7.

Temperature effects in reactor

7.1Temperature change during reaction
How comes Changes of temperature in the
reaction ??
Changes of temperature in the reaction happens
 by the nature of the reaction

 deliberately (by heat exchange

with the surroundings)
The nature of the reaction
 The temperature change comes during the
reaction through bond breaking and forming
and this is accompanied by the evolution
(exothermic) or absorption (endothermic) of
heat.
 Exothermic Exothermic
TR
TR
Isothermal Isothermal
T To T
To Endothermic
TR Endothermic TR

t V, L,W
Figure : Temperature change during reaction for batch &
continuous operation
Under this principle it is hard to assume a
chemical reaction that has a reaction heat of zero.
Next figure shows schematic diagram of
temperature change during reaction in a batch
and continuous operation
Exothermic reaction in adiabatic reactor

TR
r

L, V, W

Figure : Conversion (X), Temperature (T) and the

Rate of reaction (r) versus the Length (L), Volume
(V) or Weight of a catalyst (W)
Endothermic reaction in adiabatic reactor

TR

r
L, V, W

Figure : Conversion (X), Temperature (T) and the Rate of

reaction (r)versus the Length (L), Volume (V) or Weight of
a catalyst (W)
If there is a chemical reactions, the
following changes occur :
Temperature,
conversion, and These are
reaction rate interrelated
Volume / Pressure to each other

and are important parameters to the Design

of a reactor(size and time)
This relation also depends on the heat
liberated (exothermic) or heat absorbed
(endothermic) during the reaction.
Change of temperature on the reacting
fluid, some times is Undesirable

e.g. for Exothermic rxn

 Undesirable temperature change causes
 Product decrease( equilibrium)
n
 low production rate Pr  B
(B) t
C
 fast rate of reaction(explosive)

 Damage the reactor

Undesirable temperature change is
controlled
I. by Supply (endothermic) or withdrawal
(exothermic) of heat during the
reaction,
II by division of a fixed-bed reactor
into section with intermediate
cooling or heating of the mixture

III. by addition of an inert compound,

or excess reactant for reducing
temperature changes
 I. Supply (endothermic) or withdrawal
(exothermic) of heat during the
reaction,

Q Q

(a) (b)

Figure : Heating (a) or cooling (b) of the reactor

for endothermic or exothermic conditions
Coolant
Heater

(a) (b)
Figure : Batch reactor with cooling (a) and
with heating (b)
Notice !!
Strong cooling / heating / also affects the
path, irrespective of whether it is strong or
poor or medium cooling/ heating
Effect of cooling in Exothermic reactions

Poor cooling
Poor cooling

T XA Moderate cooling
Moderate Cooling

Strong cooling

To
Strong cooling

L, V, W L, V, W

Figure : The effect of cooling on the temperature and

conversion against the Length (L), Volume (V) or Weight of
a catalyst (W)
Supply or Withdraw of heat during reaction is
effected by the so called

Heat Transfer fluid, coolant

Heat Transfer Equipment,

Heat transfer fluid
As a heat transfer fluid,
we prefer to use water.

If we use other fluids / Coolant,

the more practical difficulties
may be encountered due to the
Cost,

 corrosion,

 specific & latent

Table : Heat transfer fluids /Coolant that are
commonly used, with working temperature range
Media Range Usage

Various -400C to Low temperature duties

Fluorocarbons +200C
NaCl - brine -200C to Low temperature duties,
+200C aqueous coolant
Water / Steam 00C to Used as liquid phase or
2000C (10 liquid/vapor system
bar)
Heat-transfer 300C to Stable, low viscosity mineral
Oils 3200C oils for liquid circulation (e.g
mobiltherm 600)
Dowtherm A 200C to Diphenyl oxide as liquid or
4000C liquid/vapour system
Inorganic Salts 1500C to Mixture of sodium, nitrite,
4500C nitrate, and potassium nitrate
Another method for

Undesirable temperature change

control are

II by division of a fixed-bed reactor

into section with intermediate
cooling or heating of the mixture

III. by addition of an inert compound,

or excess reactant for reducing
temperature changes
7.2 Temperature effects on reaction rates

Let us consider the following highly exothermic

reaction is carried out adiabatically in a batch reactor

A B
Our object is to calculate the reaction time for
60% conversion.
•Mole balance and design equation

X A, f
dX A
tr  C A,O 
0 ( rA )
• Rate Law, for first order reaction is

 rA   kC A

• Stoichiometry
Liquid phase
V f  V0 C A  C A,0 1  X A 

• Combining and canceling the entering

concentration

X A, f
dX A
tr  
0 k (1  X A )
In adiabatic reaction, temperature is changing during the
course of reaction i.e., k is also varying, it is a function
of temperature.,
This forces us not to take k outside the integral,
Recalling the Arrhenius equation  E  1 1 
k  k0 exp    
R  T T 
 0 
X A. f
dX A
tr  
0 K o exp  E  1  1  1  X A 
 R  T T 
  o 

To solve this Integral, we need a relation of XA and T.

i.e The Energy Balance
Hence, the design of non-isothermal reactors involves the
simultaneous solution of both material and energy
balances
7.3 Finding Workable /Optimum/
temperature profiles for non- isothermal
reactors

•There are Four core variables in reactor

• temperature, T

• Concentration / Conversion XA

• reaction rate (-rA) and

• the size of the reactor, V , time , tr

These core variables (T, C, r, V/ tr) in a
chemical reactor influence

the design and

performance

Since the temperature influences

We should find
the rate of reaction, workable
/operating/
temperature in
the conversion
the reactor which
satisfy the
the size of a reactor, parameters
Finding Workable temperature for Non-
isothermal reaction
Adiabatic

T
r
Non-Adiabatic

Positive Negative

T L
Figure : Relationship between the temperature,
rate of reaction and the length in non-isothermal
Looking to the above Figure, Generally, one
can see two conflicting situation in rxn:
high temperature offers high
reaction rate. This is positive
but
high temperature obtained with high
volume of reactor. This is negative

These are two conflicting situation !!!!!

Require optimum operating
temperature
 Optimum operating temperatures in
the reactor
Definition
are those at which the chemical
reactor shows an economically
justifiable maximum production
rate per unit length of reactor in
terms of the desired product
Of course, our target in the design of a reactor,
 is to find the size of a reactor for a
specified conversion.
This is not also the end,
 we have further to consider if it is
possible to minimize the size of the
reactor.
This means we have to establish,
optimum operational temperature range,
which gives
 maximum conversion, T(X)
 plausible (acceptable) rate of
reaction within the small
size (length) of the reactor.
r(V)
We have to see r(V)
As an example, Looking to the design equation
X
A dX A
V F
R A,0  (r )
0 A N-2
The minimum volume will be achieved
if the reaction rate is maximum
at all positions in the reactor
Therefore, Optimum operating temperature in the
reactor at any given position will be that for which
the rate of reaction is maximum at
any conversion level.
We have to find the relationship b/n, the rate of
reaction
r[T,C(X] is the basic
information necessary
 to the conversion, to determine optimum
operating temperature
 to temperature, in the reactor
 Optimum operating temperatures
in the reactor
are those at which the chemical
reactor shows an economically
justifiable maximum
production rate per unit length
of reactor in terms of the
desired product
This means we have to establish,
 maximum conversion,
 maximum rate of reaction
 Minimem size of the reactor.
 to determine the workable / optimum
We have to work temperature/ sequence,

 which minimizes the reactor volume or

the time of the reaction for a given
conversion

 at the same time achieving the

maximum rate of reaction at all
positions in the reactor.

r(T , C(X))
o n not to forget that to achieve this
ti
e n different reactions give different
t
At solution.
7.3.1 Optimum operating temperature
for irreversible reaction
Consider the reaction A P
The rate of disappearance of reactant A
r(T , X )  kC
r a te

A A
 A(e-E RT ) C (1 - X )
A,0 A
ct i o n

 A(e-E RT ) f (X )
A
m rea

r(T , X )  A(e-E RT ) f (X ) (a)

A A
 r r
I II
u

r  f (T )
Maxim

I
r  f (X )
II A
where f(XA) is usually a decreasing function of XA
From r  f ( X ) a rise in the fractional conversion
II A
brings about a
fall in the rate of reaction.

Since E is positive
r  f (T )  A(e-E RT )
I

Temperature increasing, will increase the rate

exponentially
This compensate the falling of the rate
in rIi i.e.,
the rate increases with the temperature at any
composition.
This is, therefore, to deduce that
the optimum operating temperature in the
reactor will be the highest temperature that
is possible.
Of course, this conclusion has a limit due to
 the properties of the construction
materials and
 the formation of the side reactions.
For irreversible reactions, the drawn
n

conclusion applies for both

sio
lu

endothermic and exothermic

nc

reactions (use highest temperature

Co

r  f (T )  A(e-E RT )
I
7.3.2 Optimum operating temperature
for reversible reaction
Consider the reversible reaction,
A P
which has the rate of reaction function ability as
- E RT 1 - E -1 RT
r (T , X A )  A(e ) C A,0 (1 - X A ) - A (e ) C A,0 X A

- E RT 1 - E -1 RT
 A(e ) f ( X A ) - A (e )g( X A) (b)

g(XA), E-1applies for the reverse reaction

The function g(XA) is always an increasing function

and the concentration of product increases with

the conversion
Energy of reactant molecule Exothermic
Endothermic

E’ E

E E’
H  E - E'  0
R
H  E - E'  0
R

Distance along rxn path

Endothermic reversible reaction
In an endothermic reversible reaction ,
since E > E-1,
the rate of forward reaction increases more rapidly
with temperature than that of reverse for any conversion,

which brings that

the optimum operating temperature is
the maximum permissible
temperature.
Exothermic reversible reaction
In an exothermic reversible reaction, E’ > E
Hence, the rate of reverse reaction increases more
rapidly with the temperature than that of the
forward reaction.
On the other hand, the equation (b) depicts that

the reverse reaction will be slow at low conversion, while

the forward reaction rate will be fast.
For the rate to be maximum at any conversion, the
temperature should be
 High at low conversion where
predominantly the forward reaction takes
place
 Lower at high conversion, where the rate
of the reverse reaction is high.
Hence, for reversible exothermic reactions the
optimum operating temperature sequence is a
changing temperature. i.e., starting at high
temperature and gradually changing to a
decreasing temperature.
Next Figure shows the operating line for
minimum reactor size.
 In the figure, the net rate from the equation
(b) is plotted versus temperature; each curve
corresponds to a constant conversion.
 An optimum operating temperature is
determined by counting the maxima and is
shown by the dashed lines.
 Establishing of the optimum operating
temperature, encounters technical
difficulties and expensive costs are involved.
 Thus it is difficult to implement in the industry.
 Since most of the industries these days are
working with gas phase in the presence of a
catalyst, it is much simpler from a technical
point of view, to let the reaction proceed
 X4> X3 > X2 etc

X1 =0
r
X2
X3
X4

T
Figure : Optimum Operating Temperature sequence for an
exothermic reversible reaction.
7.4 Energy balance for chemical
reactors
Concept
 By nature Chemical reactions are
always associated with energy

 These energy changes take place

because during chemical reactions
certain bonds are cleaved(broken) and
certain new bonds are formed

 Energy is consumed during cleavage of

bonds while energy is released during
the formation of bonds
 Since the bond energy varies from one
bond to another, the chemical
reactions are always accompanied by
absorption or release of energy.

 Most of the time, this energy is in the

form of heat
The energy changes occurring during the
chemical reactions may not always appear
as heat (thermal) energy, but also as

 kinetic energy,

 potential energy,

 electrical and

 magnetic field.

But, in most reactor calculations, the terms with

thermal energy and work done on the
surroundings are of the main importance.
Energy balance
The application of the principle of
conservation of energy
the total amount of energy in an
isolated system remain constant over
Thistime,
leads to an energy balance which is in
general states that:
Rate of Rate of Rate of Rate of
Accumulation = Energy - Energy + Energy
of Energy In Out Production
For any open model system
dH
HF dt HE
Q /dQ
Analyzing the heat balance
Looking to the heat balance in a chemical reactor
[heat accumulation in a vessel] =
[heat addition] + [heat generation] -
[heat removal by coolant] - [heat
loss to surroundings].

Heat removal
From the above Fig. effect of reactor
 Heat removal capability increases with the
square of the linear dimension (see Fig.)
 Heat generation increases with the
volume of the vessel, by the cube of the
linear dimension.
1. The heat generated by a
de

reactive system will increase

lu

more rapidly than the

nc

capability of the system to

Co

remove heat when the

process is operated in a larger
vessel.
2. Here is always an evolution or
absorption of energy in the reaction
3. Generally, if the reaction temperature
is easily controlled in the laboratory,
this does not mean that the
temperature can be controlled in a
plant-scale reactor.
4. Hence a large vessel will require more
heat transfer area in the form of
immersed coils.
For any open model system of reactor
dH
HF dt HE

Q /dQ
As the starting expression for treating
heat effects (energy balance) :
 for BR and Continuous reactor

H  H UA(T T )  dH (1.10.2)
F E S dt
for Differential reactor

H  H U (T T )dA dH (1.10.2)
F E S dt
where
U - Overall heat transfer coefficient
TS - Surrounding (cooling, heating)
temperature
A - Effective area for heat transfer
dA - differential circumferential heat
transfer area
T - The temperature of the reaction
mixture
 In a batch process

HF = HE
The energy balance for batch process becomes

UA(T T )  dH (1.11)
S dt

We have to define enthalpy change,dH

The enthalpy change comes in the reaction
due to:
 the change in composition
 the change of temperature
 The enthalpy change due to the change in
composition is expressed by the energy
change due to the heat of the reaction

H (rV )dt
R

 The enthalpy change due to the change in

temperature is expressed

m C dT
T P
hence

dH  m C dT  H (rV )dt
T P R

Where : mT is the total mass of the reaction mixture; CP is

the specific heat for the composition of the mixture

Substituting the enthalpy change to the

energy balance we get for batch process

m C dT  H (rV ) UA(T T ) (1.11,1)

T P dt R S
In a continuous process where accumulation is not
existing, the energy balance equation then becomes

H  H  dH UA(T T )
E F S
The enthalpy change should be expressed
H - E dH  F C dT  H (rV ) (1.12)
E F T P R
Then, the energy balance for continuous process
is
F C dT  H (rV ) UA(T T ) (1.13)
T P R S
Where : FT is the total molal feed flow rate; CP is the molal
heat capacity of the reaction mixture
Energy balance for reactor
involving differential volume (PFR)

 Looking the change developed in

pipe reactor

T T+dT
FR,0 H dV H+dH FR
  Temperature change across the
length of a reactor for example for
exo reaction

T
dT
dL
dV

L, V
For PFR the control volume is a differential
volume
Substituting eq. (1.14.2) to the energy
balance for differential reactor (PFR)
becomes
(1.14.3)

F C dT  H (rdV ) U (T T )dA
T P R S

o t e V=AL dA=4 / D dV
l s n
P dA=ЛDdL dV=ЛD2/4 dL
where
D - is the diameter of the tube or vessel
L - the length (distance) along the reactor
from the inlet
Then, the energy balance for a PFR, as an
enthalpy balance, may be developed similarly to
continues reactor taking the consideration as

T T+dT
FR,0 H dV H+dH FR

H  H U (T T )dA dH (1.14)
F E S dt
Accumulation is not existing, the energy balance
equation then becomes

H  H U (T T )dA 0
F E S
Or

H  H  dH U (T T )dA (1.14.2)
E F S
The enthalpy change should be expressed

H E - EF  dH  FT CPdT  H R(rdV )
7.5 Reactor design involving heat in reactor
To calculate the heat effect in batch reactor, we use
the energy balance equation as

m C dT  H (rV ) UA(T T )
T P dt R S

For the rate of disappearance of A

m C dT  H (r V ) UA(T T )
T P dt R A S
7.5.1 Isothermal and non-isothermal batch
reactor design
(A)Isothermal Batch Reactor
Due to the nature of the reaction it is hard to
imagine heat of reaction is zero.,

Normally to bring in isothermal condition, the

reaction is brought immediately to that of the
surrounding by cooling (if the reaction is
exothermic) or heating (if the reaction is
endothermic) i.e., the temperature of the reacting
mixture is maintained constant through out the
course of reaction. This happens with the
assistance of the heat transfer medium under
perfectly stirring condition.
 H  0
R
T Exothermic

Initial reaction Isothermal H  0

R
Temperature

Endothermic
H  0
R
tr
Figure : Effect of temperature versus time in a
batch reactor
Ts

Temperature
Controller

Reactor

Steam

Heat Supply

Figure : External control of the reaction mixture

Isothermal operation, dT=0
 there is no change of reaction temperature,
i.e., constant temperature (dT = O).
m C dT  H (r V ) UA(T T )
T P dt R A S
Hence, the energy balance equation becomes

H (r V ) UA(T T )
R A S
On the other side, due to the nature of reaction
conversion and
temperature
Rate of reaction are changing with time
lly
a (r )  f (C,T )
rm A
N o
We have to bring
Rate of reaction only a function of concentration /
conversion, XA /
(r )  f (C)
A

This is done by Q  UA TS T
 
 
 
 
 

rate of heat transfer value

(heat transfer equipment)
i.e
The heat transfer equipment, control the temp

Q  UA T T
 
 


S 


control the temp is done by changing
i) The over-all heat transfer co-
efficient U, which is largely
dependant on the agitator
speed and the viscosity of
the liquid
ii) Surrounding temperature, Ts
Ts usually varies as the
te reaction proceeds (XA),
N o
because of the rate of
reaction
The surrounding temperature, TS
The surrounding temperature is adjusted to
control the rate of heat transfer (Q)
(heat transfer equipment) to achieve
(nearly) isothermal conditions in the
reactor.

This bring
the temperature in the reactor
becomes constant and
eventually the rate of reaction
will be not influenced by
temperature (r )  f (C)
A
Ts
Temperature
Controller

Reactor

Steam
TS
Heat Supply
T

Figure : External control of the reaction mixture

in endo. rxn
Finding the relationship b/n TS Vs C/ XA
By combining
H (r V ) UA(T T )
energy balance R A S

material balance
dX
r V  n A
 
 
 


 A R A,0 dt




Substituting (-rAV) from mole balance to energy

balance becomes

dX


H n

A UA T  T 




R A,0 dt S
   
   
   
The surrounding temperature is calculated

dX
H R  n A,0 dt
A
T  T 
S UA

The surrounding temperature control the

temperature change in the reactor so that
the temperature in the reactor becomes
in
Ag a

constant and eventually the rate of

reaction will be not influenced by
temperature InChEng p303 E2.5
Exercise 7.1 The elementary reaction
AB
is carried out isothermally at constant volume in a
batch reactor. The following data are given for
the reaction:
V 1.8 m3 , k  0.3 h-1 , CA,0 1500 mol / m3,   800 kg / m3,

H R  62.9 kJ / m 2  h  K,
C P  2.51 kJ / kg  K , T0  313 K, A  7.5 m 2 ,
2
U  251.4 kJ / m  h  K
Find the relation between cooling
temperature and conversion at reaction
temperature of 333 K
(B) Non – isothermal Batch Reactor
 By nature of reaction Temperature in side
the reactor may change considerably if
left unattended, and
 It may not be realistic to use isothermal
operation of a reactor as a basis for
design, particularly for a reaction that is
strongly exothermic or endothermic.
 Hence, Temperature may need to be
controlled so that it does not go too high
or too low, for high exo. and endo. rxn
For such cases Temperature must
be controlled !!
 If the temperature does not go too high o
too low, we can avoid controlling Temp.
The heat balance for non isothermal becomes,

m C dT  H (r V ) UA(T T )
T P dt R A S

Non isothermal operation convened in two cases :

1) Non adiabatic (Q # 0) : with heat

exchanger - to Control the Temp.
Non Isothermal process

2) Adiabatic (Q = 0) : with out heat

exchanger - not to control Temp.
Adiabatic
a) Design of non – isothermal Batch Reactor /
With heat exchanger/ Q #0/
TR is controlled by Q(TS)

Design Equation
m C dT  H (r V ) UA(T T )
T P dt R A S
(-rA) is a function of conversion and
temperature
(rA)  f ( X A ,T )

We have to find(-rA) ???

Finding (-rA) as a function of conversion
and temperature
Taking as an example of a first-order elementary
reaction, the rate of reaction becomes,
 rA   kC A,0 1  X A 

and the rate constant is defined using Arrhenius

Law,
 E 
k  A exp .  
 RT 
Combining gives rate as a function of both
conversion and temperature (rA)  f ( X A ,T )

 E 
 rA   A exp  C A,0 1  X A 
 RT 
Substituting the rate equation to the energy
balance for non-isothermal operation gives,

m C dT  Aexp  E C 1 X  H V UA T T
      
      
 
T P dt 
 RT A,0




A R





 S







The Equation involve four variables

tR , XA, V ,T
For constant volume, the variable are reduced to

time of reaction,

 conversion and

 temperature.

Note
The most important parameter is
the reaction time or eventually the
size of a reactor for a particular
conversion
The time of a reaction required for a particular
conversion involves simultaneous solutions of
the
Material balance
X A. f
dx A
tr  C A,0 
0  rA 

and energy balances

m C dT  Aexp  E C 1 X  H V UA T T
      
      
 
T P dt 
RT A,0

 A 

 R R 

 S 








B ut Simultaneous solution of material
and energy balance in:

 analytical form is difficult and

 numerical methods or analogy

simulation must be used.

Analytical solution is possible for a first - order

reaction by using the so called trial and error
method

See Book p53…and Ex. 2.6

 In designing non-isothermal, there are

!
n!
a lot of questions to be answered
io
nt
to design a reactor, such as
te

type of materials of
At

construction,

Non – Isothermal heat transfer

process equipment
require etc.
two designs
 Reactor design
 Heat exchanger design - used to
control T

Reactor design
require to use the material balance
and the energy balance
b) Design of Adiabatic / Q =0/ Batch Reactor
(non – isothermal Reactor) /
TR Not controlled
Operate without any heat addition or removal
(without any heat transfer equipment)
Based on these facts adiabatic reactors are
inexpensive and are used almost in all the
industry

u t Free temperature of reaction is

B difficult to conduct !!!!!!
Hence
Adiabatic reactors can be used :
1. For not excessive temperature change. In
such case conversion and yield can be
attained without any problem
Also we use for
2.High exothermic reaction: In such case inert or excess
of one reactant /heat sink/ can be added so that the
desired conversion and yield are not adversely
affected by excessive temperature change.
The energy balance for non isothermal adiabatic batch
reactor without heat transfer (Not controlled) becomes
Using energy balance for non isothermal
m C dT  H (r V ) UA(T T )
T P dt R A S

Energy balance for

m C dT  (H )(r V )
adiabatic reduced to T P dt R A
or

dT dX A
mT C P  n A,0  H R 
dt dt

m C dT  n  H dX
 
 

T P A,0 R A






Equation Shows:
• Time is not involved
Eliminates the need for
simultaneous stepwise solution
n
io

of the mass and energy balances

nt
te

which was the case for non

At

isothermal reaction
Differentiation of equation for the initial condition of X A  X A,0
and T = TO and final condition of X A  X A, f and T  T f

 
m C T T   H n X X
     
   
   
T P 0

 R A,0 A A.,0














with the initial condition, X A,0  0 the equation can be rearranged

 H R n A,0 X A (2.33.1)
T - T0 
mT C P

Let
 H R n A,0
Tad 
mT C P

Where Tad is the adiabatic temperature rise of the

reaction mixture
Substitution and rearranging becomes

(2.33.2)
T  T0  Tad X A
 This adiabatic temperature rise indicates
about how much the temperature of the

n
io reaction mixture would rise if the reaction is to
nt
proceed adiabatically to completion. XA=0
te
At

T T  T (1)
0 ad
The relationship between the temperature and the
conversion in an adiabatic reactor gives.

1
XA  T  T0  (2.33.3)
Tad

or
T T  T X
0 ad A
Plotting Conversion versus temperature from
the equation gives
1
XA  T  T0  XA
Tad

a slope of value
T0

1 m C
Slope   b  T P
T
ad
 H n 
R A,0


The sign of the slope depends on that of enthalpy

change: (-) exothermic,(+) endothermic
The sign of the slope depends on that of enthalpy
change

H  0
R
XA
H  0
R

Slope
T0 T
Characteristics of the adiabatic temperature rise
 H R n A,0
Tad 
mT C P
It's value depends on the initial composition
(initial condition) ,Heat of reaction and
heat capacity
 The higher value of adiabatic
temperature i.e., the gradient rise is an
indication of a stronger thermal effect
of the reaction mixture
These thermal effects can be subdued through the
 dilution of the mixture
 addition of excessive amounts of some
of the reactants or inerts (increased
inerts Cp rises)
 ∆HR > 0 Isothermal
∆HR < 0
Increase Increase
inert inert

XA
Decrease inert Decrease inert

To T

Figure 2.14 The effects of addition of inert to the reaction

mixture and the variation of conversion versus
temperature in an adiabatic operation.
Exercise 7.2 The elementary reaction
A B
is carried out in constant volume in a batch
reactor. The following data are given for
the reaction:
V 1.8 m3; k  0.3 h-1 ; CA,0 1500 mol / m3;
  800 kg / m3; H R  62.9 kJ / mol;
CP  2.51 kJ / kg K; T0  313 K;

Find the highest adiabatic temperature of

the reaction
7.5.2 Isothermal and non-isothermal PFR
reactor design
General energy balance for PFR is

F C dT  H (rdV ) U (T T )dA
T P R S

For disappearance of reactant A becomes

F C dT  H (r dV ) U (T T )dA
T P R A S
dA - differential circumferential heat
transfer area
 o t e
N

U (T T )dAUa (T T )dV
S S
Where a is the heat exchange/ Transfer
area a=4 / D
o t e If L is the reactor length and D is its
l s n diameter of the reactor
P
dA=ЛDdL
dV=ЛD2/4dL
dA=4 / D dV
We have Conversion and size of reactor for PFR
from material balance has
F dX  (r )dV
A,0 A A
The Energy balance for Plug flow reactor
conversion, size of reactor and temperature give
us

FT CPdT  H R F A,0dX A U (TS T )dA

We know
dA=4 / D dV
Substuiting we get

4U (Ts T )
FT CPdT  H R F A,0dX A  dV (3.10.1
D

This equation is analogue to the equation of batch reactor

energy balance.

mT CPdT  H Rn A,0dX A UA(TS T )dt

The only change is in batch reactor, where we

speak in terms of change of time, but in plug flow,
it is in terms of change in volume
(A) Isothermal Operation dT / dV =0, then
The reaction temperature across the length of the reactor
is constant i.e the energy balance equation (3.10)
becomes
H R F A,0dX A U (Ts T )dA

4U (Ts T )
or (H R )F A,0dX A  dV
D
Rearranging the equation also gives the differential
equation describing the change of conversion with volume
of a reactor for isothermal condition.

dX A 4U (TS T )

dV R D(H R )F A,O
The temperature necessary from the heat
exchanger to cool or heat to maintain the
isothermal operation is calculated by using

dX D(H R )F A,0 dX
H R  n A,0 A TS  T 
U
A
dV R
TS  T  dt

UA

The equation
 simply means that during the process /reaction/
heat evolution or absorption can be regulated by
using heat exchanger (cooling or heating), TS or
changing the flow rate of the substance
 depicts that cooling / heating temperature
medium is a function of both the rate of
reaction /conversion/ as well as the length of the
Exercise 7.3 Consider the gas phase
decomposition reaction A 2B
Q

T = 1000K T = 1000K

is carried out in a plug flow reactor. The reactor is to be

jacketed as we see in the Figure, so that a high
temperature gas stream can supply the energy necessary
to maintain the isothermal operation. Determine the
temperature profile of the external heating gas down the
length of the reactor that would be necessary to maintain
the isothermal operation.
Pure reactant is injected in the reactor is taken as
a temperature of 1000K.  H=78758 J / mol
acetone. The heat transfer area per unit volume
of pipe is 150m-1, rate constant, k, is 3.58 s-1, the
initial concentration of A is 18.8 mol / m3, the
overall heat transfer coefficient is 110 J/m2.s.K.,
volumetric flow rate is 0.002 m3/s. The area of
the pipe is 5.56x10-4 m2.
B) Non Isothermal Operation

FT CPdT  (H R )F A,0dX A U (TS T )dA

Note: Temperature is free:- Something to done!!!

We can carried out Non Isothermal

Operation in two cases:
i) Controlled temperature (Non Isothermal)

With heat transfer, Q

ii) Non controlled temperature / adiabatic process

With out heat transfer, Q=0
i) Controlled temperature, With heat transfer, Q
Non isothermal operation of a plug flow reactor, is
required to find the relationship
 the reaction temperature
 conversion and
 volume of the reactor.
And the solution will be simultaneous solution of
Energy balance
FT CPdT  (H R )F A,0dX A U (TS T )dA

Material balance X dX
V  F  A, f A
R A,0 0 (r )
A

te Method of solution is identical to BR

N o
non isothermal operation
ii)Non controlled temperature Adiabatic Operation
Adiabatic reactor of plug flow
 is working without any addition of heat or removal. In
another words,
it works without the use of heat exchanger, Q=0.

U (TS T )dA  0
 This type of reactor may be materialized by simple
insulation of the reactor against loss of heat

 This simplified the use of adiabatic reactors for most of

the industrial production.
Of course the rise and fall of the temperature leads to
unfavorable equilibrium with exothermic and endothermic
reaction. This problem is solved by using multi stage
operation.
 X3>X2>X1>
To Z=0

T1 , X 1 T1 X3
T2

T
2
T X2
T3 , X 2
T
3 X1
T4 4

X1

T5, X5 Z = TLo T5 T
Product

Feed
Figure : Cooling to the desired, temperature by using
indirect heat exchanger in fixed bed reactors.
Then the energy balance equation is reduced for adiabatic
condition to
F C dT  (H )F dX
R P R A,0 A

Integrating and rearranging gives (H )F

T T  R A,0 X
(H )F 0 F C A
Let R A,O R P
T 
ad F C
R P
Substituting equation we obtained the adiabatic energy
balance equation
T T  T X
0 ad A

or T  T X
ad A
The adiabatic temperature Tad
(H )F
T  R A,O
ad F C
R P
is one of the most important characteristics of the mixture.
 It's value depends on initial
the
composition (initial condition) ,Heat of
reaction and heat capacity
 The higher value of adiabatic temperature i.e.,
the gradient rise is an indication of a stronger
thermal effect of the reaction mixture
These thermal effects can be subdued through the
 dilution of the mixture
 addition of excessive amounts of some
of the reactants or inerts (increased
inerts Cp rises)
Analyzing adiabatic energy balance equation
(H )F
T T  R A,0 X
0 F C A
R P
If Cp is constant and the heat of reaction is
independent of temperature then adiabatic
energy balance equation is reduce to
C T
X  P
A  H
R
The resulting lines are straight for all
practical purposes since the variation of
the denominator term of these equations is
relatively small. This is shown in the next
Fig.
 1.0
Isothermal
Endothermic Exothermic
XA

To = Temperature of the feed

Note that 0
With increased inerts Cp rises, and these curves
become more closely vertical C T
X  P
A  H
R
 C T
X  P
A  H
R
Note that
With increased inerts Cp rises, and these curves
become more closely vertical
7.5.2.1Adiabatic Temperature and
Equilibrium Conversion in reactors
Equilibrium Constants in reversible
reactions
In any chemical reaction,
equilibrium is the state in which
both reactants and products are
present at concentration which
have no further tendency to
change with tine
We have two types of Equilibrium
Constants in reversible reactions
 Chemical Equilibrium Constants (Kinetics)
 Thermodynamics Equilibrium Constants
(Free energy)
 Chemical Equilibrium Constants
(Kinetics)

The equilibrium state results

when the forward reaction
proceeds at the same rate as the
reverse

 Thermodynamics Equilibrium
Constants (Free energy)
The Equilibrium state is obtained
when G 0  0
R
A) Chemical Equilibrium Constants
For the reaction kf
A B
kr
Forward reaction dC
r  A  k C
A,1 dt f A
dC
Reverse reaction r  A k C
A,2 dt r B
Kinetically, at equilibrium, the forward reaction
proceeds at the same rate as the reverse i.e the
net rate becomes zero

r (C )  rr (C ) (3.34)
f A,eq B,eq
 k C  krC (3.34.1)
f A, B,eq
eq

This brings
k C
(3.34.2)
Keq  f  B,eq
k C
r A,eq
Where Keq - Chemical Equilibrium Constants

Consider a general reaction system

kf
aA + b B cC + d D
kr
Kinetically, at equilibrium, the net rate becomes
zero
r (C C C C )  rr (C C C C )
f A,eq B,eq C,eq D,eq A,eq B,eq C,eq D,eq

k Ca Cb  krCc Cd
f A,eq B,eq C,eq D,eq

k Cc Cd
f  C,eq D,eq  Keq
k Ca C b (3.34.3)
r
A,eq B,eq
Class work 3.3 kf
A + B 2C
kr
Determine the rate of reaction
Forward reaction dC
r  A  k C C
A,1 dt f A B
dC 2
Reverse reaction r  A  krC
A,2 dt C
Chemical equilibrium constant
k C2
Keq  f  C,eq
k C C
r A,eq B,eq
The net rate of reaction dC
r  A r r
A dt A,1 A,2
dC
r  A  k C C  k C 2
A dt f A B r C
dC
At equilibrium r  A  k C C  k C 2  0
A dt f A B r C
k
k f
k 
Keq  f or r
K 
2 

k

eq C 

r r   -k C


C - C , eq 


A f  A,eq B,eq K





eq 


 

C 2
C C  C,eq The reaction
When A,eq B,eq
K stops --- rA =0
eq
Graph of equilibrium conversion
and temperature
XA,e =f(T)

rA=0
Endo rA=0 Exo

XA,e XA.e

T T
 te Equilibrium conversion Vs Temperature
o
N in adiabatic operation

Endo- and exo- thermic

Fig. General shape of the temperature-conversion

plot for different reaction rates and types
Note
The highest conversion that can be
achieved in reversible reactions is the
equilibrium conversion.

For the reaction

A B

 C 


Rate Law r


  kf C

 - B,eq 


A 
 A,eq K eq


 
 
 
At equilibrium (-rA =0)

C
C  B,eq
A,eq K eq
Stoichiometry: (Fv,f = Fv,0 ) yields
C X
C (1 - X ) A,0 A,eq
A,0 A,eq K eq
Solving for XA,e gives
K eq (T )
X 
A,eq 1  K eq (T )

Keq  100,000exp -33.78 T - 298

   
If Keq is given 







T









Then XA,e becomes

100,000exp -33.78  T - 298  
  T  
X eq 

1  100,000exp -33.78   T - 298  
  
 T  
 XA,eq

Figure : Effect of temperature on equilibrium

conversion using equation (e).
B) Thermodynamics Equilibrium Constants
 The Equilibrium state is obtained when G 0  0
R

 From mass law we aA + bB cC + dD

c d
CC ,eq . C D ,eq
(3.33)
K
C Aa ,eq . C B b,eq

Where K – Thermodynamic Equilibrium Constant

Free energy and the Thermodynamic Equilibrium Constant

have a relation
0
 G R   RT ln K
Equilibrium Constant and Temperature
from thermodynamic point of view
Van't Hoff equation relates equilibrium composition
to temperature:
d ( - G 0 / RT) H 0
R  T  d ln K (a)
dT RT 2 dT
Van't Hoff equation can be integrated from 298 K
to any temperature T to yield :
T H 0
ln K  ln K   T dT (b)
T 298 RT 2
298
Enthalpy change of reaction varies with T as:
T
 H (T)   H (T )   C p dT
T T 298 (c)
298
An approximate estimate of equilibrium constant
at any time , ignore the second term in equation (
c ) , then equation ( b ) , became :

0
H  1

1 

ln K  ln K  298  -


T 298 R

T


298 

For endothermic reactions,

the equilibrium constant, K, increases
with increasing temperature.

For exothermic reactions,

the equilibrium constant, K decreases
with increasing temperature.
 K>>1
irreversible rxn

Figure : The equilibrium constant as a

function of temperature for an exothermic
and endothermic reaction
 0
H  1

1 

ln K  ln K  298  -


T 298 R

T


298 

Figure : The equilibrium constant as a

function of temperature for an exothermic
reaction
Equilibrium Conversion and Temperature
Consider the reaction A R
XA,eq – equilibrium conversion is defined by
C - C
X  A,0 A,eq
A,eq C
A,0
C C X X
K  R,eq  A,0 A, eq  A, eq
C C (1 - X ) 1 - X
A,eq A,0 A,eq A,eq
or
X  K
A,eq 1  K (e)

Where: XA,eq – equilibrium conversion

The equilibrium constant can be written

C B,eq
K
C A,eq

C  C - C X (1.1.3)
A,eq A,0 A,0 A,eq
C  C X (1.1.4)
B,eq A,0 A,eq
where C A,eq and C B,eq are equilibrium concentrations of
X A and B ;
equilibrium conversion of A
Substitution the magnitude to the above eq., we get
equilibrium conversion

K
X A,eq 
1 K


K  100000 exp  33.78

T  298 




 T 



100000exp 33.78 T  298 

  T 
X eq 
1 
 100000exp  33.78  T  298 
 
 T 
Substitution Equation ( d ) to ( e ) allow us to find
the variation of the equilibrium conversion, with
temperature. This is shown in the following
Figure

XA,eq

Figure : Effect of temperature on equilibrium

conversion using equation (e).
 XA,e =f(T)
rA=0
rA=0

XA,e XA.e
Mass
Mass
balance
balance Exo
Endo

T T

Figure : The equilibrium conversion as a

function of temperature for an endothermic
and exothermic reaction
 XA,e =f(T)
rA=0
rA=0

XA,e XA.e
Mass
Mass
balance
balance Exo
Endo

T T

Figure : The equilibrium conversion as a

function of temperature for an endothermic
and exothermic reaction
Note
Since Thermodynamic Equilibrium
constant is derived from mass
balance

the relation XA,eq and K simply

noted XA,M (equilibrium conversion
from mass balance)
Exercise 7.4 The elementary gas phase reversible
reaction
R Z
is carried out in a plug flow reactor. Using the
following data.
Keq 100000exp  33.78 T  298
   
  
  



 T 


(H )  20000 cal / mol

F R  F 1 mol / s
R,O T
C  50 cal / mol . K.
P,R
i)Make a plot of the adiabatic equilibrium
conversion as a function of temperature.
(ii) Determine the adiabatic temperature and
conversion when pure A is fed to the reactor at a
temperature of 300 K.
Exercise Fogel p513
For the elementary solid -catalyzed liquid-phase
reaction

make a plot of equilibrium conversion as a

function of temperature. Determine the adiabatic
equilibrium temperature and conversion when
pure A is fed to the reactor at a temperature of
300 K.
Graphical methods to find
 maximum conversion

 the size of reactor

in adiabatic reactor
1) Finding maximum conversion in
adiabatic operation
Maximum conversion that can be
achieved in an exothermic
/endothermic/ reaction carried out
adiabatically can be found using

intersection of adiabatic line

(energy balance) T T  T X
0 ad A

at a graph of
equilibrium
conversion and temperature
XA,e=f(T)
Fig. Finding maximum conversion in adiabatic
operation

(a) Endothermic b) Exothermic

XA,eq Equilibrium XA,eq

XA,max
XA,max
Energy Energy
balance balance
T T  T X
0 ad A
T0 T0
Adiabatic
Adiabatic
Temperature
Temperature
Note that in exothermic reaction
 both temperature and conversion
increase down the length of the
reactor, the equilibrium
conversion decreases
2) Find the size of Plug Flow Reactor for
adiabatic reaction f (-r ) X A , f dX A
A

VR  FA,0 
O ( rA )
VR=FA,0 x Area of the integral

Area of the integral XA,e= f (-rA)_

i) to find the size of Plug Flow Reactor for
an endothermic reaction: Finding -rA
a) Plot equilibrium conversion for various
rate of reaction the conversion-
temperature chart with reaction rate as
parameter.
rA=0
XA,eq rA=1
rA=2

T
b) Draw adiabatic operating line to the curve

Endothermic operation

XA,eq

Energy
balance
T T  T X
0 ad A
T
c) Tabulate intersection of the rate for various XA
along this adiabatic operating line, XA= f(-rA)
Endothermic operation
XA,eq

X3,eq
X2,eq
X1,eq
X0,eq
T
d) Plot the 1 /(-rA) versus XA

X A , f dX
VR  FA,0  A
O ( rA )

XA
e) Find the area of Integral X A , f dX
A
VR  FA,0 
O ( rA )
 ii) to find the size of Plug Flow Reactor for
an exo thermic reaction
For exothermic reactions that have a
large temperature rise during
reaction, the rate rises from a very
low value to a maximum at some
r

intermediate XA, then falls

be
em

r
m

V
 r
be

XA
em

Fig. General shape of the temperature-conversion

plot for different reaction rates
to find the size of Plug Flow Reactor we use
Similar procedure with some modification
rA=0

XA,eq

T
XA
Fig. Finding reactor size for exothermic adiabatic
operations of plug flow reactors.
The best adiabatic operations of a single plug
flow reactor are found graphically by trial and
error method

 by shifting the operating line (changing

the inlet temperature) to where the rates
have the highest mean value.
For exothermic reactions this means

 Straddling (get) the locus of maximum

rates as shown in next Fig. A few trials will
locate the best inlet temperature, that
which minimizes V / FA,0.
 rA=0

Figure: Best location for the adiabatic operating line. For

plug flow, a trial and error search is needed to find this
line(OCTANE p 224)
7.5.2.2 Heat effect involving phase changes in
Adiabatic Reactor
A large number of chemical reactions are carried out
adiabatically with involving phase changes. In
consequence, we shall further refine our energy balance
for the case of change in heat capacity and heat of
reaction as a function of temperature
Taking the adiabatic energy balance,
F C dT  (H )F dX
R P,R R A,0 A
or F
R C dT  (H )dX
F P,R R A
A,0
RC P, R dT  (H R )dX A
Integrated using mean capacity

 ˆ
C (T T )  (H ) X
 R P,R 0 R A
and conversion versus reaction temperature will be

 ˆ
C (T T )
 R P,R 0
X 
A (H )(T )
R

Heat of reaction at any temperature using reference

temperature TR (usually 298 K) is given

H R (T )  H 0 R (TR )  T C P dT
TR

C (T )    T  T 2
P
C (T )      T  T 2
P
Substituting to conversion equation gives

 ˆ
C (T T )
 R P,R 0
X 
A 



 T 

 H 0R(T )   C DT





R P 

 T 


 R 


or the temperature of the reaction as a function of

conversion will be

X A  H R (TR )    RCˆ P, RTO  X AC PTR

T 
  RCˆ P, R  X AC P
7.5.3 Temperature effect on an adiabatic fixed -
bed gas reactors
Gas/solid adiabatic catalyzed reaction is carried
out in a plug flow reactor,
 the reactants are fed continuously into
one end of a tube and
 the reactor products flow out at the other
end.
During the reaction
if it is an exothermic reaction ,
the temperature of the gas stream will
increase across the reactor length
if it is an endothermic reaction,
the temperature of the gas stream will
drop within the reactor length
 Exothermic Endothermic

Tmax, workable temp

To
T
Tmax, workable temp
To

X X

Figure : Temperature and Conversion behaviors in

adiabatic reactors.
IN Exo Rxn High Temperature change
in the reaction might exceed workable
temperature Tmax

Tmax
Tmax, workable temp
T

To

L, V, W
This High unworkable Temperature change causes

Unfavorable reaction condition

such as

 Hot spot if it is exothermic rxn

 Lower equilibrium conversion

 hot spot
 the heat generation along the tube is
uneven and

 at the middle of the reaction it can exceed

Tmax (hot spot) so that the reactor is
unworkable

FR
FR,0 T=20 C
0
T=3000C
Hot spot problem can be solved
i) By using very narrow tubes,

ii) Adding an inert gas or an excess of one of

the reactants to the reactor

the industrial reactors must contain several

thousands of tubes,
R
 to ensure a high surface/volume
e
a ratio for heat transfer / efficient
s heat transfer /
o
n  to get adequate reactor capacity
s
at an acceptable pressure drop,
 the industrial reactors must contain several
thousands of such tubes, built together in a single
shell in which the coolant is flowing.
Figure: Multi tube Fixed bed reactor.
This allow efficient heat transfer for
exothemic or endothemic reactions.
 Gas inlet
Thermocouple

Baffles outlet

Gas outlet

Figure : Multi tube Fixed bed reactor

Unfavorable Temperature causes
Lower conversion, Equ, Conv
Exothermic rxn
XA

XA,eq unworkable Temperature

Isothermal

XA,eq
T2 > T1

T0 T1 T2 T
Increasing conversion, Equ. Conv
Four methods applied to extend the
conversion to the desired level before
exceeding workable temperature Tmax
moderate A) Using indirect heat exchanger
exothermic reaction
B) Direct cooling or quenching
between two or more beds
Highly
C)
exothermic
Stepwise Quenching
reaction
D) Adding an inert gas or an
excess of one of the reactants
to the reactor feed.
A) Using indirect heat exchanger

In this method, the beds are sub-divided into two or

more so that each bed does not exceed Tmax.
- Used for moderate exothermic reaction
To To Tmax T T
To

To T

X’
X
T
T T

Figure : Cooling to the desired, temperature by using

indirect heat exchanger in fixed bed reactors.
 X3>X2>X1>
To Z=0

T1 , X 1 T1 X3
T2

T
2
T X2
T3 , X 2
T
3 X1
T4 4

X1

T5, X5 Z = TLo T5 T
Product

Tmax
Feed
Figure : Cooling to the desired, temperature by using
indirect heat exchanger in fixed bed reactors.
B) Direct cooling or quenching between two or
more beds
This is used mostly in the case of

high exothermic reaction, i.e., for

too high temperatures and

 it is not useful through the usage of indirect

heat exchangers.

 Here one of the reactants is injected in cold

stage into the reaction stream between
consecutive beds. The following Figure shows
such methods.
 To

Quench To
(Reactant)

Figure 4.13 Direct cooling between beds in fixed

bed reactor
 To Z=0
To
T1
Xeq

T1 X1
Z X
X3
T2 T2

T3 X2

T3 X2
X1
T4
T5

T
T5 X3 Z=L T To

Feed Product Tmax

C) Stepwise Quenching
Used for high exothermic reaction
It is similar to the previous method, but the
difference is that

instead of sub-dividing the beds, it will be carried

out in the beds placed differently and by using
perforated tubes.

Disadvantage of this method over the previous

one is that it is somewhat sloppy and it is difficult
to design for.

The following Figure depicts such a method

Quench Quench

O O O O O O
O O O O O
O
O O O O O
O O O O O
O
O O
O
O O
O
O
 D) Adding an inert gas or an excess of one of the
reactants to the reactor feed
(H )F
Remember T T  R A,0 X
0 F C A
T  T  T X R P
adiabatic 0 ad A
temperature T  T X
change ad A  
  H F
T   R  A,0
The adiabatic temperature rise Tad ad F C
R P
 It's value depends on the initial composition
(initial condition), Heat of reaction, and
Heat capacity
 The higher value of adiabatic temperature
y

rise i.e., the gradient rise is an indication

all

of a stronger thermal effect of the

er
en

reaction mixture
 H  0
R
XA
H  0
R

Slope
T0 T
 ∆Tad = 0 With increased inerts Cp rises,

  H F
 and these curves become more
T   R A,0

ad F C
R P
closely vertical
H  0
R
XA
H  0
R

Slope
T0 T
 
  H F

T   R A,0

ad F C
R P
These thermal effects can be subdued through the
nce dilution of the mixture -Heat sink-
He
 addition of excessive amounts of some
of the reactants or inerts FR , Cp
The addition of
s reduced temperature in the reaction and
r t g a
i ne
es s plays advantageous role in increasing
c
ex tant the conversion.
ea c
r
addition method has disadvantage over the other
methods because of its requirement of a large size
of the reactor to accommodate both the reaction
7.5.4 Heat effect on Continuous Stirred
Tank Reactor
The continuous flow reactor is considered to be the Open
System as shown in the following Fig.

T0

T; XA,f

TS
Here, we consider the application of the energy balance
equation for flow process,
F C dT  H (rV ) UA(T T ) (a)
T P R S
 Coil
TS

Q
TS b

Figure : Addition or removal of heat in a CSTR, a) heating

or cooling jacket; b) a coil placed inside the reactor
7.5.4.1 Isothermal CSTR
In the case of isothermal,
i.e., when the temperatures of the
reacting mixture entering and leaving the
reactor are equal,
T 0 = TR
The energy balance (a) reduces to

UA(T T )  H (rV ) (5.11)

S R

Q  (H )(r )V  (H )F X  Qg

t R A R A,0 A
Where
Qt UA(T T ) Qt – Rate of Heat removal /add by
S heat transfer/
Qg  (H )F X Qg –rate of Heat
R A,0 A
production /heat produce by
Analyzing Rate of Heat removal, Qt and Heat
production , Qg as a function of reactor (rxn) temp
Rate of Heat removal as a function of reaction temp
Qt UA(T T )
Qt S

T
TS
Reaction (Reactor) temperature
Rate of Heat production as a function of rxn temp
Qg  (H )(r )V (-rA)  Ae E RT ( X A)
R A
Qg  (H R ) Ae E RT ( X A)(V )
Rate of Heat production /generation have the sigmoid
shape

Qg

T
reaction (Reactor) temperature
7.5.4.2 Non isothermal CSTR
For non isothermal operation, the energy balance
equation (a) F C dT  H (rV ) UA(T T )
T P R S (5.12)

 By assuming the specific heat of the

reaction, composition and the heat of
reaction do not depend on the
temperature (H )(r )V  (H )F X
R A R A,0 A
the energy balance equation (5.12) can be written as

(H )F UA(T - T )
(T - T )  R A,0 X  S
0 F C A F C (5.13)
R P R P
 Qg  (H R )F A,0 X A
Qt UA(T T )
S
Substituting and rearranging we get

Qg Qt
T  T0  
FRCP FRCP

The reaction (Reactor) temperature T

is obtained graphically by combining
heat production and heat removals
as a function of temperature into one
graph
 Qg
Qg ,Qt
Qt

T
Reactor temperature
From the Figure, one can see
the possibilities of several solutions to
find the rxn temp. and is therefore
known as the multiplicity of steady
states.
Heat production and Heat removal as
a function of rxn temperature
i) Heat production
The heat production, Qg Vs T
Qg  (H )(rV )
R

 shows different characteristics based on the

batch and flow process.
a) Heat production, Qg in the case of batch
exothermic reaction
dn
Qg  (H )(rV )  (H ) j
R R dt
 the temperature will rise as the reaction
proceeds, and the production of heat
increases, when the reactant is depleted,
then the reaction slows down and the heat
of production ceases.

Qg

T
Figure : Heat production rate as a function of
reactor temperature in batch process
b) Heat production, Qg In the case of continuous
exothermic reaction, CSTR
Qg  (H )(rV )  (H )F X
R R A,0 A
(5.15.1)
Heat production values, Qg are affected mainly by heat of
reaction, feed rate and conversion
we have to see the effect of Conversion and
reactor Temperature
Conversion as a function of rxn (reactor)
temperature we obtain using material
balance
For a first – order reaction

V  V  X X
 F  A  A
F F C C ( - r ) kC (1 - X )
A,0 V ,0 A,0 A,0 A A,0 A
 X
  A
F k (1 - X )
A

conversion becomes
k
X  F
A 1  k
F
conversion in terms of rxn Temperature becomes

 AeE / RT
X  F
A 1   AeE / RT
F
Graphically representation of Conversion as a
function of rxn (reactor) temperature
 AeE / RT
X  F
A 1   AeE / RT
F

XA

T
Figure : Conversion as a function of rxn (reactor)
temperature in continuous process (CSTR)
 Now, Heat production /generation / , Qg as a
function of rxn (reactor) temperature we obtain
by substituting conversion
 AeE / RT
X  F
A 1   AeE / RT
F
Then, Heat of production
Qg  (H )(rV )  (H )F X
R R A,0 A

 AeE / RT
Qg  H F F (5.15.2)
R A,0 1   AeE / RT
F
Since Qg is proportional to XA, a plot of Qg
versus T would have the same shape as the
plot of X versus T.
  AeE / RT
Qg  H F F
R A,0 1   AeE / RT
F

Qg

T
Figure : Heat production rate as a function of rxn
(reactor) temperature in continuous process
About FIGURE
 Generally heat production/ generation/
rate curve as a function of reactor
temperature in continuous process have
the sigmoid shape as indicated in Figure.
 The shape is different due to the opposing
effects of increased rate constant and
diminished concentration of reactants.
 During the reaction, the reactor
temperature rises and causes to attain
high value of the rate constant and as a
result the curve must flatten off.
 For conversions greater than about 50%, the
effect of decreasing the reactant concentration
makes Qg increase less rapidly with temperature,
and Qg approaches a limiting value
corresponding to complete or equilibrium
Analyzing the equation (5.15.2)

 AeE / RT
Qg  (H )F F
R A,0 1   AeE / RT (5.15.2)
F

Temperature
At low values of T, the reaction rates are low and
therefore little or no heat is generated and equation
(5.15.2) reduced to
E / RT (5.15.3)
Qg  (H )F  Ae
R A,0 F

High values of T, the reaction rates are fast, the reaction

goes to completion, and the equation (5.15.2) becomes

Qg  (H ) F (5.15.4)
R A,0
Qg  (H )F  AeE / RT
R A,0 F At high T

At low T Qg  (H ) F
Qg R A,0

Exothermic for
Complete reaction

T
Figure 5.9b Heat production rate as a function of
rxn (reactor) temperature in continuous process
Flow rate and the reactor volume
 AeE / RT
Qg  (H )F F
R A,0 1   AeE / RT
F

Qg

Increasing 
F
T
Figure : Variation of heat production with space tim
ii) Heat Removal, Qt Vs rxn (reactor) T
Looking to the energy balance F C dT  H (rV ) UA(T T )
T P R S
Heat removal in the reactor comes
Heat removal by the heat exchanger
Qt  UA(T T )
S
Heat removal by the inflow and out
flow of fluid Qr  F C dT
T P
Total (Modified) heat removal then becomes
QR = Qt+ Qr
for TS= TF
Q  F C (T T )  UA(T T ) [F C UA](T T )
R T P F S T P S
A plot of QR versus T is a straight line with slope (FT CP +
UA). This is shown in the next Fig.
Q  F C (T T )  UA(T T ) [F C UA](T T )
R T P F S T P S

QR

Slope =(FT CP + UA)

T
TS= TF
rxn (reactor) temperature
Taking again Energy balance for non isothermal
equation for CSTR
F C dT  H (rV ) UA(T T )
T P R S
(H )F X  F C dT  UA(T T ) (5.16.1)
R A,0 A T P S

Assuming a single pure reactant takes place in the reaction,

F F
A,0 T
(H )F X  F C (T T )  UA(T T )
R A,0 A A,0 P 0 S

and the heat transfer temperature is identical to the

surrounding temperature,
T T
0 S
 ( H ) F X  F C (T T )  UA(T T )
R A,0 A A,0 P 0 0

(  H ) F X F C
R A,0 A  A,0 p (T T )  UA (T T )
F Cp F Cp 0 F Cp 0
A,0 A,0 A,0

(H ) X UA (T T )
R A  (T T ) 
Cp 0 F Cp 0
A,0

Let

  UA
F C (5.17)
A,0 P
 (H ) X
R A  (T T )  Z (T T )
Cp 0 0

(H ) X  C p(T T )  C pZ (T T )
R A 0 0

(H ) X  C p(1 Z )(T T )

R A 0 (5.16.2)
Hence, a modified definition, the heat removal in the
process of non-isothermal is expressed by equation
(H R ) X A  QR  C p(1 Z )(T T0)

Q  C p(1 Z )(T T )
R 0 (5.18)

QR

T0 T
Characteristics of Heat removal curve, QR
From the equation
Q  C p(1 Z )(T T )
R 0
 A plot of QR versus T is a straight line
with a slope CP(1 + Z).

 the heat removal increases linearly

with temperature.
From the graph
 As the entering temperature T0 is
increased, the line retains the same
slope but shifts to the right as shown in
the following Fig.
 QR

Increasing T0

Figure :Variation of the heat removal line with

inlet temperature
  If one increase Z by either
  UA decreasing the feed rate or
F C
A,0 P increasing the heat exchange area
the slope, CP(1 + Z) increases
and the ordinate moves to the left
Z=∞ as shown in the following Fig.

Z=0
QR

Increase Z

T0 T
Figure 11d Variation of heat removal line with the
change of parameter Z
7.5.4.2.1Finding Reaction temperature
(steady states condition) in non-
isothermal operation
F C dT  H (rV ) UA(T T )
T P R S
Rearranging we have
(H ) X  C p(1 Z )(T T )
R A 0
Qg  Q
R
Heat of production
Qg  (H ) X X  f (T)
R A A
X  f (-r )
A A
Conversion from material balance for a 1st order
reaction
material balance for CSTR.
X
A  V
F X  (-r )V (-r ) F
A,0 A A
A A,0
Rearranging for a first order reaction
V  V  X X
 F  A  A
F F C C ( - r ) kC (1 - X )
A,0 V ,0 A,0 A,0 A A,0 A
X
  A
F k (1 - X )
or A
k  Ae  E / RT
X  F X  F
A 1  k
F
A 1   AeE / RT
F
Qg  (H ) X
R A  AeE / RT
Qg  (H ) F
R 1   AeE / RT
F
  AeE / RT
X  F
A 1   AeE / RT
F

XA

T
Figure: Conversion and temperature for irreversible rxn
from material balance in an adiabatic CSTR
  AeE / RT
Qg  (H ) F
R 1   AeE / RT
F

Qg

T
Figure: Heat Production and temperature for irreversible
rxn in an adiabatic CSTR
Q  C p(1 Z )(T T )
R 0

QR

T
Figure: Heat Removal and temperature for irreversible rxn
in an adiabatic CSTR
Analysing the two functions
 AeE / RT
Qg  (H ) F Exponential
R 1   AeE / RT
F
Q  C p(1 Z )(T T ) Linear
R 0
Qg  Q
R  AeE / RT
(  H ) F  Cp(1 Z)(T -T )
R 1   AeE / RT 0
F
Linear
Exponential
In an exothermic reactions which are conducted
in CSTR reactor, there may be a stability
problem because of the dramatically change of
heat production due to the exponential increase
reaction rate with increasing Temperature
  Reactor Stability is to occur in CSTR
at steady state,
(H ) X  C p(1 Z )(T T )
R A 0

Qg  Q
R Steady State Operation
 The Steady State Operation, obtained by
superimposing the two curves
Qg and QR respectively.
Note If this equality does not hold in
exactness, the reactor is not at
steady - state and the reaction
temperature will change with time.
  Thus the steady states at different
locations are represented by
points of intersection of the heat
production curve with the heat
removal line, plotted as a function
of the reactor temperature.

Hence
 The reaction temperature in a
steady state must have a value
which satisfies the equation
(5.16.3). Q  Q
g R
 Qg
Qg ,QR
QR

T
From the above Figure,
 one can see the possibilities of several
solutions and is therefore known as the
multiplicity of steady states.
 The positions of such points are, therefore,
dependent on the values of the variables
which appear on both Qg and QR. Here
three cases may be distinguished
 QR b
e
QR
d

QR
c
Qg
a
T

Figure 5.11 Heat production and heat removal curves

Let us examine the three cases
Case 1: The intersection at 'a' represents the situation, where
insufficient heat is produced from the reaction, that
corresponds to the extremely low, perhaps almost to zero
rate of reaction. The reaction mixture is so effectively
cooled that steady operation is possible only at low
temperature and results a very low degree of conversion.

Case 2: An intersection point 'b', corresponds to the

situation, where more than enough heat is
produced from the reaction and complete
conversion is secured. If such an intersection is
obtained under conditions, where no heat is being
put in the system, the reaction is said to be capable
of being operated auto thermally
Case 3: Under certain conditions there exist
three intersection points 'c', 'd' and 'e'. The first
and the last of these are of the same type as 'a'
and 'b' respectively and for which the same
reasons are forwarded as for Case 1 and 2.

Point 'd', on the other hand is unstable state

because with small rise in temperature,

the heat produced is greater than the heat

removed and thus the temperature would
continue to rise until point 'e' is reached.
small fall in temperature
the heat removal is greater than the heat
production by the reaction and the conversion
lowers down, and the point 'c' is attained.
7.5.4.3 Adiabatic CSTR
Using general energy balance,
F C dT  H (rV ) UA(T T ) (5.12)
T P R S
adiabatic condition gives,

F C dT  H (rV )  0
T P R

F C dT  (H )F X
T P R A,0 A

the reaction temperature changes with

conversion,
 Finding Adiabatic Operating Temperature
for a given conversion

F C dT  (H )F X
T P R A,0 A

we must relate conversion and

Adiabatic Operating Temperature
from
 energy and

 material balance
i. Conversion and Adiabatic Operating
Temperature from energy balance
Energy balance equation F C dT  (H )F X
T P R A,0 A

FRC P (T - T0 )  FA,0X A ( H R ) (5.17.1)

or
FRC P (T - T0 )  CA,0 FV, ,0X A (H R )
Rearranging gives

F C (T -T )
X  R P 0
A C F (- ) (5.17.2)
A,0 V ,0 R
Recalling C F (- )
T  A,0 V ,0 R
ad F C
R P
Substituting we get the relation between
conversion and temperature as given by energy
balance.

1
XA  ( T - T0 ) (5.17.3)
Tad

Next Figure shows the characteristics of

conversion and temperature as given by the
energy balance equation (5.17.3) and we call it
adiabatic operating line
 XA
∆HR= 0
adiabatic
operating line

∆HR>0 ∆HR< 0

T0 T

Figure: Conversion and temperature from energy balance

in an adiabatic CSTR
ii) Conversion and Adiabatic Operating
Temperature from material balance.
X
Design equation F X  (-r )V A  V
A,0 A A (-r ) F
Rearranging for a first order reaction A A,0
V  V  X X
 F  A  A
F F C C ( - r ) kC (1 - X )
A,0 V ,0 A,0 A,0 A A,0 A
X
  A
F k (1 - X )
A k
conversion then becomes X  F
A 1  k
F
conversion in terms of temperature becomes
 AeE / RT
X  F
A 1   AeE / RT
F
  AeE / RT
X  F
A 1   AeE / RT
F

XA

T
Figure: Conversion and temperature for irreversible rxn
from material balance in an adiabatic CSTR
 XA

T
Figure: Conversion and temperature for reversible rxn
from material balance in an adiabatic CSTR
Fig. Conversion in a CSTR reactor as a function of
T and θF from the material balance equation.

θF

θF

T
Solution to
 find Adiabatic Operating Temperature for
a given conversion

we must combine conversion from

 energy and

 material balance
 F C (T -T )
Energy balance X  R P 0
A C F (- )
A,0 V ,0 R
 AeE / RT
Material balance X  F
A 1   AeE / RT
F

F C
R P,R
(T -T )
0  Ae -E RT
X   F
A C F (- 1   Ae-E RT
A,0 V ,0 R F

The solution of these equations can be determined in the

following Figure using graphical method as stated earlier
in the steady state condition
Here three cases may be distinguished. These are shown
 Equ. (5.17.2)

XA XA

Equ. (5.17.2)

Equ. (5.18.4)

T
T
Figure Adiabatically energy balance for conversion versus
temperature in the steady state condition
Fig. Three types of solutions to the energy and
material balances for exothermic irreversible
reactions.
Consider reactant fluid fed at a given rate (fixed
θFor V / FA,0) to a CSTR reactor. At each reactor
temperature there will be some particular conversion
which satisfies the material balance equation
Looking to the equation F X  (-r )V
A,0 A A
 At low temperature the rate is low so this
conversion is low.
 At higher temperature the conversion
rises and approaches the equilibrium.

 At a still higher temperature we enter the

region of falling equilibrium so the
conversion for given T will likewise fall.
Next Fig. illustrates this behavior for different T
Fig. Solution of energy and material balances for
reversible exothermic reaction.
 
  H F

T   R A,0

ad F C
R P
These thermal effects can be subdued through the
nce dilution of the mixture -Heat sink-
He
 addition of excessive amounts of some
of the reactants or inerts FR , Cp
The addition of
s reduced temperature in the reaction and
r t g a
i ne
es s plays advantageous role in increasing
c
ex tant the conversion.
ea c
r
addition method has disadvantage over the other
methods because of its requirement of a large size
of the reactor to accommodate both the reaction
Exercise 7.5 A first-order liquid phase reaction is
carried out adiabatically in a CSTR in the
following reaction, ,s
-1

A  P
-12000
k  1.8 x 10 e 5 RT

The density is 1.2 g / cm3 and the specific heat is

0.9 cal /g .0C. The volumetric flow rate is 200
cm3 / s and the reactor volume is 10 liters. If the
heat of reaction (-∆HR) = 46000 cal / g . mol and
the feed temperature is 20 0C. What are the
possible temperatures and conversions for stable
operations at a feed concentration of 4 g.mol /
liters?