t)f (t 0 + , CD,0 + ) = 0.2 ∗ (0.08(CBo + ) − 0.13(CDo + )) = 0.0219
2 2 2 2
s4 = (∆t)f(t 0 + ∆t, CD,0 + s3 ) = 0.2 ∗ (0.08(CBo + q 3 ) − 0.13(CDo + s3 )) = 0.0249
1
s= (s + 2s2 + 2s3 + s4 ) = 0.0220
6 1
Therefore,
CD1 = CD0 + s = 0.5 + .0220 = 0.5220 mol/L
The concentration of D at t = 0.2 hours is 0.5220 mol/L.

85 | P a g e
Therefore,
t CA CB CC CD
0 7.0000 2.0000 0.0000 0.5000
0.2 6.5043 2.4030 0.0706 0.5220
0.4 6.0538 2.7437 0.1531 0.5494
0.6 5.6440 3.0294 0.2456 0.5809
0.8 5.2707 3.2670 0.3465 0.6158
1 4.9302 3.4623 0.4543 0.6532
1.2 4.6193 3.6206 0.5677 0.6924
1.4 4.3350 3.7465 0.6856 0.7329
1.6 4.0747 3.8441 0.8072 0.7741
1.8 3.8361 3.9170 0.9314 0.8155
2 3.6170 3.9685 1.0576 0.8569

Problem 5.7
A pair of reactions
k1
A + B → 2C
k2
A+C →D
is carried out in a constant volume batch reactor with k1 = 0.1 ft3/(lb-mol) (min) and k2 =
0.05 ft3/(lb-mol) (min). The concentrations of A and B are such that at time t = 0, CA0 =
3CB0= 0.9 lb-mol/ft3. The concentrations of C and D at initial time t = 0 are CC0 = CD0 = 0.0
lb-mol/ft3. Determine the concentrations of A, B, C, and D as a function of time for the
duration of 12 minutes.
Ans.
The rate of disappearance of A will be equal to -rA = k1CACB + k2CACC

86 | P a g e
The rate of disappearance of B will be equal to -rB = k1CACB
−dCA
= k1 CA CB + k 2 CA CC
dt
−dCB
= k1 CA CB
dt
At time t = 0
CA = CA0 and CB = CB0
At time t = t
CA = CA and CB = CB
Amount of A and B reacted will be equal to CA0 - CA and CB0 – CB
Using stoichiometry
The mole balance for A and B will be
A+B
A+ =D
2
3A B
+ = D
2 2
So, by applying mole balance
3nD nC
+ = n A 0 − nA
2 2
nC nD
+ = nB0 − nB
2 2
On solving the two equations we get
nD = (nA0 − nA ) − (nB0 − nB )

nC = 3(nB0 − nB ) − (nA0 − nA )
Dividing it with volume on both the sides
Putting CA0 = 3CB0 = 0.9 lb-mol/ft3
CC = CA − 3CB
Similarly
CD = 0.6 + CB − CA
dCA
= −k 2 CA (CA − 3CB ) − k1 CA CB
dt
dCA
= −k 2 CA2 + 3k 2 CA CB − k1 CA CB
dt
dCA
= −0.05CA2 + 0.05CA CB
dt

87 | P a g e
On applying the Runge-Kutta Method for Δt = 0.5 min we get
1
CA,n+1 = CA,n + (k1 + 2k 2 + 2k 3 + k 4 )
6
k1 = (∆t)f(t n , CA,n )
∆t k1
k 2 = (∆t)f(t n + , CA,n + )
2 2
∆t k2
k 3 = (∆t)f(t n + , CA,n + )
2 2
k 4 = (∆t)f(t n + ∆t, CA,n + k 3 )
1
CB,n+1 = CB,n + (l1 + 2l2 + 2l3 + l4 )
6
l1 = (∆t)f(t n , CB,n )
∆t l1
l2 = (∆t)f(t n + , CB,n + )
2 2
∆t l2
l3 = (∆t)f(t n + , CB,n + )
2 2
l4 = (∆t)f(t n + ∆t, CB,n + l3 )
For t = 0.5 min,
Taking
dCA
f(t n , CAn ) = = −0.05CA2 + 0.05CA CB
dt
1
CA,n+1 = CA,n + (k1 + 2k 2 + 2k 3 + k 4 )
6
l1 + 2l2 + 2l3 + l4
CB,n+1 = CB,n + ( )
6
k1 = 0.5 ∗ (−0.05 ∗ 0.92 + 0.05 ∗ 0.9 ∗ 0.3) = −0.0135
l1 = 0.5 ∗ (−0.1 ∗ 0.9 ∗ 0.3) = −0.0135

0.0135 2 0.135 0.0135

k 2 = 0.5 ∗ (−0.05 ∗ (0.9 − ) + 0.05 ∗ (0.9 − ) ∗ (0.3 − ))
2 2 2
= −0.0134

0.0135 0.0135
l2 = 0.5 ∗ (−0.1 ∗ (0.9 − ) ∗ (0.3 − )) = −0.0131
2 2

0.0134 2 0.0134 0.0131

k 3 = 0.5 ∗ (−0.05 ∗ (0.9 − ) + 0.05 ∗ (0.9 − ) ∗ (0.3 − ))
2 2 2
= −0.0134

88 | P a g e
 0.0134 0.0131
l3 = 0.5 ∗ (−0.1 ∗ (0.9 − ) ∗ (0.3 − )) = −0.01311
2 2

k 4 = 0.5 ∗ (−0.05 ∗ (0.9 − 0.0134)2 + 0.05 ∗ (0.9 − 0.0134) ∗ (0.3 − 0.0131))

= −0.0133
l4 = 0.5 ∗ (−0.1 ∗ (0.9 − 0.0134) ∗ (0.3 − 0.0131)) = −0.01272
−0.0135−2∗0.0134−2∗0.0134−0.0133
CA1 = 0.9 + = 0.8866 lb-mol/ft3
6
−0.0135−2∗0.0131−2∗0.0131−0.01272 lb−mol
CB1 = 0.3 + = 0.2869
6 ft3
lb−mol
CC1 = 0.8866 − 3 ∗ 0.2869 = 0.0259 ft3
lb−mol
CD1 = 0.6 + 0.2869 − 0.8866 = 0.0003 ft3

The concentration of A with time

t k1 k2 k3 k4 k Ca
0 0.9
0.5 -0.0135 -0.0134 -0.0134 -0.01329 -0.0134 0.886603
1 -0.01329 -0.01319 -0.01318 -0.01308 -0.01319 0.873418
1.5 -0.01308 -0.01297 -0.01297 -0.01285 -0.01297 0.860452
2 -0.01285 -0.01274 -0.01274 -0.01263 -0.01274 0.847711
2.5 -0.01263 -0.01251 -0.01251 -0.0124 -0.01251 0.8352
3 -0.0124 -0.01228 -0.01228 -0.01216 -0.01228 0.82292
3.5 -0.01216 -0.01205 -0.01205 -0.01193 -0.01205 0.810875
4 -0.01193 -0.01181 -0.01181 -0.01169 -0.01181 0.799063
4.5 -0.01169 -0.01158 -0.01158 -0.01146 -0.01158 0.787486
5 -0.01146 -0.01134 -0.01134 -0.01123 -0.01134 0.776142
5.5 -0.01123 -0.01111 -0.01111 -0.011 -0.01111 0.76503
6 -0.011 -0.01088 -0.01088 -0.01077 -0.01088 0.754147
6.5 -0.01077 -0.01066 -0.01066 -0.01054 -0.01066 0.743491
7 -0.01054 -0.01043 -0.01043 -0.01032 -0.01043 0.733058
7.5 -0.01032 -0.01021 -0.01021 -0.0101 -0.01021 0.722846
8 -0.0101 -0.01 -0.01 -0.00989 -0.01 0.71285
8.5 -0.00989 -0.00978 -0.00978 -0.00968 -0.00978 0.703068
9 -0.00968 -0.00957 -0.00957 -0.00947 -0.00957 0.693495
9.5 -0.00947 -0.00937 -0.00937 -0.00927 -0.00937 0.684126
10 -0.00927 -0.00917 -0.00917 -0.00907 -0.00917 0.674959
10.5 -0.00907 -0.00897 -0.00897 -0.00887 -0.00897 0.665988
11 -0.00887 -0.00878 -0.00878 -0.00868 -0.00878 0.657209
11.5 -0.00868 -0.00859 -0.00859 -0.0085 -0.00859 0.648618
12 -0.0085 -0.00841 -0.00841 -0.00832 -0.00841 0.640211

89 | P a g e
The variation of concentration of B with time
t l1 l2 l3 l4 l Cb
0 0.3
0.5 -0.0135 -0.0131 -0.01311 -0.01272 -0.0131 0.286896
1 -0.01272 -0.01234 -0.01235 -0.01199 -0.01235 0.274546
1.5 -0.01199 -0.01164 -0.01165 -0.01131 -0.01165 0.2629
2 -0.01131 -0.01098 -0.01099 -0.01068 -0.01099 0.251909
2.5 -0.01068 -0.01037 -0.01038 -0.01009 -0.01038 0.241531
3 -0.01009 -0.0098 -0.00981 -0.00953 -0.00981 0.231724
3.5 -0.00953 -0.00927 -0.00928 -0.00902 -0.00927 0.22245
4 -0.00902 -0.00877 -0.00878 -0.00854 -0.00878 0.213675
4.5 -0.00854 -0.00831 -0.00831 -0.00809 -0.00831 0.205366
5 -0.00809 -0.00787 -0.00787 -0.00766 -0.00787 0.197493
5.5 -0.00766 -0.00746 -0.00747 -0.00727 -0.00746 0.190028
6 -0.00727 -0.00708 -0.00708 -0.0069 -0.00708 0.182947
6.5 -0.0069 -0.00672 -0.00672 -0.00655 -0.00672 0.176224
7 -0.00655 -0.00638 -0.00639 -0.00623 -0.00639 0.169838
7.5 -0.00623 -0.00607 -0.00607 -0.00592 -0.00607 0.163767
8 -0.00592 -0.00577 -0.00577 -0.00563 -0.00577 0.157994
8.5 -0.00563 -0.00549 -0.0055 -0.00536 -0.00549 0.152499
9 -0.00536 -0.00523 -0.00523 -0.00511 -0.00523 0.147267
9.5 -0.00511 -0.00498 -0.00499 -0.00487 -0.00499 0.142281
10 -0.00487 -0.00475 -0.00475 -0.00464 -0.00475 0.137528
10.5 -0.00464 -0.00453 -0.00453 -0.00443 -0.00453 0.132994
11 -0.00443 -0.00433 -0.00433 -0.00423 -0.00433 0.128667
11.5 -0.00423 -0.00413 -0.00413 -0.00404 -0.00413 0.124534
12 -0.00404 -0.00395 -0.00395 -0.00386 -0.00395 0.120586

The concentration of C with time

t Ca Cb Cc
0 0.9 0.3 0
0.5 0.886603 0.286896 0.025916
1 0.873418 0.274546 0.04978
1.5 0.860452 0.2629 0.071753
2 0.847711 0.251909 0.091983
2.5 0.8352 0.241531 0.110607
3 0.82292 0.231724 0.127749
3.5 0.810875 0.22245 0.143525
4 0.799063 0.213675 0.158039
4.5 0.787486 0.205366 0.17139
5 0.776142 0.197493 0.183664
5.5 0.76503 0.190028 0.194945
6 0.754147 0.182947 0.205307
6.5 0.743491 0.176224 0.214819
7 0.733058 0.169838 0.223545

90 | P a g e
 7.5 0.722846 0.163767 0.231544
8 0.71285 0.157994 0.23887
8.5 0.703068 0.152499 0.245571
9 0.693495 0.147267 0.251695
9.5 0.684126 0.142281 0.257283
10 0.674959 0.137528 0.262374
10.5 0.665988 0.132994 0.267005
11 0.657209 0.128667 0.271209
11.5 0.648618 0.124534 0.275015
12 0.640211 0.120586 0.278454

The concentration of D with time

t Ca Cb Cd
0 0.9 0.3 0
0.5 0.886603 0.286896 0.000293
1 0.873418 0.274546 0.001128
1.5 0.860452 0.2629 0.002448
2 0.847711 0.251909 0.004198
2.5 0.8352 0.241531 0.006331
3 0.82292 0.231724 0.008803
3.5 0.810875 0.22245 0.011575
4 0.799063 0.213675 0.014611
4.5 0.787486 0.205366 0.017879
5 0.776142 0.197493 0.02135
5.5 0.76503 0.190028 0.024999
6 0.754147 0.182947 0.0288
6.5 0.743491 0.176224 0.032733
7 0.733058 0.169838 0.03678
7.5 0.722846 0.163767 0.040921
8 0.71285 0.157994 0.045143
8.5 0.703068 0.152499 0.049431
9 0.693495 0.147267 0.053772
9.5 0.684126 0.142281 0.058155
10 0.674959 0.137528 0.062569
10.5 0.665988 0.132994 0.067007
11 0.657209 0.128667 0.071458
11.5 0.648618 0.124534 0.075916
12 0.640211 0.120586 0.080375

We get the following values of the concentration

t Ca Cb Cc Cd
0 0.9 0.3 0 0
0.5 0.8866 0.2869 0.0259 0.0003
1 0.8734 0.2745 0.0498 0.0011

91 | P a g e
 1.5 0.8605 0.2629 0.0718 0.0024
2 0.8477 0.2519 0.092 0.0042
2.5 0.8352 0.2415 0.1106 0.0063
3 0.8229 0.2317 0.1277 0.0088
3.5 0.8109 0.2224 0.1435 0.0116
4 0.7991 0.2137 0.158 0.0146
4.5 0.7875 0.2054 0.1714 0.0179
5 0.7761 0.1975 0.1837 0.0214
5.5 0.765 0.19 0.1949 0.025
6 0.7541 0.1829 0.2053 0.0288
6.5 0.7435 0.1762 0.2148 0.0327
7 0.7331 0.1698 0.2235 0.0368
7.5 0.7228 0.1638 0.2315 0.0409
8 0.7129 0.158 0.2389 0.0451
8.5 0.7031 0.1525 0.2456 0.0494
9 0.6935 0.1473 0.2517 0.0538
9.5 0.6841 0.1423 0.2573 0.0582
10 0.675 0.1375 0.2624 0.0626
10.5 0.666 0.133 0.267 0.067
11 0.6572 0.1287 0.2712 0.0715
11.5 0.6486 0.1245 0.275 0.0759
12 0.6402 0.1206 0.2785 0.0804

Conc vs time
1
0.9
0.8
0.7 Ca
0.6 Cb
0.5 Cc
0.4 Cd
0.3
0.2
0.1
0
0 2 4 6 8 10 12 14

Problem 5.8
A continuous flow stirred tank reactor is used to decompose a dilute solution of species A.
The decomposition is irreversible and first order with velocity constant at 2.5 hr-1. The reactor
volume is 15 m3. What flowrate of feed solution can this reactor treat if 90% decomposition
is required?

92 | P a g e
Ans.
The mass component balance can be written as
(Input of moles of the jth component into the system) – (Output of moles of the jth component
out of the system) – (rate of disappearance of the jth component) = (time rate of change of the
jth component)
uCA0 = uCA + (−rA )VR
dCA
u(CA0 − CA ) = ( ) VR
dt
The concentration of A in terms of fractional conversion.
CA = CA0 (1 − XA )
CA0 − CA = CA0 XA CA0.XA = CA0 CA

u(CA0 XA ) = kCA VR
u(CA0 XA ) = kCA0 (1 − XA )VR u
k(1 − X A )VR
u=
XA
2.5 ∗ (1 − 0.9) ∗ 15
u=
0.9
u = 4.17 m3/hr
Problem 5.9
The reaction between ammonia (NH3) and formaldehyde (HCHO) to produce hexamine
N4(CH2)6 was studied at 36°C (Kermode & Stevens, * 1965) in a CFSTR of 490 dm3 stirred
at 1,800 rpm. The reaction is
4NH3 + 6HCHO → N4(CH2)6 + 6H2O
and the rate equation is
2
(−rNH3) = 0.0649 ∗ CNH3 ∗ CHCHO The reactants were each fed to the reactor at a rate of 1.5
dm /sec with an ammonia concentration of 4.02 mol/dm3 and a formaldehyde concentration
3

of 6.32 mol/dm3. Determine the exit concentrations.

Ans.
Assuming steady state condition (i.e. the accumulation = 0)
uCA0 = uCA + (−rA )VR
Where
2
−rA = 0.0649 ∗ CNH3 ∗ CHCHO
That is
2
uCA0 = uCA + 0.0649 ∗ CNH3 ∗ CHCHO

93 | P a g e
Using Stoichiometry
CA0 − CA CB0 − CB
=
4 6
CB = CB0 + 1.5 ∗ (CA0 − CA )
CB = 0.29 + 1.5CA
The residence time was found out to be equal to be V/ν = (490)/ (3) = 163.33 sec
CA0 = CA + 0.00649 ∗ τ ∗ CA ∗ CB2
Putting the value of CB in the equation
CA0 = CA + 10.6 ∗ CA ∗ (0.29 + 1.5CA )2

23.85CA3 + 9.22CA2 + 1.89CA − 4.02 = 0

Now by using the Newton-Raphson Method we will find the root of the equations
df
= 71.55CA2 + 18.44CA + 1.89
dCA
Initial guess of the root will be equal to x0 = 0.5
By applying the newton Raphson method, we get on the first iteration
f(x )
x1 = x0 - f′ (x0 )
0

2.21125
x1 = 0.5 –
28.9975

x1 = 0.4237
On second iteration we get
f(x )
x2 = x1 - f′ (x1 )
1

0.25
x2 = 0.4237 – 22.548

x2 = 0.4126
On third iteration we get
f(x2 )
x3 = x2 -
f′ (x3 )

0.00465
x3 = 0.4126 - 21.679

x3 = 0.4124
The second and the third iteration are approximately the same so the root will be 0.4124
So, the value of CA will be equal to 0.4124 mol/dm3
And the value of CB will be CB = 0.29 + 1.5*0.4124
CB = 0.9086 mol/dm3

94 | P a g e
Problem 5.10
The pair of reactions
k1
A + B → 2C
k2
A+C →D
are conducted in a four-stage CFSTR with CA0 = 0.9 mol/m3, CB0 = 0.3 mol/m3, and CC0 =
CD0 = 0 mol/m3. The residence time in each stage is 10 minutes. Determine the exit
concentrations of A and B in the four CFSTRs. The rate expressions are (–rA) = k1CACB +
k2CACC and (–rB) = k1CACB, where k1 = 0.3 m3/mol•min and k2 = 0.15 m3/mol•min.
Ans.
VR
Mean Residence time = = 10 min
u

By applying the material balance on A we get

uCA0 = uCA + (−rA )V
-rA = k1CA1CB1 + k2CA1CC1
uCA0 = uCA + (k1 CA1 CB1 + k 2 CA1 CC1 )V
Using stoichiometry
The mole balance for A and B will be
A+B
A+ =D
2
3A B
+ = D
2 2
So, by applying mole balance
3nD nC
+ = n A 0 − nA
2 2
nC nD
+ = nB0 − nB
2 2
On solving the two equations we get
nD = (nA0 − nA ) − (nB0 − nB )

nC = 3(nB0 − nB ) − (nA0 − nA )
Dividing it with volume on both the sides
Putting CA0 = 3CB0 = 0.9 lb-mol/ft3
CC = CA − 3CB
Similarly
CD = 0.6 + CB − CA

95 | P a g e
 CA0 = CA1 + τCA1 ∗ (k1 CB1 + k 2 ∗ (CA1 − 3CB1 ))

0.9 = CA1 + 10CA1 ∗ (0.3CB1 + 0.15 ∗ (CA1 − 3CB1 ))

0.9 = 1.5CA2 1 − 1.5CA1 CB1 + CA1

Applying the material balance for the component B
uCB0 = uCB + (−rB )V
-rB = k1CACB
u(CB0 − CB1 ) = k1 CB1 CA1 VR
CB0 − CB1 = k1 τCB1 CA1
0.3 − CB1 = 3CB1 CA1
So, the equation for the first CSTR becomes
0.9 = 1.5CA2 1 − 1.5CA1 CB1 + CA1
0.3 = CB1 + 3CB1 CA1
0.3
From the second equation we get the value of CB1 = 1+3C
A1

Substituting this value in the first equation we get

4.5CA3 1 + 4.5CA2 1 − 2.15CA1 − 0.9 = 0
By applying the Newton Raphson method, we get
f(x )
x1 = x0 - f′ (x0 )
0

f ′ (x) = 13.5CA2 + 9CA − 2.15

The roots of the above equation are (-0.8533,0.1866)
As the value should always be positive therefore
The initial guess of the root will be x0 = 0.5
By applying the newton Raphson method, we get on the first iteration
f(x )
x1 = x0 - f′ (x0 )
0

−0.2875
x1 = 0.5 – ( )
5.725

x1 = 0.55021
On second iteration we get
f(x )
x2 = x1 - f′ (x1 )
1

0.0289
x2 = 0.55021 – ( 6.889 )

96 | P a g e
 x2 = 0.54601
On third iteration we get
f(x )
x3 = x2 - f′ (x2 )
2

0.0002
x3 = 0.54601 – ( 6.789 )

x3 = 0.546
The second and the third iteration are approximately the same so the root will be 0.546
The value of CA1 will be equal to 0.546 mol/m3
The value of CB1 will be equal to 0.1137 mol/m3
Similarly
By applying mass balance on component, A and B on other reactors we get the equations as
The equation of second reactor will be
1.5CA2 2 − 1.5CA2 CB2 + CA2 = CA1
CB1 = CB2 + 3CB2 CA2
The equation of third reactor will be
1.5CA2 3 − 1.5CA3 CB3 + CA3 = CA2
CB2 = CB3 + 3CB3 CA3
The equation of fourth reactor will be
1.5CA2 4 − 1.5CA4 CB4 + CA4 = CA3
CB3 = CB4 + 3CB4 CA4
Now by substituting the value of CB in the above equation we get
CBn−1
CBn =
1 + 3CAn
The equation for the other reactors will become
4.5CA3 n + 4.5CA2 n − 1.5CAn CBn−1 − 3CAn CAn−1 + CAn = CAn−1
Where n stands for the position/number of the reactor
We can solve these equations by using the Newton Raphson method
f ′ (CAn ) = 13.5CA2 n + 9CAn − 1.5CBn−1 − 3CAn−1 + 1
For the second reactor the equation becomes
f(CA2 ) = 4.5CA3 2 + 4.5CA2 2 − 0.80855CA2 − 0.546

f ′ (CA2 ) = 13.5CA2 2 + 9CA2 − 0.80855

97 | P a g e
Let us assume the initial root to be equal to 0.3
By applying the newton Raphson method, we get on the first iteration
f(x )
x1 = x0 - f′ (x0 )
0

−0.262
x1 = 0.3 – (3.10645)

x1 = 0.3843
On second iteration we get
f(x )
x2 = x1 - f′ (x1 )
1

0.0632
x2 = 0.3843 – (7.8382)

x2 = 0.3762
On third iteration we get
f(x )
x3 = x2 - f′ (x2 )
3

0.0264
x3 = 0.3762 – ( 4.885 )

x3 = 0.3707
On fourth iteration we get
f(x )
x4 = x3 - f′ (x3 )
3

0.0023
x4 = 0.3707 – ( 4.387 )

x3 = 0.3701
The third and the fourth iteration are approximately the same so the root will be 0.3701
The value of CA2 will be equal to 0.3701 mol/m3
The value of CB2 will be equal to 0.05387 mol/m3
For the third reactor the equation becomes
f(CA3 ) = 4.5CA3 3 + 4.5CA2 3 − 0.191CA2 − 0.3701

f ′ (CA2 ) = 13.5CA2 2 + 9CA2 − 0.191

Let us assume the initial root to be equal to 0.3
By applying the newton Raphson method, we get on the first iteration
f(x )
x1 = x0 - f′ (x0 )
0

0.0991
x1 = 0.3 – ( 3.724 )

x1 = 0.2734

98 | P a g e
On second iteration we get
f(x )
x2 = x1 - f′ (x1 )
1

0.006
x2 = 0.2734 – (3.2786)

x2 = 0.27157
On third iteration we get
f(x )
x3 = x2 - f′ (x2 )
3

0.00005
x3 = 0.27157 – ( 3.2487 )

x3 = 0.27157
The second and the third iteration are approximately the same so the root will be 0.27157
The value of CA3 will be equal to 0.27157 mol/m3
The value of CB3 will be equal to 0.02959 mol/m3
For the fourth reactor the equation becomes
f(CA3 ) = 4.5CA3 3 + 4.5CA2 3 + 0.14905CA2 − 0.27157

f ′ (CA2 ) = 13.5CA2 2 + 9CA2 + 0.14905

Let us assume the initial root to be equal to 0.3
By applying the newton Raphson method, we get on the first iteration
f(x )
x1 = x0 - f′ (x0 )
0

0.3
x1 = 0.3 – (4.064)

x1 = 0.2262
On second iteration we get
f(x )
x2 = x1 - f′ (x1 )
1

0.0444
x2 = 0.2262 – (2.8753)

x2 = 0.2107
On third iteration we get
f(x )
x3 = x2 - f′ (x2 )
2

0.00185
x3 = 0.2107 – ( 2.6455 )

x3 = 0.2100
On fourth iteration we get

99 | P a g e
 f(x )
x4 = x3 - f′ (x3 )
3

−0.00014
x4 = 0.21 – ( )
2.6344

x3 = 0.2100
The third and the fourth iteration are approximately the same so the root will be 0.2100
The value of CA4 will be equal to 0.2100 mol/m3
The value of CB4 will be equal to 0.01815 mol/m3

Problem 5.11
(1) For a cascade of N CFSTRs of equal volume, VR, in which the first order forward reaction
A → P occurs with a throughput u, show that the system fractional conversion is
1
1−
kV N
(1 + uR )

whatever the feed concentration of A.

(2) A sample CFSTR of volume VR has one inlet stream rate u, containing A at concentration
CA0 and a second inlet stream of rate αu, containing B at concentration CB0. The reaction is A
+ B → 2P with the rate first order with respect to both A and B. Obtain an expression for the
concentration of A at the reactor exit in terms of VR and the conditions in the feed streams.
Ans.
(a). By applying the material balance on species A we get
uCA0 = uCA + (−rA )V
Where (−rA ) = k1 CA
The equation then becomes
uCA0 = uCA + k1 CA V
On rearranging we get
uCA0 C A0
CA = or CA = k V
u+ k1 V 1+( 1 )
u

For the second CSTR, the exit concentration CA2

CA1
C A2 =
k1 V
1+( u )

For the nth CSTR, the exit concentration CAn

100 | P a g e
 CA0
CAn = n
k1 V
(1 + ( u ))

CAn 1
= n
CA0 k1 V
(1 + ( u ))

1
1 − XA = n
k1 V
(1 + ( u ))

1
XA = 1 − n
k1 V
(1 + ( u ))

k
(b) The reaction A + B → 2P and the rate expression of species A and B is (-rA) = (-rB) =
kCACB
uCA0 = u(1 + α)CA + k1 CA CB V
Or
uCA0
CA =
u(1 + α) + kVR CB
Applying the material balance on species B is
αuCB0 = u(1 + α)CB + kCA CB V
uαCB0
CB =
u(1 + α) + kCA VR
Putting the value of CB in the value of CA
uCA0
CA =
uαCB0
u(1 + α) + kVR ∗ ( )
u(1 + α) + kCA VR
(1 + α)kVR CA2 + {u(1 + α)2 + (αCB0 − CA0 )kVR }CA − u(1 + α)CA0 = 0
On solving the above Quadratic equation, we get the value of CA as

√(u(1 + α2 ) + (αCB0 − CA0 )kVR )2 + 4u(1 + α)2 kCA0 VR

CA =
2(1 + α)kVR

101 | P a g e
Problem 5.12
Styrene (A) and butadiene (B) are to be treated in a series of CFSTRs each possessing 26.5
m3 capacity. The initial concentration of A is 0.795 and B is 3.55 kg mol/m3. The flowrate is
20 m3/hr. The rate equation is (–rA) = 0.036*CA*CB kg • mol/m3 * hr. Determine the
intermediate conversions, if the eleventh stirred tank is required to effect 80% conversion of
the limiting reactant.
Ans.
Given that A is the limiting reactant and the reaction follows a second order kinetics
−rA = 0.036 ∗ CA ∗ CB
26.5
The mean residence time of one reactor will be τ = = 1.325 hr
20

As the volume of all the reactors are same the mean residence will also be the same for all the
reactors.
CA XA
For conversion in CSTR the equation will be τ = kC 0 C
A B

The reaction is taken place as A+B→ P hence by stoichiometry we can show that CA0 – CA =
CB0 – CB as the number of moles of A consumed will be equal to the number of moles of B
consumed.
As the exit concentration of A at the 11th reactor will be 20% of the initial concentration
hence CAexit = 0.2*0.795 = 0.159 mol/m3 and the exit concentration of B will be 2.914 mol/m3
Calculating the conversion in the nth tank
CAn−1 ∗ XA
τ=
(0.036CA2 n−1 (1 − XA ) ∗ (M − XA ))
CBn−1
Where M = C
An−1

For the first reactor we get the equation as

C A0 ∗ X A
τ=
(0.036CA2 0 (1 − X A ) ∗ (M − XA ))

XA
1.325 =
(0.036 ∗ 0.795(1 − XA ) ∗ (4.465 − XA ))
On rearranging we get it in the form of quadratic equation
X
0.0379215 = X2 −5.465XA
A A +4.465

0.0379215XA2 − 1.2072XA + 0.1693 = 0

The equation is in the form of aX2 + bX +c = 0
0.5
−b−(b2 −4∗a∗c)
Now XA = 2∗a

102 | P a g e
As XA should be less than or equal to 1 we neglect the positive part of the discriminant
Upon solving the quadratic equation, we get the value of XA1 = 0.1408
Similarly, for calculating the conversion for the rest of the reactors we have to use the same
technique
As it is in the form of a quadratic equation
X An
τ=
kCAn−1 (1 − XAn ) ∗ (M − XAn )
X An
kτCAn−1 =
XA2 n − (M + 1)XAn + M

kτCAn−1 XA2 n − kτCAn−1 (M + 2)XAn + MkτCAn−1 = 0

CBn−1
a = kτCAn−1 , b = kτCAn−1 (M + 2) , c = MkτCAn−1 where M = C
An−1

The values of the coefficients are

a b c
0.037922 -1.20726 0.169335
0.032579 -1.19657 0.163992
0.028097 -1.18761 0.159511
0.024311 -1.18004 0.155725
0.021094 -1.1736 0.152508
0.018347 -1.16811 0.14976
0.01599 -1.16339 0.147403
0.01396 -1.15933 0.145374
0.012207 -1.15583 0.143621
0.010688 -1.15279 0.142102
0.009369 -1.15015 0.140783
0.008221 -1.14786 0.139635
Similarly, we get values of conversion for the rest of the reactors in the same way
Position of reactor Conversion
1 0.1408
2 0.259
3 0.358
4 0.4437
5 0.5162
6 0.578
7 0.6318
8 0.678
9 0.718
10 0.752
11 0.8

103 | P a g e
Problem 5.13
A well-mixed batch reactor is used for performing the isothermal liquid phase reaction

Each reaction step is first order with respect to reactant A and the
Initial concentration of A is 1.0 kmol/m3.
(1) Determine the yield of B with respect to A for any given initial concentration.
(2) Determine the time required to achieve a 60% conversion of A
to B or C.
Solution:

(1)
Assumptions
➢ Assuming the reaction is first order in a constant volume batch system.
➢ Assuming density is constant throughout.
Notations:
➢ CA = Concentration of A
➢ CB = Concentration of B
➢ CC = Concentration of C
➢ k1 = Rate constant for reaction between A and B
➢ k2 = Rate constant for reaction between A and C
➢ F = Flow rate of feed into the reactor
➢ ρ = Density of the system

Total continuity equation:

[Mass Flow into the system ] − [Mass flow out of the system ]
= [Time rate of change mass inside the system ]
dV lb
Fρ = ,( )
dt s
Component balance equation:
[(−Rate of reaction )] = [rate of concentration change ]
= [−(rate constant ∗ Component concentration)]

104 | P a g e
 ⅆCA
(−rA ) = = −(k1 + k 2 ) ∗ CA (1)
ⅆt
ⅆCB
(+rB ) = = k1 ∗ CA (2)
ⅆt
ⅆCC
(+rC ) = = k 2 ∗ CA (3)
ⅆt

Integrating Equation (1) between the boundary conditions t = 0, CA = CA0 and t = t, CA = CA

gives
CA = CA0 ∗ e−(k1+k2)∗t (4)
Substituting Equation (4) into Equation (2) gives
ⅆCB
= k1 ∗ CA0 ∗ e−(k1+k2)∗t (5)
ⅆt

Integrating Equation (5) between the boundary conditions gives

CB = ((k1 ∗ CA0 )/ ( k1 +k 2 ))*{1-e−(k1+k2)∗t } (6)
The yield of B with respect to A is YB
YB = CB /CA0
= ((k1 ∗ CA0 )/(k1 + k 2 ))*{1-e−(k1+k2)∗t }/CA0
k1
= (k ) ∗ {1 − e−(k1+k2)∗t }
1 +k2

Substituting the values of k1 and k2 in terms of time t gives the yield of B with respect to A as
YB = 0.8 ∗ (1 − e−2.5∗t )
(2)
The time required to achieve 60% conversion of A to B or C is
C
Conversion of A, XA = 1 − C A = 0.6
A0
CA
= 0.4 = e−(k1+k2)∗t
CA0

CA
= ln ln 0.4 = −(k1 + k 2 ) ∗ t
CA0
That is,
ln ln 0.4 = -2.5*t
t = 0.366 hr (≃22 min)

Problem 5.14
The decomposition of phosphine in the gas phase 4PH3(g) → P4(g) + 6H2 at 650°C is first
order. The specific rate is given by
18,963
k = − + 2T + 12.3 (sec)−1
T

105 | P a g e
Determine what size plug flow reactor, operating at 650°C and 5.0 atm, produces 85%
conversion of the feed consisting of 4 kg/mols of pure phosphine per hour.
Solution:
The rate constant k at 650°C (923 K) is
18,963
k = − + 2923 + 12.3
923
k=0.0033 sec-1 (12 hr-1)
Consider the reaction 4PH3(g) → P4(g) + 6H2 or 4A → C + 6D, where A = PH3, C = P4, and
D = H2. Because the reaction is first order, then
Assumptions:
➢ The reaction is of first order
➢ The density of the reactants and products remains constant
➢ The feed rate remains constant
➢ The rate constant remains constant for a particular temperature
➢ Plug flow behaviour remains constant
Notations:
➢ k = Rate constant of a reaction at a particular temperature
➢ CA = Concentration of A
➢ CB = Concentration of B
➢ CC = Concentration of C
➢ CD = Concentration of D
➢ A = PH3
➢ C = P4
➢ D = H2
Equations to be used:
(−rA ) = k ∗ CA
kg.mol
= 12*CA m3 .hr

The volume of plug flow reactor is given by

0.85
dXA
VR = u ∗ CA0 ∗ ∫
0 −rA
At constant pressure of 5.0 atm, the concentration CA is
1 − XA
CA = CA0 ∗ ( )
1 + ƐA ∗ XA
Therefore, the volume of the plug flow reactor is
0.85
dXA
VR = u ∗ CA0 ∗ ∫
1−X
0 k ∗ CA0 ∗ (1 + Ɛ ∗AX )
A A

Integration of the above equation yields

106 | P a g e
 u 0.85
VR = {−(ƐA ∗ XA ) −ln ln (1 − XA )[1 + ƐA ]}
k 0.0
Where u = volumetric flowrate m3/hr
ƐA = (7-4)/4 = 0.75
XA = 0.85
kg.mol
FA0 = 4 = u*CA0
hr

Assuming an ideal gas

p∗V= n∗R∗T
n pA0 kg. mol
= CA = ( )
V R∗T m3

1.atm
Gas constant R = 0.08206 gmol.K

PA0 = 5.0 atm

T = 923 K
5 atm
CA0 = ( 3 )
0.08206 ∗ 923 m . atm
.K
kgmol. K
kg.mol
= 0.066 m3

FA0
u = CA0

4 m3
u = ( hr )
0.066

m3
u = 60.59 ( hr )

60.59
VR = {−(0.75 ∗ 0.85) −ln ln (1 − 0.85)(1 + 0.85) } m3
12
VR = 14.5 m3
Problem 5.15
Consider an aqueous feed of A and B (600 l/min, 150 mmol of A/l, 300 mmol of B/l) that is
being converted to product in a plug flow reactor. The stoichiometry and rate equation are:
A+B->C (-rA)=300CACB mol/min
Find the volume of the reactor needed for 95% conversion of A to product.
Solution:
Assuming that the reaction is second order, the design equation for a plug flow reactor is

107 | P a g e
 CAF XA
VR dCA dXA
τPlug = = −∫ = CA0 ∫
u CA0 (−rA ) 0 (−rA )

From the stoichiometry CB = CB0 – (CA0 – CA), the conversion of XA is (CA0 – CA)/CA0.
Therefore, CA = CA0(1 – XA) and CA0 – CA = CA0XA. The rate expression for the second order
is
mol
(−rA ) = kCA CB
min
1
k = 300
mol. min
The design equation in terms of the fractional conversion XA becomes
XAF =0.95
VR dXA
= CA0 ∫
u 0 kCA CB
XAF =0.95
dXA
= CA0 ∫
0 kCA0 (1 − XA )(CB0 − CA0 XA )
where CB0/CA0 = θB
0.95
VR dXA
= CA0 ∫ 2
u 0 kCA0 (1 − XA )(θB − XA )
Integration of the above equation involving partial fractions and further manipulation yields
u θB − XA XAF =0.95
VR = ( )}
kCA0 (θB − 1) 1 − XA XA =0
u = 600 1/min CA0 = 150 mmol/l CBO=300 mmol/l
k=300 l/(mol.min) θB = CB0/CA0= 2.0
600 2 − 0.95 2−0
VR = −3
{ln ln −ln ln }
300 ∗ 150 ∗ 10 ∗ (2 − 1) 1 − 0.95 1−0
VR = 31.34 L

Problem 5.16
Hougen and Watson in an analysis of Kassel’s data for the homogeneous, vapor-phase
dehydrogenation of benzene in a tubular-flow reactor considered two reactions:
1. 2C6 H6 (g) → C12 H10 (g) + H2 (g)
2. C6 H6 (g) + C12 H10 (g) → C18 H14 (g) + H2 (g)
The rate equations are:
15200 pD pH lb moles benzene reacted
r1 = 14.94 ∗ 106 e− T (p2
B − ) ( )
K1 hr. ft 3

108 | P a g e
 15200
r2 = 8.67 ∗ 106 e− T ( pD pB
pT pH lb moles triphenyl produced or diphenyl reacted
− ) ( )
K2 hr. ft 3
Where, pB = partial pressure of benzene, atm
pD = partial pressure of diphenyl, atm
pT = partial pressure of triphenyl, atm
pH = partial pressure of hydrogen, atm
K1 , K 2
= equilibrium constants for the two reactions in terms of partial pressures
The data on which the rate equations are based were obtained at a total pressure of 1 atm and
temperatures of 1265°F and 1400°F in a 0.5-in. tube, 3ft long.
To design a tubular reactor that will operate at 1 atm pressure and 1400°F:
1. Determine the total conversion of benzene to di- and triphenyl as a function of space
velocity.
2. Determine the reactor volume required to process 10,000 lb/hr of benzene (the feed is
pure benzene) as a function of the total conversion.
3. Determine the space velocity for the maximum concentration of diphenyl. Assume
that the reaction is operated isothermally and that no other recations are significant.
Solution:
Since the reactor is isothermal, the equilibrium constants K1 and K2 are estimated at 1400°F
from equations developed by Hougen and Watson. The results are: K1 = 0.312, K2 = 0.48
At 1400°F, the two rates in terms of the disappearance rate of benzene are
pD pH
r1 = 14.94 ∗ 106 e−14.7 (p2B − )
0.312
p p
= 6.23 (p2B − 0.312
D H
) …… (1)
pT pH
r2 = 8.67 ∗ 106 e−14.7 ( pD pB − )
0.48
pT pH
= 3.61 ( pD pB − ) …… (2)
0.48

The design equation for a plug flow reactor:

XA =XAf
V dXA
= ∫
F −rA
XA =0

If the mass balances are based on benzene, then the two equations are
V ⅆX1
= ∫ …… (3)
F r1

V ⅆX2
= ∫ …… (4)
F r2

109 | P a g e
Where the conversions X1 is the pound moles of benzene disappearing by reaction 1 per
pound mole of the feed, and the conversion X2 is the pound moles of benzene disappearing
by reaction 2 per pound mole of the feed.
Based on 1 mole of entering benzene, the moles of each component at conversions X1 and X2
are
Component Mole at conversions X1 and X2
Hydrogen (H2) (1/2) X1 + X2
Diphenyl (C12H10) (1/2) X1 - X2
Benzene (C6H6) 1- X1 - X2
Triphenyl (C18H14) X2
Total moles 1.0

Since the total mole equals 1.0, the mole fractions of each component are also given by these
quantities. If the components are assumed to behave as ideal gases, then the partial pressures
are:
Component Mole at conversions X1 and X2
Hydrogen (H2), pH 1.0[(1/2) X1 + X2] = (1/2) X1 + X2
Diphenyl (C12H10), pD (1/2) X1 - X2
Benzene (C6H6), pB 1- X1 - X2
Triphenyl (C18H14), pT X2

Substituting the partial pressures of the components in equations (1) and (2) gives,
1 1
( X1 −X2 )( X1 +X2 )
r1 = 6.23 ∗ {(1 − X1 − X2 )2 − 2 2
} …… (5)
0.312
1
1 X2 ( X1 +X2 )
r2 = 3.61 ∗ {(1 − X1 − X2 ) (2 X1 −X2 ) − 2
} …… (6)
0.48

Substituting equations (5), (6) in equations (3), (4), values of exit conversions X1 , X2 , and
the composition of the components are evaluated for various values of V/F using RK4
method.
Equations (5) and (6) can be written as
1 1
ⅆX1 ( X1 −X2 )( X1 +X2 )
= r1 (X1 , X2 ) = 6.23 ∗ {(1 − X1 − X2 )2 − 2 2
} …… (7)
ⅆ(V/F) 0.312
1
ⅆX2 1 X2 ( X1 +X2 )
= r2 (X1 , X2 ) = 3.61 ∗ {(1 − X1 − X2 ) (2 X1 −X2 ) − 2
} …… (8)
ⅆ(V/F) 0.48

The formulae involved to solve the equations using RK4 method are:
1
X1,j+1 = X1,j + (p1 + 2p2 + 2p3 + p4 )
6
V V
p1 = (∆ )f(( )j , X1,j )
F F

110 | P a g e
 V
V V ∆F p1
p2 = (∆ ) ∗ f(( )j + , X1,j + )
F F 2 2
V
V V ∆F p2
p3 = (∆ ) ∗ f(( )j + , X1,j + )
F F 2 2
V V V
p4 = (∆ ) ∗ f(( )j + ∆ , X1,j + p3 )
F F F

Conversion X1 :
V/F p1 p2 p3 p4 p X1
0.0000 0.0000
0.0050 0.0312 0.0302 0.0302 0.0293 0.0302 0.0302
0.0100 0.0293 0.0284 0.0284 0.0275 0.0284 0.0586
0.0150 0.0275 0.0266 0.0267 0.0258 0.0266 0.0852
0.0200 0.0258 0.0250 0.0250 0.0243 0.0250 0.1102
0.0250 0.0243 0.0235 0.0235 0.0228 0.0235 0.1338
0.0300 0.0228 0.0221 0.0221 0.0214 0.0221 0.1558
0.0350 0.0214 0.0207 0.0207 0.0201 0.0207 0.1766
0.0400 0.0201 0.0195 0.0195 0.0189 0.0195 0.1960
0.0450 0.0189 0.0183 0.0183 0.0177 0.0183 0.2143
0.0500 0.0177 0.0172 0.0172 0.0166 0.0172 0.2315
0.0550 0.0166 0.0161 0.0161 0.0156 0.0161 0.2476
0.0600 0.0156 0.0151 0.0152 0.0147 0.0151 0.2628
0.0650 0.0147 0.0142 0.0142 0.0138 0.0142 0.2770
0.0700 0.0138 0.0134 0.0134 0.0129 0.0134 0.2904
0.0750 0.0129 0.0125 0.0126 0.0122 0.0126 0.3029
0.0800 0.0122 0.0118 0.0118 0.0114 0.0118 0.3147
0.0850 0.0114 0.0111 0.0111 0.0107 0.0111 0.3258
0.0900 0.0107 0.0104 0.0104 0.0101 0.0104 0.3362
0.0950 0.0101 0.0098 0.0098 0.0095 0.0098 0.3460
0.1000 0.0095 0.0092 0.0092 0.0089 0.0092 0.3552
0.1050 0.0089 0.0086 0.0086 0.0084 0.0086 0.3638
0.1100 0.0084 0.0081 0.0081 0.0079 0.0081 0.3719
0.1150 0.0079 0.0076 0.0076 0.0074 0.0076 0.3795
0.1200 0.0074 0.0072 0.0072 0.0069 0.0072 0.3867
0.1250 0.0069 0.0067 0.0067 0.0065 0.0067 0.3934
0.1300 0.0065 0.0063 0.0063 0.0061 0.0063 0.3998
0.1350 0.0061 0.0059 0.0060 0.0058 0.0060 0.4057
0.1400 0.0058 0.0056 0.0056 0.0054 0.0056 0.4113
0.1450 0.0054 0.0053 0.0053 0.0051 0.0053 0.4166
0.1500 0.0051 0.0049 0.0049 0.0048 0.0049 0.4215
0.1550 0.0048 0.0046 0.0046 0.0045 0.0046 0.4262
0.1600 0.0045 0.0044 0.0044 0.0042 0.0044 0.4305
0.1650 0.0042 0.0041 0.0041 0.0040 0.0041 0.4346
0.1700 0.0040 0.0039 0.0039 0.0037 0.0039 0.4385
0.1750 0.0037 0.0036 0.0036 0.0035 0.0036 0.4421

111 | P a g e
 0.1800 0.0035 0.0034 0.0034 0.0033 0.0034 0.4456
0.1850 0.0033 0.0032 0.0032 0.0031 0.0032 0.4488
0.1900 0.0031 0.0030 0.0030 0.0029 0.0030 0.4518
0.1950 0.0029 0.0028 0.0028 0.0027 0.0028 0.4546
0.2000 0.0027 0.0027 0.0027 0.0026 0.0027 0.4573
0.2050 0.0026 0.0025 0.0025 0.0024 0.0025 0.4598
0.2100 0.0024 0.0024 0.0024 0.0023 0.0024 0.4621
0.2150 0.0023 0.0022 0.0022 0.0021 0.0022 0.4644
0.2200 0.0021 0.0021 0.0021 0.0020 0.0021 0.4664
0.2250 0.0020 0.0020 0.0020 0.0019 0.0020 0.4684
0.2300 0.0019 0.0018 0.0018 0.0018 0.0018 0.4702
0.2350 0.0018 0.0017 0.0017 0.0017 0.0017 0.4719
0.2400 0.0017 0.0016 0.0016 0.0016 0.0016 0.4736
0.2450 0.0016 0.0015 0.0015 0.0015 0.0015 0.4751
0.2500 0.0015 0.0014 0.0014 0.0014 0.0014 0.4765
0.2550 0.0014 0.0013 0.0013 0.0013 0.0013 0.4779
0.2600 0.0013 0.0013 0.0013 0.0012 0.0013 0.4791
0.2650 0.0012 0.0012 0.0012 0.0011 0.0012 0.4803
0.2700 0.0011 0.0011 0.0011 0.0011 0.0011 0.4814
0.2750 0.0011 0.0010 0.0010 0.0010 0.0010 0.4825
0.2800 0.0010 0.0010 0.0010 0.0009 0.0010 0.4834
0.2850 0.0009 0.0009 0.0009 0.0009 0.0009 0.4844
0.2900 0.0009 0.0009 0.0009 0.0008 0.0009 0.4852
0.2950 0.0008 0.0008 0.0008 0.0008 0.0008 0.4860
0.3000 0.0008 0.0008 0.0008 0.0007 0.0008 0.4868
0.3050 0.0007 0.0007 0.0007 0.0007 0.0007 0.4875
0.3100 0.0007 0.0007 0.0007 0.0006 0.0007 0.4882
0.3150 0.0006 0.0006 0.0006 0.0006 0.0006 0.4888
0.3200 0.0006 0.0006 0.0006 0.0006 0.0006 0.4894
0.3250 0.0006 0.0005 0.0005 0.0005 0.0005 0.4899
0.3300 0.0005 0.0005 0.0005 0.0005 0.0005 0.4904
0.3350 0.0005 0.0005 0.0005 0.0005 0.0005 0.4909
0.3400 0.0005 0.0004 0.0004 0.0004 0.0004 0.4914
0.3450 0.0004 0.0004 0.0004 0.0004 0.0004 0.4918
0.3500 0.0004 0.0004 0.0004 0.0004 0.0004 0.4922
0.3550 0.0004 0.0004 0.0004 0.0004 0.0004 0.4926
0.3600 0.0004 0.0003 0.0003 0.0003 0.0003 0.4929
0.3650 0.0003 0.0003 0.0003 0.0003 0.0003 0.4932
0.3700 0.0003 0.0003 0.0003 0.0003 0.0003 0.4935
0.3750 0.0003 0.0003 0.0003 0.0003 0.0003 0.4938
0.3800 0.0003 0.0003 0.0003 0.0002 0.0003 0.4940
0.3850 0.0002 0.0002 0.0002 0.0002 0.0002 0.4943
0.3900 0.0002 0.0002 0.0002 0.0002 0.0002 0.4945
0.3950 0.0002 0.0002 0.0002 0.0002 0.0002 0.4947
0.4000 0.0002 0.0002 0.0002 0.0002 0.0002 0.4949
0.4050 0.0002 0.0002 0.0002 0.0002 0.0002 0.4951

For V/F = 0.005 hours,

112 | P a g e
 1 1
ⅆX1 ( X1 −X2 )( X1 +X2 )
Taking f((V/F)j , X1,j ) = ⅆ(V/F) = 6.23 ∗ {(1 − X1 − X2 )2 − 2 2
}
0.312

1
X1,j+1 = X1,j + (p1 + 2p2 + 2p3 + p4 )
6
Take j = 0, we get
1 1
V V 2 ( X1,0 −X2,0 )( X1,0 +X2,0 )
2 2
p1 = (∆ F)f(( F)0 , X1,0 ) = 0.005 ∗ (6.23 ∗ {(1 − X1,0 − X2,0 ) − }) =
0.312

0.0312
V
V V ∆ p1 p1
F
p2 = (∆ F) ∗ f((F)0 + , X1,0 + ) = 0.005 ∗ (6.23 ∗ {(1 − (X1,0 + )−
2 2 2
2 1 p q 1 p q
q1 ( (X1,0 + 1 )−(X2,0 + 1 ))( (X1,0 + 1 )+(X2,0 + 1 ))
2 2 2 2 2 2
(X2,0 + )) − }) = 0.0302
2 0.312

V
V V ∆ p2 p2
F
p3 = (∆ F) ∗ f((F)0 + , X1,0 + ) = 0.005 ∗ (6.23 ∗ {(1 − (X1,0 + )−
2 2 2
2 1 p q 1 p q
q2 ( (X1,0 + 2 )−(X2,0 + 2 ))( (X1,0 + 2 )+(X2,0 + 2 ))
2 2 2 2 2 2
(X2,0 + )) − }) = 0.0302
2 0.312

V V V
p4 = (∆ F) ∗ f(( F)0 + ∆ F , X1,0 + p3 ) = 0.005 ∗ (6.23 ∗ {(1 − (X1,0 + p3 ) −
1 1
2 ( (X1,0 +p3 )−(X2,0 +q3 ))( (X1,0 +p3 )+(X2,0 +q3 ))
2 2
(X2,0 + q 3 )) − }) = 0.0293
0.312

1
p= (p + 2p2 + 2p3 + p4 ) = 0.0302
6 1
Therefore,
X1.1 = X1,0 + p = 0 + 0.0302 = 0.0302
The conversion X1 at t = 0.005 hours is 0.0302.

Conversion X2:
V/F q1 q2 q3 q4 q X2
0.0000 0.0000
0.0050 0.0000 0.0001 0.0001 0.0003 0.0001 0.0001
0.0100 0.0003 0.0004 0.0004 0.0005 0.0004 0.0005
0.0150 0.0005 0.0006 0.0006 0.0007 0.0006 0.0011
0.0200 0.0007 0.0008 0.0008 0.0008 0.0008 0.0019
0.0250 0.0008 0.0009 0.0009 0.0010 0.0009 0.0028
0.0300 0.0010 0.0011 0.0011 0.0011 0.0011 0.0038
0.0350 0.0011 0.0012 0.0012 0.0012 0.0012 0.0050
0.0400 0.0012 0.0013 0.0013 0.0013 0.0013 0.0063
0.0450 0.0013 0.0013 0.0013 0.0014 0.0013 0.0076
0.0500 0.0014 0.0014 0.0014 0.0014 0.0014 0.0090
0.0550 0.0014 0.0014 0.0014 0.0015 0.0014 0.0104

113 | P a g e
0.0600 0.0015 0.0015 0.0015 0.0015 0.0015 0.0119
0.0650 0.0015 0.0015 0.0015 0.0015 0.0015 0.0134
0.0700 0.0015 0.0015 0.0015 0.0015 0.0015 0.0150
0.0750 0.0015 0.0015 0.0015 0.0016 0.0015 0.0165
0.0800 0.0016 0.0016 0.0016 0.0016 0.0016 0.0181
0.0850 0.0016 0.0016 0.0016 0.0016 0.0016 0.0196
0.0900 0.0016 0.0016 0.0016 0.0016 0.0016 0.0212
0.0950 0.0016 0.0015 0.0015 0.0015 0.0015 0.0227
0.1000 0.0015 0.0015 0.0015 0.0015 0.0015 0.0243
0.1050 0.0015 0.0015 0.0015 0.0015 0.0015 0.0258
0.1100 0.0015 0.0015 0.0015 0.0015 0.0015 0.0273
0.1150 0.0015 0.0015 0.0015 0.0015 0.0015 0.0288
0.1200 0.0015 0.0015 0.0015 0.0015 0.0015 0.0303
0.1250 0.0015 0.0015 0.0015 0.0014 0.0015 0.0317
0.1300 0.0014 0.0014 0.0014 0.0014 0.0014 0.0332
0.1350 0.0014 0.0014 0.0014 0.0014 0.0014 0.0346
0.1400 0.0014 0.0014 0.0014 0.0014 0.0014 0.0359
0.1450 0.0014 0.0014 0.0014 0.0013 0.0014 0.0373
0.1500 0.0013 0.0013 0.0013 0.0013 0.0013 0.0386
0.1550 0.0013 0.0013 0.0013 0.0013 0.0013 0.0399
0.1600 0.0013 0.0013 0.0013 0.0013 0.0013 0.0412
0.1650 0.0013 0.0012 0.0012 0.0012 0.0012 0.0424
0.1700 0.0012 0.0012 0.0012 0.0012 0.0012 0.0437
0.1750 0.0012 0.0012 0.0012 0.0012 0.0012 0.0449
0.1800 0.0012 0.0012 0.0012 0.0012 0.0012 0.0460
0.1850 0.0012 0.0011 0.0011 0.0011 0.0011 0.0472
0.1900 0.0011 0.0011 0.0011 0.0011 0.0011 0.0483
0.1950 0.0011 0.0011 0.0011 0.0011 0.0011 0.0494
0.2000 0.0011 0.0011 0.0011 0.0011 0.0011 0.0505
0.2050 0.0011 0.0010 0.0010 0.0010 0.0010 0.0515
0.2100 0.0010 0.0010 0.0010 0.0010 0.0010 0.0525
0.2150 0.0010 0.0010 0.0010 0.0010 0.0010 0.0535
0.2200 0.0010 0.0010 0.0010 0.0010 0.0010 0.0545
0.2250 0.0010 0.0009 0.0009 0.0009 0.0009 0.0554
0.2300 0.0009 0.0009 0.0009 0.0009 0.0009 0.0563
0.2350 0.0009 0.0009 0.0009 0.0009 0.0009 0.0572
0.2400 0.0009 0.0009 0.0009 0.0009 0.0009 0.0581
0.2450 0.0009 0.0009 0.0009 0.0008 0.0009 0.0590
0.2500 0.0008 0.0008 0.0008 0.0008 0.0008 0.0598
0.2550 0.0008 0.0008 0.0008 0.0008 0.0008 0.0606
0.2600 0.0008 0.0008 0.0008 0.0008 0.0008 0.0614
0.2650 0.0008 0.0008 0.0008 0.0008 0.0008 0.0622
0.2700 0.0008 0.0008 0.0008 0.0007 0.0008 0.0629
0.2750 0.0007 0.0007 0.0007 0.0007 0.0007 0.0637
0.2800 0.0007 0.0007 0.0007 0.0007 0.0007 0.0644
0.2850 0.0007 0.0007 0.0007 0.0007 0.0007 0.0651
0.2900 0.0007 0.0007 0.0007 0.0007 0.0007 0.0658
0.2950 0.0007 0.0007 0.0007 0.0007 0.0007 0.0664

114 | P a g e
 0.3000 0.0007 0.0006 0.0006 0.0006 0.0006 0.0671
0.3050 0.0006 0.0006 0.0006 0.0006 0.0006 0.0677
0.3100 0.0006 0.0006 0.0006 0.0006 0.0006 0.0683
0.3150 0.0006 0.0006 0.0006 0.0006 0.0006 0.0689
0.3200 0.0006 0.0006 0.0006 0.0006 0.0006 0.0695
0.3250 0.0006 0.0006 0.0006 0.0006 0.0006 0.0701
0.3300 0.0006 0.0006 0.0006 0.0005 0.0006 0.0706
0.3350 0.0005 0.0005 0.0005 0.0005 0.0005 0.0711
0.3400 0.0005 0.0005 0.0005 0.0005 0.0005 0.0717
0.3450 0.0005 0.0005 0.0005 0.0005 0.0005 0.0722
0.3500 0.0005 0.0005 0.0005 0.0005 0.0005 0.0727
0.3550 0.0005 0.0005 0.0005 0.0005 0.0005 0.0732
0.3600 0.0005 0.0005 0.0005 0.0005 0.0005 0.0736
0.3650 0.0005 0.0005 0.0005 0.0005 0.0005 0.0741
0.3700 0.0005 0.0004 0.0004 0.0004 0.0004 0.0745
0.3750 0.0004 0.0004 0.0004 0.0004 0.0004 0.0750
0.3800 0.0004 0.0004 0.0004 0.0004 0.0004 0.0754
0.3850 0.0004 0.0004 0.0004 0.0004 0.0004 0.0758
0.3900 0.0004 0.0004 0.0004 0.0004 0.0004 0.0762
0.3950 0.0004 0.0004 0.0004 0.0004 0.0004 0.0766
0.4000 0.0004 0.0004 0.0004 0.0004 0.0004 0.0770
0.4050 0.0004 0.0004 0.0004 0.0004 0.0004 0.0774

For V/F = 0.005 hours,

1
1 ⅆX 1 X2 ( X1 +X2 )
2
Taking f((V/F)j , X1,j ) = ⅆ(V/F) = 3.61 ∗ {(1 − X1 − X2 ) (2 X1 −X2 ) − }
0.48

1
X1,j+1 = X1,j + (p1 + 2p2 + 2p3 + p4 )
6
Take j = 0, we get

V V 1
p1 = (∆ F)f(( F)0 , X1,0 ) = 0.005 ∗ (3.61 ∗ {(1 − X1,0 − X2,0 ) (2 X1,0 −X2,0 ) −
1
X2,0 ( X1,0 +X2,0 )
2
}) = 0.0000
0.48

V
V V ∆ p1 p1
F
p2 = (∆ ) ∗ f(( )0 + , X1,0 + ) = 0.005 ∗ (3.61 ∗ {(1 − (X1,0 + ) − (X2,0 +
F F 2 2 2
p 1 p q
q1 1 p1 q1 (X2,0 + 1 )( (X1,0 + 1 )+(X2,0 + 1 ))
2 2 2 2
)) (2 (X1,0 + ) −(X2,0 + )) − }) = 0.0001
2 2 2 0.48

V
V V ∆ p2 p2
F
p3 = (∆ F) ∗ f((F)0 + , X1,0 + ) = 0.005 ∗ (3.61 ∗ {(1 − (X1,0 + ) − (X2,0 +
2 2 2
p 1 p q
q2 1 p2 q2 (X2,0 + 2 )( (X1,0 + 2 )+(X2,0 + 2 ))
2 2 2 2
)) (2 (X1,0 + ) −(X2,0 + )) − }) = 0.0001
2 2 2 0.48

115 | P a g e
 V V V
p4 = (∆ F) ∗ f(( F)0 + ∆ F , X1,0 + p3 ) = 0.005 ∗ (3.61 ∗ {(1 − (X1,0 + p3 ) − (X2,0 +
1
1 (X2,0 +q3 )( (X1,0 +p3 )+(X2,0 +q3 ))
2
q 3 )) (2 (X1,0 + p3 )−(X 2,0 + q 3 )) − }) = 0.0003
0.48

1
p = 6 (p1 + 2p2 + 2p3 + p4 ) = 0.0001

Therefore,
X2,1 = X2,0 + q = 0 + 0.0001 = 0.0001
The conversion X2 at t = 0.005 hours is 0.0001.
Compositions of the components:
V/F X1 X2 X1 + X2 C6H6 C12H10 C18H14 H2
0.0000 0.0000 0.0000 0.0000 1.0000 0.0000 0.00000 0.0000
0.0050 0.0302 0.0001 0.0303 0.9697 0.0150 0.00013 0.0152
0.0100 0.0586 0.0005 0.0591 0.9409 0.0288 0.00051 0.0298
0.0150 0.0852 0.0011 0.0863 0.9137 0.0415 0.00110 0.0437
0.0200 0.1102 0.0019 0.1121 0.8879 0.0533 0.00187 0.0570
0.0250 0.1338 0.0028 0.1365 0.8635 0.0641 0.00279 0.0697
0.0300 0.1558 0.0038 0.1597 0.8403 0.0741 0.00384 0.0818
0.0350 0.1766 0.0050 0.1816 0.8184 0.0833 0.00501 0.0933
0.0400 0.1960 0.0063 0.2023 0.7977 0.0918 0.00626 0.1043
0.0450 0.2143 0.0076 0.2219 0.7781 0.0996 0.00760 0.1148
0.0500 0.2315 0.0090 0.2405 0.7595 0.1068 0.00899 0.1247
0.0550 0.2476 0.0104 0.2581 0.7419 0.1134 0.01043 0.1342
0.0600 0.2628 0.0119 0.2747 0.7253 0.1195 0.01192 0.1433
0.0650 0.2770 0.0134 0.2904 0.7096 0.1251 0.01343 0.1519
0.0700 0.2904 0.0150 0.3053 0.6947 0.1302 0.01497 0.1601
0.0750 0.3029 0.0165 0.3194 0.6806 0.1349 0.01651 0.1680
0.0800 0.3147 0.0181 0.3328 0.6672 0.1393 0.01807 0.1754
0.0850 0.3258 0.0196 0.3454 0.6546 0.1433 0.01963 0.1825
0.0900 0.3362 0.0212 0.3574 0.6426 0.1469 0.02119 0.1893
0.0950 0.3460 0.0227 0.3687 0.6313 0.1503 0.02273 0.1957
0.1000 0.3552 0.0243 0.3794 0.6206 0.1533 0.02427 0.2019
0.1050 0.3638 0.0258 0.3896 0.6104 0.1561 0.02580 0.2077
0.1100 0.3719 0.0273 0.3992 0.6008 0.1586 0.02731 0.2133
0.1150 0.3795 0.0288 0.4083 0.5917 0.1610 0.02880 0.2186
0.1200 0.3867 0.0303 0.4170 0.5830 0.1631 0.03027 0.2236
0.1250 0.3934 0.0317 0.4252 0.5748 0.1650 0.03172 0.2284
0.1300 0.3998 0.0332 0.4329 0.5671 0.1667 0.03315 0.2330
0.1350 0.4057 0.0346 0.4403 0.5597 0.1683 0.03456 0.2374
0.1400 0.4113 0.0359 0.4473 0.5527 0.1697 0.03594 0.2416
0.1450 0.4166 0.0373 0.4539 0.5461 0.1710 0.03729 0.2456
0.1500 0.4215 0.0386 0.4601 0.5399 0.1721 0.03862 0.2494
0.1550 0.4262 0.0399 0.4661 0.5339 0.1732 0.03992 0.2530
0.1600 0.4305 0.0412 0.4717 0.5283 0.1741 0.04120 0.2565
0.1650 0.4346 0.0424 0.4771 0.5229 0.1749 0.04245 0.2598
0.1700 0.4385 0.0437 0.4822 0.5178 0.1756 0.04367 0.2629

116 | P a g e
0.1750 0.4421 0.0449 0.4870 0.5130 0.1762 0.04486 0.2659
0.1800 0.4456 0.0460 0.4916 0.5084 0.1767 0.04603 0.2688
0.1850 0.4488 0.0472 0.4959 0.5041 0.1772 0.04718 0.2716
0.1900 0.4518 0.0483 0.5001 0.4999 0.1776 0.04829 0.2742
0.1950 0.4546 0.0494 0.5040 0.4960 0.1779 0.04939 0.2767
0.2000 0.4573 0.0505 0.5077 0.4923 0.1782 0.05045 0.2791
0.2050 0.4598 0.0515 0.5113 0.4887 0.1784 0.05149 0.2814
0.2100 0.4621 0.0525 0.5146 0.4854 0.1786 0.05251 0.2836
0.2150 0.4644 0.0535 0.5179 0.4821 0.1787 0.05350 0.2857
0.2200 0.4664 0.0545 0.5209 0.4791 0.1787 0.05447 0.2877
0.2250 0.4684 0.0554 0.5238 0.4762 0.1788 0.05542 0.2896
0.2300 0.4702 0.0563 0.5266 0.4734 0.1788 0.05634 0.2914
0.2350 0.4719 0.0572 0.5292 0.4708 0.1787 0.05724 0.2932
0.2400 0.4736 0.0581 0.5317 0.4683 0.1787 0.05811 0.2949
0.2450 0.4751 0.0590 0.5341 0.4659 0.1786 0.05897 0.2965
0.2500 0.4765 0.0598 0.5363 0.4637 0.1785 0.05980 0.2981
0.2550 0.4779 0.0606 0.5385 0.4615 0.1783 0.06062 0.2995
0.2600 0.4791 0.0614 0.5405 0.4595 0.1782 0.06141 0.3010
0.2650 0.4803 0.0622 0.5425 0.4575 0.1780 0.06218 0.3023
0.2700 0.4814 0.0629 0.5444 0.4556 0.1778 0.06293 0.3036
0.2750 0.4825 0.0637 0.5461 0.4539 0.1776 0.06367 0.3049
0.2800 0.4834 0.0644 0.5478 0.4522 0.1773 0.06438 0.3061
0.2850 0.4844 0.0651 0.5494 0.4506 0.1771 0.06508 0.3073
0.2900 0.4852 0.0658 0.5510 0.4490 0.1769 0.06576 0.3084
0.2950 0.4860 0.0664 0.5525 0.4475 0.1766 0.06642 0.3094
0.3000 0.4868 0.0671 0.5539 0.4461 0.1763 0.06707 0.3105
0.3050 0.4875 0.0677 0.5552 0.4448 0.1761 0.06770 0.3115
0.3100 0.4882 0.0683 0.5565 0.4435 0.1758 0.06831 0.3124
0.3150 0.4888 0.0689 0.5577 0.4423 0.1755 0.06891 0.3133
0.3200 0.4894 0.0695 0.5589 0.4411 0.1752 0.06949 0.3142
0.3250 0.4899 0.0701 0.5600 0.4400 0.1749 0.07005 0.3150
0.3300 0.4904 0.0706 0.5611 0.4389 0.1746 0.07061 0.3158
0.3350 0.4909 0.0711 0.5621 0.4379 0.1743 0.07114 0.3166
0.3400 0.4914 0.0717 0.5630 0.4370 0.1740 0.07167 0.3174
0.3450 0.4918 0.0722 0.5640 0.4360 0.1737 0.07218 0.3181
0.3500 0.4922 0.0727 0.5649 0.4351 0.1734 0.07268 0.3188
0.3550 0.4926 0.0732 0.5657 0.4343 0.1731 0.07316 0.3194
0.3600 0.4929 0.0736 0.5665 0.4335 0.1728 0.07363 0.3201
0.3650 0.4932 0.0741 0.5673 0.4327 0.1725 0.07409 0.3207
0.3700 0.4935 0.0745 0.5681 0.4319 0.1722 0.07454 0.3213
0.3750 0.4938 0.0750 0.5688 0.4312 0.1719 0.07498 0.3219
0.3800 0.4940 0.0754 0.5694 0.4306 0.1716 0.07540 0.3224
0.3850 0.4943 0.0758 0.5701 0.4299 0.1713 0.07582 0.3230
0.3900 0.4945 0.0762 0.5707 0.4293 0.1710 0.07622 0.3235
0.3950 0.4947 0.0766 0.5713 0.4287 0.1707 0.07661 0.3240
0.4000 0.4949 0.0770 0.5719 0.4281 0.1705 0.07699 0.3245
0.4050 0.4951 0.0774 0.5725 0.4275 0.1702 0.07737 0.3249

117 | P a g e
At t = 0.005 hours,
XC6H6 = 1 − X1 − X2 = 0.9697
1
XC12 H10 = X − X 2 = 0.0150
2 1
XC18 H14 = X2 = 0.00013
1
X H2 = X + X2 = 0.0152
2 1

V/F r1 r2
0.0050 5.8532 0.0524
0.0100 5.4983 0.0976
0.0150 5.1642 0.1366
0.0200 4.8499 0.1699
0.0250 4.5543 0.1983
0.0300 4.2766 0.2223
0.0350 4.0157 0.2425
0.0400 3.7706 0.2593
0.0450 3.5405 0.2731
0.0500 3.3244 0.2843
0.0550 3.1216 0.2931
0.0600 2.9313 0.3000
0.0650 2.7527 0.3050
0.0700 2.5851 0.3085
0.0750 2.4277 0.3107
0.0800 2.2801 0.3116
0.0850 2.1416 0.3116
0.0900 2.0116 0.3107
0.0950 1.8895 0.3090
0.1000 1.7750 0.3066
0.1050 1.6675 0.3037
0.1100 1.5666 0.3003
0.1150 1.4718 0.2965
0.1200 1.3829 0.2923
0.1250 1.2993 0.2879
0.1300 1.2209 0.2832
0.1350 1.1472 0.2784
0.1400 1.0780 0.2734
0.1450 1.0130 0.2683
0.1500 0.9519 0.2631
0.1550 0.8945 0.2578
0.1600 0.8406 0.2525
0.1650 0.7899 0.2472
0.1700 0.7423 0.2419

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0.1750 0.6975 0.2366
0.1800 0.6554 0.2313
0.1850 0.6158 0.2261
0.1900 0.5786 0.2209
0.1950 0.5437 0.2158
0.2000 0.5108 0.2108
0.2050 0.4798 0.2058
0.2100 0.4507 0.2009
0.2150 0.4234 0.1960
0.2200 0.3977 0.1913
0.2250 0.3734 0.1866
0.2300 0.3507 0.1821
0.2350 0.3293 0.1776
0.2400 0.3091 0.1732
0.2450 0.2901 0.1689
0.2500 0.2723 0.1647
0.2550 0.2555 0.1605
0.2600 0.2397 0.1565
0.2650 0.2249 0.1526
0.2700 0.2109 0.1487
0.2750 0.1978 0.1449
0.2800 0.1854 0.1413
0.2850 0.1738 0.1377
0.2900 0.1628 0.1342
0.2950 0.1525 0.1307
0.3000 0.1428 0.1274
0.3050 0.1337 0.1241
0.3100 0.1252 0.1209
0.3150 0.1171 0.1178
0.3200 0.1095 0.1148
0.3250 0.1024 0.1119
0.3300 0.0957 0.1090
0.3350 0.0894 0.1062
0.3400 0.0834 0.1034
0.3450 0.0779 0.1008
0.3500 0.0726 0.0982
0.3550 0.0677 0.0956
0.3600 0.0631 0.0932
0.3650 0.0587 0.0908
0.3700 0.0547 0.0884
0.3750 0.0508 0.0861
0.3800 0.0472 0.0839
0.3850 0.0438 0.0817
0.3900 0.0406 0.0796
0.3950 0.0377 0.0776
0.4000 0.0349 0.0756
0.4050 0.0322 0.0736

119 | P a g e
 FIGURE 1

FIGURE 2
Figure 1 shows the plots of the rates of each reaction as a function of V/F. In both instances,
the rates decrease toward zero as V/F increases.
Figure 2 shows the plot of the total conversion, XT = X1 + X2 versus V/F.
The reactor volume required to process 10,000 lb/hr of benzene is estimated from the
components table. For a total conversion of 50.8 %,
V 10,000
= 0.2 ⟹ V = 0.2F = 0.2 ∗ = 25.64 ft 3
F 78

The components table also shows the compositions of benzene, di-phenyl, tri-phenyl and
hydrogen. At a fixed federate, increasing V/F values correspond to movement through the
plug flow reactor (i.e., increasing reactor volume). Thus, these results illustrate how the
composition varies with position in the reactor. Here, the mole fraction of benzene decreases

120 | P a g e
steadily as the reaction mixture progresses in the reactor, while the composition of diphenyl
increases and reaches a maximum between 1684 and 1723 hr-1 and thereafter decreases. This
is often typical of an intermediate in consecutive reactions.

Problem 5.17:
Acetic anhydride is hydrolyzed at 40°C in a CFSTR. The reactor is initially charged with
0.57 m3 of an aqueous solution containing 0.487 kmol/m3 of anhydride. The reactor is heated
quickly to 350 K, and at that time, a feed solution containing 0.985 kmol/m3 of anhydride is
run into the reactor at the rate of 9.55 × 10–4 m3 /sec. At the instant the feed stream is
introduced, the product pump is started and the product is withdrawn at 9.55 × 10–4 m3 /sec.
The reaction is first order with a rate constant of 6.35 × 103 sec-1 .

1. Perform the unsteady state balance and solve to obtain the startup transient in the product
stream concentrations of anhydride and acid.
2. Determine the concentrations of anhydride and acid after 120 sec.

Solution:
The reaction is
CH3CO-O-CO-CH3 + H2O → 2CH3COOH
Acetic anhydride Water Acetic acid
or A + B → 2C. Assuming that the reaction is first order with respect to the anhydride,
component A

121 | P a g e
Notations:
➢ CA0 = feed concentration, kmol/m3
➢ CAint = initial concentration at time t = 0, kmol/m3
V
➢ ť = uR = mean residence time, sec
➢ VR = volume of reactor, m3
➢ k = rate constant, sec-1
➢ CA0 = 0.985 kmol/m3
➢ CAint = 0.485 kmol/m3
➢ VR = 0.55 m3
➢ u = 9.55 * 10-4 m3/sec
➢ k = 6.35 * 103 sec-1
Component balance:
The unsteady state material balance of component A is
dCA
u ∗ CA0 = u ∗ CA + (−rA )VR + VR ∗
dt

Rearranging the equation we get,

dCA 1 1
+ ( + k) ∗ CA = ∗ CA0 (1)
dt ť ť
dCA 1
= (CA0 − CA ) − k ∗ CA (2)
dt ť
Both Equations are first order differential equations, which can be solved to determine the
transient concentration of the anhydride.
The transient concentration of acetic anhydride from Equation (1) with a first order
irreversible reaction is obtained from Equation (2)
1+k∗ť
−( )∗t
CA0 + {CAint (1 + kť) − CA0 } ∗ e ť
CA (t) =
1 + kť
VR 0.55
ť= = = 575.916 sec
u 9.55 ∗ 10−4

122 | P a g e
 1 + k ť = 1 + 6.35 ∗ 10−3 ∗ 575.916 = 4.657
0.985 0.485 ∗ 4.657 − 0.985 4.657
CA (t) = +{ } ∗ e−(575.916)∗t
4.657 4.657
Therefore, the startup anhydride concentration is
0.985 0.485 ∗ 4.657 − 0.985 4.657
CA (t) = +{ } ∗ e−(575.916)∗t
4.657 4.657

Problem 5.18
Consider the application of chemical reactor technology to a commercial reactor.8 Figure 5-
40 illustrates a simplified flow diagram of ethylene glycol production. Consider the reactions
in the formation of glycol:
● Hydration of ethylene oxides to ethylene glycol.
● Reactions of part of the glycol with ethylene oxide to form diethylene glycol.
● Further reaction of the ethylene glycol with ethylene oxide.
Solution:

In the following example, ethylene glycol product was manufactured to a specification that
limited the diethylene glycol and higher glycol content; formation of these materials caused a
loss in yield.

Reactions are series-parallel and are represented by-

A+B->R reaction constant=k1
A+R->S reaction constant=k2
A+S->T reaction constant=k3

123 | P a g e
Where A = ethylene oxide
B = water
R = ethylene glycol
S = di-ethylene glycol
T = tri-ethylene glycol
Considering the above reactions at constant volume (i.e., constant density) in a batch system,
rates of disappearance for A, B, R, and S are:
CA
(−rA ) = − = k1 CA CB + k 2 CA CR + k 3 CA CS
dt
dCB
(−rB ) = − = k1 CA CB
dt
dCR
(−rR ) = − = k 2 CA CR − k1 CA CB
dt
dCS
(−rS ) = − = k 3 CA CS − k 2 CA CR
dt
The rate of formation of T is
dCT
(rT ) = = k 3 CA CS
dt
For batch and plug flow reactors:
dCR k1 CA CB − k 2 CA CR
=
dCB −k1 CA CB
k 2 CR
= −1 +
k1 CB
Where R = CR and B = CB:
dR k2 R
= −1 +
dB k1 B
Rearranging:
dR k 2 R
− = −1
dB k1 B
The above equation is a first order differential equation of the form
dy
+ P(y) = Q I. F = e∫ Pⅆx
dx
dy
e∫ Pⅆx + e∫ Pⅆx P(y) = e∫ Pⅆx Q
dx
The general solution is e∫ Pⅆx y= e∫ Pⅆx Qdx + C. The integrating factor is

124 | P a g e
 K K k1
I. F. = e∫ Pⅆx = e− ∫BⅆB , where P = =
B k2 B
−K
e−Klnln B = elnln (B) = B −K
Multiplying the integrating factor by both the left and right sides of equation gives
dR −K K
(B ) − R. B −K = −1. B−K
dB B
Or
d
(RB−K ) − KRB−K−1 = −B−K
dB
d
(RB−K ) = −B−K
dB

−K
B−K+1 1
RB = −[ + R0 + ]
1−K 1−K
and
BK − B
R= + R 0 BK
1−K
The concentration of R is
CBK − CB
CR = + CR0 CBK
1−K

The design equations for a CFSTR with perfect mixing, constant fluid density, and steady state
operation are as follows. If u is the volumetric flowrate and K = k1/k2, relative reaction rate
constant, where k1, k2, and k3 are the specific reaction rate constants for reactions. The rate
expressions of A, B, R, S, and T are
(−rA ) = k1 CA CB + k 2 CA CR + k 3 CA CS
(−rB ) = k1 CA CB
(−rR ) = k 2 CA CR − k1 CA CB
(−rS ) = k 3 CA CS − k 2 CA CR
(+rT ) = k 3 CA CS
The material balances of components A, B, R, S, and T are:

125 | P a g e
 Input rate = Output rate + Disappearance by reaction + Accumulation
Mass balance on A is
u ∗ CA0 = u ∗ CA + (−rA )VR
u ∗ CA0 = u ∗ CA + (k1 CA CB + k 2 CA CR + k 3 CA CS ) ∗ VR
Mass balance on B is
u ∗ CB0 = u ∗ CB + (−rB ) ∗ Vr
u ∗ CB0 = u ∗ CB + k1 CA CB VR
Mass balance on R is
u ∗ CR0 = u ∗ CR + (−rR )VR
Mass balance on S is
u ∗ CS0 = u ∗ CS + (−rS ) ∗ VR
Mass balance on T is
u ∗ CT0 + (+rC )VR = u ∗ CT
0 = uCT − k 3 CA CS VR
Rearranging the equations:
u(CB0 − CB ) = k1 CA CB VR
u(CR − CR0 ) = (k1 CA CB − k 2 CA CR )VR
Dividing equations yields,
CR − CR0 (k1 CA CB − k 2 CA CR ) ∗ VR
=
CB0 − CB k1 CA CB VR
That is,
CR − CR0 k 2 CR
=1−
CB0 − CB k1 CB
Or
R − R0 k 2 CR
=1−
B0 − B k1 CB
Rearranging this equation for R in terms of B0, B, R0, and K = k1/k2 gives
B{(B0 − B) + R 0 }
R=
B + K(1 − B)
Or
CB {(1 − CB ) + CB0 }
CR =
CB + K(1 − CB )

126 | P a g e
Davis et al. [9] have performed studies on the batch hydration of ethylene oxide. Their work
determined the value of the product distribution constant K. This value is used in equation to
determine the expected performance in a plug flow reactor. This value is also used in
equation to illustrate the poor performance that would be obtained with complete
backmixing. The results show that the plant reactor falls between the plug flow and
backmixing reactor lines. The distance between lines (2) and (3) in figure below measures the
degree of backmixing. There is considerable departure from the theoretical plug flow curve.
This shows that there is room for improvement in the process of eliminating or reducing
backmixing. The wide deviation from batch performance is possibly caused by:
• Case 1: Backmixing in the reactor.
• Case 2: Buildup of ethylene glycol in the recycle to the reactor.
• Case 3: Buildup of other reaction products in the recycle.
Since the reactors were a series of baffled tanks, Case 1 is most likely. Case 2 can be
evaluated quantitatively by using the kinetics applicable to the reaction and making suitable
changes to allow for the recycling of ethylene glycol.

Case 3 is extremely unlikely because the impurities formed are water-soluble and should,
therefore, be removed by the water purged from the system. A longitudinal tubular reactor in
place of a high backmixing reactor results in substantial savings in processing costs because
selectivity and productivity are increased.

127 | P a g e
THE END

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