TEMPERATURE EFFECTS

Why need to know?

Temperature effects
Real reactors may generate or absorb large amounts of heat
Effect on Reaction Temperature rate?
rate of heat addition/removal to maintain desired Reaction
Temperature ?
Reaction Temperature-what should it be?
Advantageous to operate exothermic reactors
nonisothermally
Higher temperatures lead to higher reaction rates and smaller
reactors
If temperature too high equilibrium can limit conversion
and
High temperatures can lead to hot spots and reactor failure
endothermic Reaction-how much heating is required ?


Exothermic: generate heat, negative
Endothermic: absorb heat, positive

Hi
0
: Heat of formation [kJ/mol];
zero for elementary substances.
Heat of Reaction /mole A

Reference state: 25
o
C & 1 atm

TR: Reference temperature and pressure: It is usually
taken as the standard temperature and pressure of
the enthalpy of formation.
Heat of Reaction: The enthalpy change
when stoichiometric quantities of reactants react
Completely in a single reaction to form products
at the same temperature and pressure.
H
R
is the heat of reaction as written in the given
stoichiometry- energy per mole
Heat of reaction -the energy per mole of component i = HR/
i

moles of i that reacted =n
i,r
=(n
i0
- n
i
)=
rate of heat release/absorption by reaction of i =
molar rate of reaction of i =(F
i0
F
i
)=

RAPID REVIEW
Heat capacity: Energy/mole-K

average Heat capacity =

Enthalpy of i at T
Enthalpy of formation at =
Enthalpy change (T
R
T) for no phase change):






Heat of Reaction /mole A:

*





Heat of Reaction /mole A at T
R





*
















Heats of Reaction














There are inerts I present in
the system.
What is the heat of reaction
at 400C? What assumption
have you made


Hint 1: What is the heat of
reaction at 298 C?
What is delta Cp?

NONISOTHERMAL REACTOR:
RATIONALE


LET US CALCULATE THE VOLUME OF A PLUG
FLOW REACTOR NECESSARY TO ACHIEVE 70%
CONVERSION.
THE CHEMICAL REACTION IS EXOTHERMIC AND
THE REACTOR IS OPERATED ADIABATICALLY.
AS A RESULT, THE TEMPERATURE WILL
INCREASE WITH CONVERSION DOWN THE
LENGTH OF THE REACTOR.



NONISOTHERMAL REACTOR: RATIONALE

Van't Hoff Equation:
For the special case of:
Integrating the Van't Hoff Equation gives
If reaction first order and reversible

Analysis of Nonisothermal
Reactors
The energy balance is an accounting of rate
of:
heat flow into the reactor with reactants
heat flow out of the reactor with
products
heat generated/absorbed by reaction
heat added/removed from reactor
work done by stirrers and friction
Inflow
stream:F
i0
,T
i0
,E
i0,

C
Pi0,
P
i0,
H
i0

Outflow stream:
F
i
, T
i
, E
i,
C
Pi0
,P
i,
H
i0

Q
W
s

Control volume of
reactor
The statement of conservation of energy
for this system takes the form:
( rate of energy accumulation in system )

=[rate of energy entering system by inflow]

-[rate of energy leaving system by outflow]

+[ rate of heat added to system ]

+[ rate of work done on system ] (1)
Complete energy analysis is complicated
simplifying assumptions often made!
convenient to split the work term into 3 parts:
W
f
, the work done by the flow streams
while moving material into and out of the
reactor,
Ws, the shaft work being done by stirrers,
compressors, etc., and
W
b
, the work done when moving the system
boundary.


*2
total energy may be regarded as composed of many
forms:
total energy arise from the internal, kinetic and
potential energies.
kinetic and potential energies and boundary work
negligible.
If flow work=
then
Some work is done in just pushing the fluid through the control volume.
This is flow work, W
f
..
The flow work then is the sum of all of the work terms for all
of the inlet and outlet lines, or
W
F
=W
in
+ W
out
= (PV)
in
-- (PV)
out

S(E
k
+ E
p
+ U )
in
- S(E
k
+ E
p
+ U )
out
+ Q +(W
F
+W
S
)
Since H = U + PV (definition of enthalpy and neglecting changes in E
k
and E
P
)
S F
i
(0 +0 +H)
in
- S F
i
(0 + 0+ H)
out
+ Q + W
S

S(E
k
+ E
p
+ U + PV)
in
- S(E
k
+ E
p
+ U + PV)
out
+ Q +W
S

NOTE;H=enthalpy/mole and F
i
is molar flow rate
balance equation 2 may be written in terms of enthalpy
(H
i
= U
i
+PV
i
) as follows:
In terms of molar flow rate and enthalpies:
Outflow
Inflow
Balance applies to all components entering and
leaving the system
Flow rate in terms of F
A0
and conversions X
A
:


*
Into balance equation:
Expanding

Using mean specific heat and expanding

*
NOTE: the different terms one has to consider before
evaluation
Inlet temperatures of different inputs
Reference temperature
Reaction temperature
Energy Equation for Batch
Reactor
Rate of work due to change in volume:
Neglecting kinetic energy, potential energy and shaft work
From Definition for enthalpy:
Calculate the temperature change for 95 % conversion of A
Q.2 The exothermic elementary liquid-phase reaction
A +B - C r = kC
A
C
B
is carried out in a batch reactor with a cooling coil to keep the reactor
isothermal at 27C. The reactor is initially charged with equal
concentrations of A and B at 2.0 mol/L and no C
1. How long does it take to reach 95% conversion?
2. What is the total amount of heat (kcal) that must be removed by the
cooling coil when this conversion is reached?
3. What is the maximum rate at which heat must be removed by the
cooling coil (kcal/min) and at what time does this maximum occur?
4. What is the adiabatic temperature rise for this reactor and what is its
significance?
Rate constant, k =0.01725 L/mol-min, at 27C
Heat of reaction, H
R
=-10 kcal/mol A, at 27C
Partial molar heat capacities, C
PA
=C
PB
=20 cal/molK, C
PC
=40
cal/mol K
Reactor volume, V
R
=1200 L
Solution to Q.2
1. Assuming
constant density,
-r
A
=-[dC
A
/dt]
= kC
A
C
B
= kC
A
2

Because from the stoichiometry of the
reaction, C
A
= C
B

t=(1/0.01725)x(1/0.05x2.0-1/2.0)=551 min
i.e. for 95% conversion
2. What is the total amount of heat that must be removed?
Energy balance equation for the batch reactor with heat
transfer now becomes
in equation yields
* note the difference between the total heat transfer
and the rate of heat transfer
Integrating both sides of equation:
3.maximum rate at which heat must be removed by the
cooling coil (kcal/min) and at what time does this maximum
occur?
Maximum cooling rate occurs when C
A
is maximum: C
A
= C
A0
at t=0
4. The adiabatic temperature rise is calculated from the
energy balance for the case of no heat-transfer Q=0

Substituting from material balance dN
A
/dt =-r
A
V
R
and
multplying both sides by dt gives:
V
R
C
P
dT= H
R
dN
A

T=T-T
0
= H
R
(N
A
N
A0
)/V
R
C
P
= H
R
(N
A
N
A0
)/
Integrating both sides of the equation:
=[-10]x[-0.95x2.0x1200]/(1200(20x2+20x2)x.001=237.5K
(N
A
N
A0
)
Calculate the temperature change for 95
% conversion of A
solution
The adiabatic temperature rise is calculated from the energy balance for the case of no
heat-transfer Q=0;

This leads to
Recall that we have ; r=
i
r
i
Hence ; r=
A
r
A
= -r
A
Hence ; -r V
R
=
A
r
A
= r
A
V
R

From mole balance for batch reactor; dN
A
/dt= r
A
V
R
Hence; (-r V
R
)H = (-r V
R
)H=( r
A
V
R
)H
Hence; V
R
C
p
=(-r V
R
)H =( r
A
V
R
)H= ( dN
A
/dt) H
V
R
C
p
dT= dN
A
H
It follows that:
Integrating both sides;
V
R
C
p
dT= dN
A
H
At T=T
0
, N
A
= N
A0


T=T-T
0
= H
R
(N
A
N
A0
)/V
R
C
P

Strictly speaking the term changes as the reaction and hence temperature progress. It
should therefore not be removed from the integral term. As an approximation however one
may assume that :

=(-10)x(0.05x2.0-2.0)x1200/96=237.5 K
=V
R
(C
PA
x C
AO
+ C
PB
x C
BO
+0)= 1200(20x2+20x2=96000 cal/K= 96 kcal/K

There is no C at the beginning of the reaction and N
A0
=C
A0
x V
R
=2.0 x 1200 mole

At 95% conversion, N
A
= N
A0
(1-0.95)=0.05 N
A0
=0.05x2.0x1200 mole
Application to flow reactors in steady state
At steady state





For adiabatic operation

negligible shaft work,

Solution



As inerts are increased, you reach the same
conversion at a lower temperature

Solution




As inerts are increased, the same conversion is reached at a
lower temperature
Effects of inerts on T and X
ADIABATIC OPERATION: =0
hence

Assuming all components enter at temperature (T
0
)
And adding to numerator:
-
ADIABATICOPERATION: T vs. X
A
=0
Assumes negligible and exothermic reaction
I

increasing inerts will increase and hence
decrease slope
Temperature increases for exothermic reactions
Temperature decreases fore endothermic reactions

For adiabatic operation2

conversion increases for exothermic reactions

*











The EB gives the relation between X
A
and
temperature at any point in the reactor
CSTR: For adiabatic IRREVERSIBLE
reaction
If T or X
A
is known; to calculate V
EB is used to calculate X
A
or T



Substitute into MB to required volume:
V=F
A0
X
A
/(- r
A
)
Remember(- r
A
)is a function of temperature
Hence temperature is required to evaluate it

Q1
What temperature must the reactor be operated at to achieve
80% conversion in a CSTR?
Q2.
What is the heat duty of the heat exchanger inside the
reactor?
What is the heat duty of the heat exchanger placed outside
the reactor if reactor effluent must be at 25
0
C before storage
Approximate the heat capacity of the reaction mixture with
that of water.
CSTR: For adiabatic IRREVERSIBLE
reaction1
If V is known: to calculate T or X
A

EB is used to calculate T as a function of X
A




MB is used to calculate T as a function of X
A

MB and EB solved simultaneously:
-graphically
numerically

Graphical
530
540
550
560
570
580
590
600
610
620
630
0 0.2 0.4 0.6 0.8 1 1.2
T

X
A
EB
MB
CSTR with heat transfer:two methods
Cooling coils
Jackets
Material balance unchanged, Neglecting volume of
coils
EB: Neglecting W
s
for high flow rate of coolant/heating fluid
inlet temperature = outlet temperature




CSTR with heat transfer2
substituting for yields




simplifying yields





This EB equation is solved simultaneously with the MB
Equation for T, X
A
and volume









PFR: For adiabatic IRREVERSIBLE reaction1
negligible shaft work done on or by the fluid in a
PFR
No Heat transfer- adiabatic reaction
Hence temperature changes along the length of the
reactor
conversion changes along the length of the reactor
The EB is used to calculate the relation between X
A

and temperature along the length of the reactor
Algorithm Adiabatic Reactions:1
Choose(initial) X
A

Calculate T from Adiabatic Energy Balance:


Calculate k (Arrhenius equation)
Calculate K
C
or K
p
(Van't Hoff equation)-for
Reversible Reactions
Calculate C
A
, C
B
e.g.
[C
A
=F
A
/ =F
A0
(1-X
A
)T/T
0

0
(1+
A
X
A
)]
Calculate -r
A

Increment X and then repeat calculations.
Plot F
A0
/(-r
A
) vs. X
A
or
use some numerical technique to find V
Plot for an exothermic, adiabatic reaction
Algorithm Adiabatic Reactions:2
X
A
T T/T
0
k K -r
A
[F
A
/-r
A
]
0
X1 T1

T1/T
0

X2 T2

T2/T
0

X3 T3

T3/T
0

X4 T4

T4/T
0

Algorithm Adiabatic Reactions:3
Q1:The vapour-phase cracking of acetone to ketene and
methane:

is first-order with respect to acetone and the specific reaction
rate can be expressed by
where k is in s
-1
and T is in Kelvin. In this design, it is desired to feed 8000 kg of
acetone per hour to a tubular reactor. The reactor consists of
a bank of 1000 tubes (o.D. = 26.6 mm). We will consider two
cases:
(a) the reactor is operated adiabatically;
(b) The reactor is surrounded by a heat exchanger where the
heat-transfer coefficient is
and the ambient temperature is 1150 K.



(c)What is the arrangement of the tubes?
Solution:
Step1: X
A
=0
The inlet temperature and pressure are the same for both cases at 1035
K and 162 kPa, respectively
Step2:At X
A
=0, T = T
0
= 1400K; T
R
=298K

DH
r
= Sn
i
DH
i
0
=cH
C
0
+bH
B
0
-aH
A
0
=-1x74.81+1x[-61.09]-1x-216.67
=88.77 kJ/mole

Assume: C
PA
=13.39; C
PB
=20.04; C
PC
=26.63 J/mole-K
D C
P
= cCp
C
+ bCp
B
-aCp
A
=26.63+20.04-13.39 =33.28J/mole-K =0.03328 kJ/mole-K
=1 X C
PA
=13.39=13.39 J/mole-K =0.0139 kJ/mole-K; since only pure acetone was fed
Into energy balance equation yields;
T=1400-XA[88.77+0.03328 x( 1400-298)]/[0.01339+0.03328XA]
=1400-125.44XA/[0.01339+0.03328XA]
k=exp(34.34-34222/T); C
A0
=P
A0
/RT=162/8.309 X 1400=0.0139 mol/L

A
=[2-1]/1=1; C
A
=C
A0
[1-XA]/(1+XA)

DH
r
= Sn
i
DH
i
0
=cH
C
0
+bH
B
0
-aH
A
0
=-1x74.81+1x[-61.09]-1x-216.67
=88.77 kJ/mole

Assume: C
PA
=126.15; C
PB
=67.87; C
PC
=55.55 J/mole-K
D C
P
= cCp
C
+ bCp
B
-aCp
A
=55.55+67.87-126.15 =-2.725J/mole-K =0.002725 kJ/mole-K
=1 X C
PA
=126.15=126.15 J/mole-K =0.12615 kJ/mole-K; since only pure acetone was fed
Into energy balance equation yields;
T=1400-XA[88.77-0.002725 x( 1400-298)]/[0.12615-0.002725XA]
=1400-85.76XA/[[0.12615-0.002725XA]
k=exp(34.34-34222/T); C
A0
=P
A0
/RT=162/8.309 X 1400=0.0139 mol/L

A
=[2-1]/1=1; C
A
=C
A0
[1-XA]/(1+XA)

Two differential equations have two unknowns and
can be solved simultaneously
total energy may be regarded as composed of many
forms:
total energy arise from the internal, kinetic and
potential energies.
only these forms of energy considered here.