CHE 471
Course Lecturer:
Course Outline:
Temperature and pressure effects:
Single reaction heat effects
optimum temperature progression
Adiabatic & Nonadiabatic 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)
• 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.
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).
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
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?
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
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 Jmol1
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
K2 H r 1 1
ln 20
K1 R T2 T1
K2 H r 1 1
ln
K 298 8.314 T2 298
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 :
For E.g.
For exothermic reactions
• Plug flow with an
arbitrary temperature
profile path AB
• Nonisothermal plug
flow with 50% recycle –
path CD
• Mixed flow – single
point point E.
Construction of the rateconversiontemperature
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
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
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
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 firstorder 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
'
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 Jmol1A
At steady state :
•
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.
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 interstage
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
τ V 0.8 dX A liter
= = Area shaded in the curve = 0.405
CAO FAO 0
rA optimum path ABCDE mol.min
1 R E3 E1 k30
ln
Topt E3 E2 E1 E2 k20
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