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CHENG 322 1
Dr. Shaker Haji, University of Bahrain 3/29/2012
In this Chapter
8.1 Rationale
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Dr. Shaker Haji, University of Bahrain 3/29/2012
8.1 Rationale
dT
What else is needed? F3 (X ,T )
dW
How is it obtained?
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Dr. Shaker Haji, University of Bahrain 3/29/2012
The 's signify that Q & W are not exact differentials of a state function.
E is the total energy of the system
For an open system, the energy balance for the case of one
species entering and leaving (e.g. J/s):
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Dr. Shaker Haji, University of Bahrain 3/29/2012
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Dr. Shaker Haji, University of Bahrain 3/29/2012
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Dr. Shaker Haji, University of Bahrain 3/29/2012
By substitution:
Does this Eq. account for the phase change within the reactor?
Yes, through (Hi0 Hi).
Thus, If a phase change takes place during the course of a
reaction, this form of the energy balance must be used
n
FA0 i H i H i 0 (FA0 X ) H rxn (T ) Q W
i 1
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Dr. Shaker Haji, University of Bahrain 3/29/2012
n
FA0 i H i H i 0 (FA0 X ) H rxn (T ) Q W
i 1
(Hi Hi 0) = CPl
T0 i
(Hi Hi 0) = C Pi dT ; If CPi is constant, then: (Hi Hi 0) = CPi (TT0)
T0
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Dr. Shaker Haji, University of Bahrain 3/29/2012
n
FA0 i H i H i 0 (FA0 X ) H rxn (T ) Q W
i 1
Hrxn(T ) i.Hi(T ) or
In general:
H rxn
o
(T R )
This Eq. gives the heat of rxn at any T in terms of the standard heat
of rxn (1 bar) at a reference T (usually 298 K) & the CP term.
Techniques for determining Hrxn at P above 1 bar can be found
elsewhere.
However, for the rxn of H2 & N2 at 400oC, it was shown that Hrxn
increased by only 6% as P was raised from 1 atm to 200 atm!
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Dr. Shaker Haji, University of Bahrain 3/29/2012
n
FA0 i H i H i 0 (FA0 X ) H rxn (T ) Q W s
i 1
n
FA0 i C P i T i T i 0 (FA0 X ) H rxn
o
(T R ) C P T T R Q W s
i 1
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Calculate the heat of reaction for the synthesis of NH3 from H2 & N2 at
150oC in kcal/mol of N2 reacted and also in kcal/mol of H2 reacted.
Additional information:
CP of gases: NH3: 8.92, N2: 6.984, and H2: 6.992 cal/mol.K.
CP of liquid NH3: 30.0 cal/mol.K.
Hvap of NH3: 5.581 kcal/mol at Tn = 33.4oC.
Hof (25oC) of NH3: 11,020 cal/mol.
Solution
N2 + 3H2 2NH3 H rxn (T ) H rxn
o
(TR ) CP T TR
Horxn (150oC) = 22,040 + (10.12)(125K) = 22,040 1,265
=23.31 kcal/mol N2 = 7.77 kcal/mol H2
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Dr. Shaker Haji, University of Bahrain 3/29/2012
0.2
XEB = X 0.15
calculated
through energy 0.1
XEB
balance
0.05
Almost linear
relationship 0
500 550 600 650 700
T (oC) @ adiabatic PFR exit
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Dr. Shaker Haji, University of Bahrain 3/29/2012
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Information:
liquid phase rxn, Q = 0, k = 31.1 h1 at 360 K, T0 = 330 K
FA0 = 0.9X163 = 146.7 kmol/h Feed: 90% A, 10 % inert (mol)
Additional Information:
Solution
Solution
2. Rate law: ,
Therefore, T T 0 H rxn
o
X C i Pi
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Dr. Shaker Haji, University of Bahrain 3/29/2012
3. Stoichiometry:
4. Combine:
CBe CA0 X e
From K C KC
C Ae CA0 (1 X e )
Hand Calculation
T T 0 H rxn
o
X C
i Pi
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Hand Calculation
Computer Calculation
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Q U A (T a T )
U a (T a T )V
SI Units:
U [J/(s m 2 K)], U A [J/(s K)]
U a [J/(s m3 K)]
For the shown system, carry out an energy balance on the volume V.
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Dr. Shaker Haji, University of Bahrain 3/29/2012
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Dr. Shaker Haji, University of Bahrain 3/29/2012
The T in thiss case will raise to 360 K at the reactor exit. At this T, a P
of 1.5 MPa is generated (Vapor Pressure) which is greater than the
rupture pressure of the glass vessel being used.
So what do you suggest?
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Does the
temperature rise
above 325 K?
When the heat transfer fluid maintains a constant T & when it does not?
If the flow rate of the heat transfer fluid is sufficiently high with
respect to the heat exchanged with the reacting mixture, then the heat
transfer fluid temperature will be constant.
Otherwise, T of heat transfer fluid (Ta) will vary along the
length of the reactor.
Derive a differential equation for Ta wrt to V.
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Dr. Shaker Haji, University of Bahrain 3/29/2012
, from CP definition:
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Case 1:
Isothermal Operation
Conversion
(Xexit=0.50)
Rate of Reaction
Temperature
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Case 2:
Adiabatic Operation
Conversion
(Xexit=0.16)
Rate of Reaction
Temperature
Case 3:
With Heat Exchange
Constant Ta
Conversion
(Xexit=0.57)
Rate of Reaction
Temperatures
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Case 4:
With Heat Exchange
Variable Ta, Co-Current Flow
Conversion
(Xexit=0.35)
Rate of Reaction
Temperatures
Case 5:
With Heat Exchange
Variable Ta
Counter Current Flow
Conversion
(Xexit=0.30)
Rate of Reaction
Temperatures
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Exothermic Reaction
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Dr. Shaker Haji, University of Bahrain 3/29/2012
or
K C (T )
Equilibrium Constant Definition: Xe
1 K C (T )
Energy Balance:
You solve these two Eqs. simultaneously to find the adiabatic T &
adiabatic Xe.
It can be solved:
analytically
using a solver
graphically
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Solution:
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Dr. Shaker Haji, University of Bahrain 3/29/2012
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Consultation time!
Case: being limited by equilibrium conversion. rxn: A B
By:
1. Changing the reactor type/operation mode (e.g. reactive
distillation).
2. Adding heat exchanger to the reactor (cooling in this case).
3. Changing the feed temperature (lower T0 in this case).
Consultation time!
Case: being limited by equilibrium conversion.
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Dr. Shaker Haji, University of Bahrain 3/29/2012
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Endothermic Reaction
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Consultation time!
Case: being limited by equilibrium conversion.
Example:
AB
A
= 0
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Dr. Shaker Haji, University of Bahrain 3/29/2012
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Solution:
Optimum T0 = 333 K
Exit conditions @
optimum T0:
T = 364 K
X = 0.7085
Notes:
X is the conversion at the exit.
Xe is calculated based on
the exit T.
CHENG 322 35
Dr. Shaker Haji, University of Bahrain 3/29/2012
How does the X varies along the reactor for the optimum T0 case ?
Notes:
X is the local conversion
Xe is calculated based on the local temperature.
How does the X varies along the reactor for the optimum T0 case ?
K C (T )
Xe
Which equations 1 K C (T )
were used to
plot these
two curves?
dX rA
dV FA0
Notes:
X is the local conversion
Xe is calculated based on the local temperature.
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Dr. Shaker Haji, University of Bahrain 3/29/2012
K C (T )
Xe
1 K C (T )
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Dr. Shaker Haji, University of Bahrain 3/29/2012
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Dr. Shaker Haji, University of Bahrain 3/29/2012
A
= 0
CHENG 322 39
Dr. Shaker Haji, University of Bahrain 3/29/2012
Xe=0.8
X=Xe=0.71
X=0.07
X=Xe=0.69
Te=332.7 K, Xe=0.75
Te=364 K, Xe=0.71
Te=380 K, Xe=0.69
X=Xe=0.69
T=380 K
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Dr. Shaker Haji, University of Bahrain 3/29/2012
CHENG 322 41
Dr. Shaker Haji, University of Bahrain 3/29/2012
Q UA T a T
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Dr. Shaker Haji, University of Bahrain 3/29/2012
CHENG 322 43
Dr. Shaker Haji, University of Bahrain 3/29/2012
Over 800 million pounds of propylene glycol were produced in 2004 and the
selling price was approximately $0.68 per pound. Propylene glycol makes up
about 25% of the major derivatives of propylene oxide. The reaction takes
place readily at room temperature when catalyzed by sulfuric acid.
CHENG 322 44
Dr. Shaker Haji, University of Bahrain 3/29/2012
Feed process variables are as follows: conditions You are feeding 2500
lbm/h (43.04 Ibmol/h) of propylene oxide (P.O.) to the reactor. The feed
stream consists of (1) an equivolumetric mixture of P.O. (46.62 ft3/h) and
methanol (46.62 ft3/h), and (2) water containig 0.1 wt % H2S04. The
volumetric flow rate of waterRON
rate of water is 233.1 ftqlh, uhich is 2.5 times the methanol-PO. Row rate. The
cornspanding
moIar feed rates of methanol and water are 71.87 and 802.8 Ib mol/h,
respectively. The
water-propylene oxide-methanol mixture undergoes a slight decrease in
volume upon mixing
You are the engineer in charge of an adiabatic CSTR producing propylene
glycol by this method. Unfortunately, the reactor is beginning to leak, and you
must replace it; you told your boss several times that sulfuric acid was
corrosive and that mild steel was a poor material for construction. There is a
nice-looking
Solution: overflow CSTR of 300-gal capacity standing idle; it is glass-
lined; and you would like to use it.
T(oF) T(oR) k H
o
rxn(T) X MB X EB
75 535 0.97 -36449 0.11 0.00
83 542 1.47 -36501.5 0.15 0.08
90 550 2.22 -36554 0.21 0.17
87 546.9 1.91 -36534.63 0.19 0.14
95 554 2.86 -36587.13 0.26 0.22
102 562 4.24 -36639.63 0.34 0.30
112 572.1 7.09 -36710.66 0.47 0.41
120 580 10.25 -36763.16 0.56 0.49
127 587 14.68 -36815.66 0.64 0.57
135 595 20.84 -36868.16 0.72 0.65
142 602 29.33 -36920.66 0.78 0.74
140 599.3 25.92 -36901.5 0.76 0.71
147 607 36.28 -36954 0.82 0.79
153 613 47.65 -36997.54 0.85 0.85
165 625 79.23 -37081.17 0.91 0.98
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Solution:
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Solution:
Mole Balance:
Energy Balance:
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Dr. Shaker Haji, University of Bahrain 3/29/2012
T(oF) T(oR) k H
o
rxn(T) X MB X EB G (T ) R(T )
70 530 0.72 -36414 0.08 0.00 2977 0
78 537 1.11 -36466.5 0.12 0.08 4390 3024
85 544 1.65 -36515.5 0.17 0.16 6142 5847
87 546.9 1.91 -36534.63 0.19 0.19 6949 6949
95 554 2.86 -36587.13 0.26 0.27 9517 9974
102 562 4.24 -36639.63 0.34 0.35 12544 12998
112 572.1 7.09 -36710.66 0.47 0.47 17090 17090
120 580 10.25 -36763.16 0.56 0.55 20493 20115
127 587 14.68 -36815.66 0.64 0.63 23688 23139
135 595 20.84 -36868.16 0.72 0.71 26516 26164
142 602 29.33 -36920.66 0.78 0.79 28902 29188
140 599.3 25.92 -36901.5 0.76 0.76 28085 28085
147 607 36.28 -36954 0.82 0.84 30184 31109
153 613 47.65 -36997.54 0.85 0.91 31601 33617
165 625 79.23 -37081.17 0.91 1.04 33627 38435
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Where
or Q UA T a T when T a1 T a 2
Rewrite the above Eq. so that the heat generation term (i.e. the heat
released term) is on the right hand side.
C T
i Pi T 0 Q / FA0 X (H rxn (T ))
or
C T
i Pi T 0 Q / FA0 (rAV / FA0 ) (H rxn (T ))
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Dr. Shaker Haji, University of Bahrain 3/29/2012
C T
i Pi T 0 Q / FA0 X (H rxn (T ))
G (T ) R (T )
T(oF) T(oR) k H
o
rxn(T) X MB X EB G (T ) R(T )
70 530 0.72 -36414 0.08 0.00 2977 0
78 537 1.11 -36466.5 0.12 0.08 4390 3024
85 544 1.65 -36515.5 0.17 0.16 6142 5847
87 546.9 1.91 -36534.63 0.19 0.19 6949 6949
95 554 2.86 -36587.13 0.26 0.27 9517 9974
102 562 4.24 -36639.63 0.34 0.35 12544 12998
112 572.1 7.09 -36710.66 0.47 0.47 17090 17090
120 580 10.25 -36763.16 0.56 0.55 20493 20115
127 587 14.68 -36815.66 0.64 0.63 23688 23139
135 595 20.84 -36868.16 0.72 0.71 26516 26164
142 602 29.33 -36920.66 0.78 0.79 28902 29188
140 599.3 25.92 -36901.5 0.76 0.76 28085 28085
147 607 36.28 -36954 0.82 0.84 30184 31109
153 613 47.65 -36997.54 0.85 0.91 31601 33617
165 625 79.23 -37081.17 0.91 1.04 33627 38435
CHENG 322 50
Dr. Shaker Haji, University of Bahrain 3/29/2012
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Dr. Shaker Haji, University of Bahrain 3/29/2012
8.7.3 Ignition-Extinction
8.7.3 Ignition-Extinction
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Test Yourself
before the ignition and 540 550 560 570 580 590 600
T(K)
extinction Ts?
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Dr. Shaker Haji, University of Bahrain 3/29/2012
Most reacting systems involve more than one reaction and do not
operate isothermally.
This section is one of the most important sections of the book.
or
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Dr. Shaker Haji, University of Bahrain 3/29/2012
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Dr. Shaker Haji, University of Bahrain 3/29/2012
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Dr. Shaker Haji, University of Bahrain 3/29/2012
=0
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Dr. Shaker Haji, University of Bahrain 3/29/2012
take place in a 10-liter CSTR. What are the effluent concentrations for
a case where: 0 = 1000 L/min, CA0 = 0.3 mol/L, & T0 = 283 K ?
Solution
V is specified
Calculate T & X (CA, CB, CC)
Graphical Solution
V is specified
Calculate T & X (CA, CB, CC)
plot the two equations (E.B. & M.B) combine the two equations then
independently plot the two sides (RHS & LHS)
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Dr. Shaker Haji, University of Bahrain 3/29/2012
1
A B
2
Example 8-11 Multiple Reactions in a CSTR B C
1 2
A B C
10
Note: = = = 0.01 , is this a realistic value?
0 1000
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