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CHEMICAL REACTION ENGINEERING II

CHE 471

Course Lecturer:

Engr. Dr. O.U. OSAZUWA


B.Eng, M.Eng, Ph.D, Engr. (COREN Reg.), MNSE
CHEMICAL REACTION ENGINEERING II
CHE 471

Course Outline:
Temperature and pressure effects:
Single reaction heat effects
optimum temperature progression
Adiabatic & Non-adiabatic operations.
Exothermic reactions in mixed flow reactors.
Multiple reactions:
product distribution and temperature.
Temperature and vessel size for maximum production.
Non ideal Flows:
residence time distribution of fluids in vessel.
Models for non ideal flow, tank in series models.
Mixing of fluids.
Class 1
Temperature & pressure effects
In selecting reactors and heat exchange systems,
Three (3) factors are considered :
1. Effects of P & T on equilibrium composition,
rate of reaction & product distribution.
2. The relationship between the heat effects
which accompanies chemical reaction and the
temperature of the reacting mixtures.
3. Economic considerations.
Operating conditions :
Pressure (P) and Temperature (T)

How does changes in P & T affect

• Equilibrium composition
• Rate of reaction
• Product distribution

Note
This enable us to determine the
optimum temperature progression.
Equilibrium composition
• reagents attains equilibrium with
products.
• Chemical equilibrium is attained
• When forward and reverse reactions
occurs at same rate.

• For the general equation,


aA  bB  cC  dD 1
• At a specified temperature, Kc is related
to the equilibrium composition

 C  D 
c d

kc  a b  2
 A   B
Rate of reaction
• Speed at which a chemical reaction takes place.
• Expressed either as concentration of product
formed or reactant consumed in a given time.
• For the general reaction
aA  bB  cC  3

d  C d A d  B d a 
d  b d c
, , , , ,  4
dt dt dt dt dt dt
Product distribution (PD)
• Multiple products formation
• Ratio of one product to another
• PD can be determined by the
energies released by each products
• Energy can be determined by the
type of reaction : (Reversible and
irreversible).

For reversible reaction


• PD depends entirely on ratio of
relative energies (ΔGo) of competing
products.
• The major product is the more
stable
   RTlnK
G o
 5

where K= equilibrium constant & ratio


of one product to
another.
For irreversible reaction (IR)
• PD not dependent on relative
stability of either products
• PD in an IR depends on the rate at
which each product is formed.
• PD in IR is dependent on the ratio
of the rate constants.
• IR does not operate under
equilibrium conditions.

• PD in an IR depends entirely on the


difference in energies between the
two competing transition states
which leads to the formation of two
different products.
Single Reaction (IR) Single Reaction (RR)
For single reaction (IR): For single reaction (RR):
• Equilibrium composition • Equilibrium
• Rate of reaction composition
• Product distribution • Rate of reaction
• Product distribution

Rate of
reaction Amount of Thermodynamics
conversion From
(pressure & temperature)
• max possible
conversion.
Stability of • Heat liberated or
reactor (pressure absorbed .
& temperature)
Heat of Reaction from Thermodynamics

• Absorbed or liberated heat during reaction at a given


temperature (T1) is dependent on
Nature of reactor
Amount of reactants
Operating conditions of the
reactor (pressure & temperature)
• Obtained from heat of reaction (ΔHr)
• When (ΔHr) is unknown the absorbed or liberated heat can be
calculated from (ΔHf) or (ΔHc)
• (ΔHf) or (ΔHc) can be obtained from standard tables obtained
using standard temperature (To=25oC)
aA  rR  sS 6 -(ΔHrT) -- Exothermic reaction
+(ΔHrT) – Endothermic reaction

• (ΔHrT) – heat transferred from the surroundings to the


reacting system

Heat of reaction & temperature


To evaluate (ΔHrT) at T2 with (ΔHrT) known at T1 we
apply law of conservation of energy;

initial kinetic energy + initial potential energy + other work =


final kinetic energy + final potential energy

•Energy can neither be created nor destroyed but can be transformed


from one form to another or transferred from one form to another
 Heat absorbed during reaction at temperature  T    2

 heat added to reactants to change their temperature from  T  to  T    2 1

 heat absorbed during reaction at temperature  T    1

 heat added to products to bring them back to  T  from  T  


2 1

H r 2    H 2  H1 reac tan ts  H r1   H 2  H1  products 7


• Where 1 & 2represents quantities measured @ T1 & T2
• In terms of specific heats
8
T2
H r 2  H r1   C p dT
T1
• Where

C p  rC pR  sC ps  aC pA 9
Note
The molar specific heats are functions of temperatures & are
represented as:
CPA   A   AT   AT 2 10 
C P R   R   RT   RT 2 11
CPs   s   sT   sT 2 12 
Substituting all parameters into (8):
 2  3
H r 2  H r1   T2  T1  
2
 T2  T1 
2

3
 T2  T1 
3
13
  r R  s s  a A 14 
  r  R  s  s  a  A 15 
  r R  s s  a A 16 
If :
• heat of reaction @ T0,
• specific heat of reactants & products @ T0 are
known, then the heat of reaction at T1 can be
calculated.
• The heat effects of the reaction can also be
calculated.
Example 9.1

A  B  2R
• At (ΔHf) or (ΔHc) the standard heat of a gas phase reaction
at 25oC is (ΔHr298K).
• The reaction will take place at 1025oC. What is the (ΔHr1025oC)
and what is the nature of the heat released?

Given Data : Average CPA= 35 J/mol.K, CPB= 45 J/mol.K,


CPR=70 J/mol.K

From an enthalpy balance (Energy balance):


Enthalpy balance (E.g. 9.1)

ΔHr 25oC = -50,000 J


1A+1B  2R
1A+1B 2R
T=25oC T=25oC
ΔHr 1025 -25oC
Reactants
heated up ΔHr1025oC Reactants
cooled
1A+1B  2R 2R
ΔHr 25 - 1025oC 1A+1B
T=1025oC T=1025oC
ΔH=nCpΔT 8

ΔH25oC = -50,000 J
ΔH25oC = ΔH25 -1025 oC + ΔH1025oC + ΔH1025 -
o
25 C
Substituting:
-50,000 J = 80,000 J+ ΔH1025oC - 140,000 J
+ ΔH1025oC = -50,000 J -80,000 J + 140,000 J
= 10,000 J
At 1025 oC the reaction is Endothermic
Class 2
Equilibrium constants from thermodynamics
From second law of thermodynamics :
• Can calculate equilibrium compositions of reacting
systems
• Difficult to achieve with real systems

aA  rR  sS
Recall
• Standard free energy ∆Go for the reaction above at T is :
r s
 f   f 
 fo  fo
 R  S
G o  rGRo  sGso  aGAo   RT ln K   RT ln a 17 
 f 
 fo
 A
K can be represented in terms of pressure, fugacity,
mole fraction & concentration :

r s r s r s r s
f f PP y y CC
Kf  R S
a
,Kp  , Ky 
R S
a
 Kc  a
R S
a
R S
18
f A P A y A CA
f = fugacity of component at
equilibrium conditions
f o = fugacity of component at
the arbitrarily selected
standard state at T
Go = standard free energy of a
reacting component
(tabulated for many
components)
K = thermodynamic Fugacity:
equilibrium constant for the a thermodynamic property of a
real gas which if substituted for
reaction. the pressure or partial pressure
in the equations for an ideal gas,
gives equations applicable to the
real gas.
EQUILIBRIUM CONVERSION
From thermodynamics:
• The rate of change of equilibrium composition related by
the equilibrium constant varies with time change .
• Represented :

d (ln K ) H r
 19 
dT RT 2
Integrating Eq. (19)

K2 H r  1 1 
ln      20 
K1 R  T2 T1 
• To account for the variation in ∆Hr, Substituting (8) into
(20) while we using the temperature dependency for Cp
represented in (10) – (16).

8
T2
H r 2  H r1   C p dT
T1

• Integrating :

T2   2 2   2  3   1 1 
T2  T1   T2  T1    H r 0  T0  T0  T0    
K2
R ln   ln   21
K1 T1 2 6  2 3   T2 T1 
• From (21) the variation of the equilibrium constant can be
calculated.
• equilibrium conversion & temperature can be calculated.
Conclusions

Effect of temperature on equilibrium conversion as predicted by


thermodynamics (pressure fixed)
Conclusions

1. The thermodynamic K is
independent on
• Pressure of the system.
• presence or absence of
inert in the system,
• kinetics of the reaction of
the system
2. CAe of the system, XAe is
dependent on
• Pressure of the system.
• presence or absence of
inert in the system,
• kinetics of the reaction
of the system
3. K>1 –
• complete
conversion,
• irreversible rxn.
4. K<1 –
• Negligible reaction
• Very low
conversion
5. XAe varies directly
with T for ∆H >1
6. XAe varies inversely
with T for ∆H < 1
7. When P is
increased gas rxns,
X varies inversely
with n
8. Decrease in inerts
for all reactions is
similar to an increase
in pressure for gas
reactions.
E.g. 9.2
Between 0oC and 100oC determine the equilibrium conversion
and constant for the elementary aqueous reaction.
a. Present the data in the form of a plot of temperature
versus conversion.
b. What restrictions should be placed on the reactor
operating isothermally if we are to obtain a conversion of 75 %
or higher ?


 ΔG 0
=-14,130Jmol 1

A  R CPA  C PR  constant
298
1
H 298  -75,300 Jmol

0
From (8)
8
T2
H r 2  H r1   C p dT
T1

C p  0  constant
Since
∆Hr is not dependent on the temperature, hence
would not be affected by temperature changes
∆Hr = ∆Hr =-75,300 Jmol-1
From (17) we can determine the equilibrium constant
at 25oC
r s
 f   f 
 fo  fo
 R  S
G o  rGRo  sGso  aGAo   RT ln K   RT ln a 17 
 f 
 fo
 A
-ΔG 0298
K 298 =exp
RT
 J 
 14130 
=exp  mol  =300
  8.314 J  298K 
  
 mol.K  

Since there is no change in ∆Hr with temperature, the


equilibrium constant K at any temperature (100oC) can
be obtained from (20)

K2 H r 1 1
ln      20 
K1 R  T2 T1 
K2 H r  1 1 
ln    
K 298 8.314  T2 298 

• Substituting values of K298 & ∆H298 & making K2 subject of


formula

Recall at equilibrium  75300 


K=exp  -24.7 
 RT 
CR C AO X Ae X Ae
K= = =
C A C AO 1-X Ae  1-X Ae
K
X Ae =
K+1

Now we have eqns. For XAe and K. we can now develop a table
for the change in XAe as a function of temperature in the range
0oC to 100oC.
Table showing K and XAe values from in the
range of 0oC to 100oC
Plot of XAe vs T (oC)
Temperature, Composition, & rate for a single
homogeneous reaction
• For a homogeneous rxn, temperature, composition
& reaction rate are related as follows :

Used to represent data when calculating


reactor sizes, & compare design alternatives
Temperature-conversion plot for different reaction types

For a given feed CAO:


• using conversion of key component of the rxn as a
measure of composition & extent of reaction,
• XA versus T plot is represented below:
Ways to obtain XA vs T plots
• Thermodynamically consistent rate expression for
the reaction (zero rate at equilibrium)
• Interpolating from a given set of kinetic data using
thermodynamic information on the equilibrium.
• Calculations & predictions directly varies with the
accuracy of the chart.
Determining the Reactor size (V)

Reactor size for a given duty (work) & given


temperature progression is determined as follows:
1. Draw the reaction path on the XA vs T plot
(operating line)
2. Find the rates at various XA along this path
3. Plot the 1/(-rA) vs XA curve for this path
4. Find the area under the curve. This gives V/FAO.
Reactor size for different flow at feed temperature (T)

For E.g.
For exothermic reactions
• Plug flow with an
arbitrary temperature
profile path AB
• Non-isothermal plug
flow with 50% recycle –
path CD
• Mixed flow – single
point -point E.
Construction of the rate-conversion-temperature
chart from kinetic data
E.g. 9.3.
Using the same system in E.g. 2, the kinetic experiments
in a batch reactor gives 58.1% conversion in 1 min at 65
oC, 60% conversion in 10 min at 25 oC. Assuming

reversible first order kinetics, find the rate expression


for this reaction and prepare the conversion-
temperature chart with reaction rate as parameter.
solution
For a reversible first-order reaction, the performance
equation for a batch reactor is:

Integrating, we obtain:
Calculating the forward rate constant
• From the batch run at
65oC (E.g. 9.2) XAe = 0.89,
substituting into eqn.
above:
k1 1min   0.581 
  ln 1  
0.89  0.89 
k1, 338  0.942 min 1

This step is repeated for the


batch run at 25oC to obtain
k1 10min   0.60 
  ln 1  
0.99  0.99 
k1, 298  0.0909 min 1
• Assuming Arrhenius
temperature dependency,
• At the T (65oC & 25oC), the
ratio of the forward rate
constants are:

• E1= Activation energy for the


forward rxn =
48,900 J/mol
From where k10 =A1

E
-
RT
0.942 = A1e
 E 
ln 0.942 = lnA1 +  - 
 RT 
48,900
-0.05975 = lnA1 -
8.314×338
lnA1 = 17.342
A1 = 34×106
• Recall that at equilibrium

k1
K
k2
 75,300 
K  exp   24.7 
 RT 

• Substituting given values into the eqn. for K


to obtain k2,
• Determining the rate expression for k2 we have:

K = k1C A - k 2 C R
 75,300   48,900 
exp -24.7+  =exp 17.34-  -k 2
 RT   RT 
 48,900   75,300 
k 2 =exp 17.34-  -exp -24.7+
 RT   RT 
  48,900 75,300  
k 2 =exp 17.34+24.7  -  + 
  RT RT 
 124,200  -1
k 2 =  42.04- min
 RT 
The reversible first-order reaction for E.g. 2 & E.g. 3
• Equilibrium & rate constant equations for the
reversible first order reaction.


 R, -rA  rR  k1C A  k2CR
A 

1

 75,300 
At equilibrium: K=exp  24.7  
 RT 
 48,900  1
Rate constants: k1  exp 17.34-  , min
 RT 
 124,200  1
k 2  exp  42.04-  , min
 RT 
Summary

From these values:


1. XA vs T chart for any specific CAO can be
represented. (refer to Figure 9.3)
2. Figure 9.3 represents CAO=1 mol/liter & CRO =0
3. For first order reaction, this plot can be used for
any CAO by multiplying all rate values on the
graph by the required scale.
XA vs T
Class 3
Optimum Temperature Progression
OTP - For a given conversion of reactant,
• The temperature progression that minimizes
V/FAO is referred to as optimum temperature
progression.
• Optimum maybe isothermal or changing
temperature.
• The optimum temperature progression could
change
1. With time for a batch reactor
2. Along the length of a plug flow reactor
3. From stage to stage for a series of mixed flow
reactors
Why do we need to know the optimum temperature
progression ?
1. It is the ideal system which we try to
approach with real systems.
2. Gives the estimate in the difference
between the real system & the ideal
system
3. For any type of reactor, at any
composition, OTP will always be at the
temperature where the rate is maximum.
4. The locus of max rates (maxima of the
different rate curves) can be found by
analyzing the r(T, C) curves
R(T,C)
Operating line for the minimum reactor size
Notes
• For irreversible rxns, rate (r) varies directly with T at any
composition.
• Highest rate occurs at the highest allowable temperature.
• Chosen T is dependent on:
1. Materials of construction
2. Increasing need for various side reactions.
• For endothermic rxns, as T increases, equilibrium conversion &
the reaction rate increases
• For exothermic reversible rxns, increase in T, increases the rate
of the forward rxn but the max attainable conversion decreases.
Heat Effects
• The heat absorbed or released by reaction
changes the reacting fluid temperature.
Hence this factor must be accounted for in
designing a reactor.
• The heat is accounted for using the material
& energy balance equation
For exothermic rxns, if heat transfer is not
able to remove all of the liberated heat, the T
of the reacting fluid increases with increase in
conversion.
for endothermic reactions, the reacting fluid
is cooled as conversion increases.
Relating Temperature change with extent of
conversion
Adiabatic Operations
• These are processes that occur without the transfer
of heat or mass of substances between a
thermodynamic system & its surroundings.
• Adiabatic processes transfer energy to its
surroundings as work.
Adiabatic operations contd.

With T1 as the reference temperature on which


enthalpies & heats of reaction are based;
Enthalpy of the entering feed :

'
H =C
1
'
p  T1 -T1  = 0 Jmol 1
A
Enthalpy of leaving stream:
H ''2 X A + H '2 1 - X A  =C''p  T2 - T1  X A +C1p  T2 - T1 1 - X A  Jmol-1A

Energy absorbed by reaction:


1
ΔH r1X A Jmol A
Recall :
input = output + accumulation + disapperance by reaction

At steady state :

0  C p'' T2  T1  X A  C p' T2  T1 1  X A    H r1 X A


Making XA the subject of formula
C'P  T2 -T1  C'P ΔT
XA = =
  
-ΔH r1 - Cp -Cp  T2 -T1  -ΔH r1 - Cp -Cp ΔT
'' ' '' '

C'p ΔT  heat needed to raise feed stream to T2 
XA = = 
-ΔH r2  heat released by reaction at T2 

-ΔH r2 =C'p ΔT, for X A =1

When C"p -C'p =0, H r independent of temperature


Cp ΔT
XA =
-ΔH r
Graphical representation of energy balance equation for
adiabatic operation for mixed flow & plug flow reactors
(operating lines)
Summary from graph
• The curves are adiabatic operating lines for the
reactor.
• XA at any point in the reactor has its corresponding
T value on the curve.
• For plug flow, the fluid in the reactor (reactant
converting to products) moves progressively along
the curve.
• For mixed flow, the fluid immediately jumps to its
final value on the curve.
• Increasing inert increases CP


Size of a reactor for a given duty
For plug flow
• Tabulate the rate for
various values of XA
along the adiabatic
operating line.
• Prepare the 1/(-rA)
versus XA plot and
integrate.
For mixed flow
• Use the rate at the
conditions within the
reactor
Minimizing V/FAO
The slope of the operating
line, Cp/-∆Hr, determines
the type of reactor that is
best.
• For small Cp/-∆Hr, (pure
gaseous reactants)
mixed flow is best.
• For large Cp/-∆Hr, (gas
with much inert or
liquid systems) plug
flow is best
Non- adiabatic operations
• In some operations, it is necessary to introduce or
remove heat from the reactor.
• We can decide to account for heat losses to the
surroundings.
• Introducing and accounting for various forms of heat
modifies the adiabatic operating line.

Q= total heat added to a reactor per mole of reactant A


Q includes the losses to the surroundings.
The energy balance eqn. becomes :

Q  C T2  T1  X A  C T2  T1 1  X A    H r1 X A


''
p
'
p

C'p ΔT- Q  net heat still needed after transfer to raise feed to T2 
XA = = 
-ΔH r2  heat released by reaction at T 2 

Cp ΔT - Q
XA =
-ΔH r1
Shift in adiabatic operating line caused by the effects of
heat exchange with the surroundings
Making the operating line approach ideal
• Use of heat exchangers with in the incoming fluid
• Use of multistage operations with inter-stage
cooling btw adiabatic sections
E.g. 9.4
Using the optimal temperature progression in a plug
flow reactor for the reaction in E.g. 9.2 & 9.3,
a) Calculate the space time & volume needed for 80
% conversion if a feed of FA0 = 1000 mol/min
where CA0 = 4 mol/liter.
b) Plot the temperature & conversion profile along
the length of the reactor.
Let the maximum allowable operating temperature
be 950C.
solution

Determining the Reactor size (V)

Reactor size for a given duty (work) & given


temperature progression is determined as follows:
1. Draw the reaction path on the XA vs T plot
(operating line)
2. Find the rates at various XA along this path
3. Plot the 1/(-rA) vs XA curve for this path
4. Find the area under the curve. This gives V/FAO.
Plot for E.g. 9.4
• Integrating graphically is to find the area under
the 1/rA vs XA curve.
• For plug flow the performance eqn. can be
evaluated using:

τ V 0.8 dX A liter
= =  Area shaded in the curve = 0.405
CAO FAO 0
 -rA  optimum path ABCDE mol.min

τ = CAO (area) = 4  0.405 = 1.62 min


V = FAO (area) = 1000  0.405 = 405 liters
E.g. 9.4b

• To plot the temperature &


conversion profile along the
length of the reactor.
 10 % increase in length is
equivalent to 10 % increase in
the area under the -1/rA vs XA
curve
 10 % = XA= 0.34 =362 K
 20 % = XA= 0.485= 354 K
This is done up to 100 % to obtain
values to plot the required
temperature , conversion profile.
Multiple reactions
• For multiple rxns, both reactor size & product
distribution are influenced by the processing
conditions.
• We are concern here with how to manipulate the
temperature to obtain
 The desired product distribution
 The maximum production of desired product in a
reactor with a given space time.
Product distribution & temperature
• For two competing steps in a multiple reaction
with rate constants k1 & k2

• The ratio changes with temperature depending on


whether E1 is greater or smaller than E2,
Influence of temperature on the relative rates of
competing rxns
• The rxn with the greater activation energy is more
temperature sensitive
• A high temperature favors the reaction of higher
activation energy
• A low temperature favors the reaction of lower
activation energy.
Types of multiple reactions & effects of T

• For parallel reactions.


 step 1 – promoted
 Step 2 – depressed
 K1/k2 – very large

if E1 > E 2 use high T 



if E1 < E 2 use low T 
• For series reactions
 The production of R is
favored if k1/k2 is increased

if E1 > E 2 use high T 



if E1 < E 2 use low T 
 For step in series, if a high
temperature is required for
an early step and a later
step requires a low
temperature then a
decreasing progression of
temperature should be
employed
• Series – parallel reaction
 E1 > E2 requires a high T,
 E1< E3 requires a low T
 For such cases an
intermediate temperature is
best because it gives the
most favorable product
distribution.

1 R  E3  E1 k30 
 ln  
Topt E3  E2  E1  E2 k20 