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Enthalpy, Heat Capacity, and Heat of Reaction and relationship between them
Rate of work
done by the
system on
the
surroundings
Rate of energy
added to the
system by
mass flow into
the system
Rate of energy
leaving the
system by
mass flow out
of the system
W s
Fin Ein
Control Volume
Q
dE
Fout Eout
Rate of
accumulation
of the energy
within the
system
F1 , E1
F1 , E1
F2 , E2
F2 , E2
...
Fn , En
Q W
...
Fn , En
F E
i 1
i in
F E
i 1
i out
dE
dt
F1 , E1
F1 , E1
F2 , E2
F2 , E2
...
Fn , En
...
Fn , En
In a chemically reacting systems, there are usually two types of work that
need to be accounted for (i) Shaft Work (e.g. work done by impellers in a
CSTR and batch reactor) and (ii) Flow Work
Rate of flow work is rate of work to
get mass into and out of the system
F PV
i 1
i in
F PV
i 1
out
F1 , E1
F2 , E2
F2 , E2
...
Fn , En
u 2i
Ei U i
g z ...
2
...
Fn , En
Ei U i
F1 , E1
F1 , E1
F1 , E1
F2 , E2
F2 , E2
...
Fn , En
Q W
...
Fn , En
F E
i 1
i in
F E
i 1
i out
dE
dt
F E
i 1
i in
dE
dt
F E
i
i 1
i out
Now,
F PV
i 1
i in
F PV
i 1
i out
FU
i 1
i in
FU
i 1
i out
dE
dt
H U PV
F H
i 1
i in
FH
i 1
i out
dE
dt
FA0 , H A0
T0
FB 0 , H B 0
...
FI 0 , H I 0
b
c
d
A B C D
a
a
a
FB , H B
...
FI , H I
H
i 1
i0
Fi 0
Out
H F
i 1
H A0 FA0
H A FA
H B 0 FB 0
H B FB
H C 0 FC 0
H C FC
H D 0 FD 0
H D FD
H I 0 FI 0
H I FI
FA FA 0 (1 X )
b
X)
a
c
FC FA 0 ( C
X)
a
d
Fd FA 0 ( D
X)
a
FI FA 0 ( I ) FI 0
FB FA 0 ( B
F
i 1
i0
F H (T )
H i 0 (T0 )
i 1
d
c
b
H D (T ) H C (T ) H B (T ) H A (T )]FA0 X
a
a
a
HRxn
n
Fi 0 H i 0 (T0 )
i 1
[
H
(
T
)
H
(
T
)]
i
i0
0
i
FA0 X [ H Rxn ]
i 1
Fi H i (T ) FA0
i 1
Fi 0 H i 0 (T0 )
i 1
[
H
(
T
)
H
(
T
)]
i
i0
0
i
FA0 X [ H Rxn ]
i 1
Fi H i (T ) FA0
i 1
H i (T ) H (Tref )
o
i
pi
dT
T Tref
Hi is available from
Chemical Engg handbook
H i 0 (T0 ) H i (T )
Therefore,
T0
Cpi dT
T
And,
T0
H
i 1
i0
(T0 ) H i (T ) i Cpi dT
T
Fi 0 H i 0 (T0 )
i 1
[
H
(
T
)
H
(
T
)]
i
i0
0
i
FA0 X [ H Rxn ]
i 1
Fi H i (T ) FA0
i 1
d
c
b
H D (T ) H C (T ) H B (T ) H A (T )]
a
a
a
H i (T ) H io (Tref )
pi
dT
T Tref
H Rxn (T ) H
where,
Cp
o
Rxn
(Tref )
T Tref
Cp dT
d
c
b
Cp D CpC Cp B Cp A
a
a
a
F1 , E1
F1 , E1
F2 , E2
F2 , E2
...
Fn , En
...
Fn , En
Q W
F E
i 1
i in
F E
i 1
i out
dE
dt
d
E
Q W s Fi H i in Fi H i out
dt
i 1
i 1
Energy Balance Equation in terms of Conversion
Q W s FA0
i 1
dE
T i Cpi dT ] FA0 X H Rxn (T ) dt
0
UA(Ta1 Ta 2 )
ln[ (T Ta1 ) /(T Ta 2 )]
UA
(m
Q UA(Ta T )
Q U (Ta T ) dA
U a (Ta T ) dV
dQ
Ta
T
Non-Isothermal Reactors
iCpi (T T0 )
n
i 1
i 1
XEB
Q 0
W 0
C
p
(
T
T
)
0
i i
te
rm
<<
If
Cp
X EB
Rx
n
C
p
(
T
T
)
i i
0
n
i 1
n
UA(Ta T )
~
Class Problem #6
The following liquid-phase reaction is carried out in a CSTR with heat
exchange:
A B
The feed stream contains A and B in equimolar ratio. The total molar
flow rate is 20 mol/s. The inlet temperature is 325 K, the inlet
concentration of A is 1.5 molar, and the ambient temperature in the
heat exchanger is 300 K.
Calculate the reactor volume necessary to achieve 80% conversion.
Additional information
U= 80 J/m2 s K
A=2 m2
HRxn(298) = -10,000 J/mol
CpA = CpB= 100 J/mol K
F
i 1
i0
H i0
FH
i 1
FA0
T0
dQ
dV
FAe
Te
V V+V
0
H i Fi
0
dV dV
dV
i 1 dV
i 1
0
H i Fi
0
dV dV
dV
i 1 dV
i 1
dQ
dV
Ta
T
V V+V
0
H i Fi
0
dV dV
dV
i 1 dV
i 1
i (rA )
a b c d
0
H i Fi
0
dV dV
dV
i 1 dV
i 1
H i (T ) H (Tref )
i
dV
i 1
n
dT
dV
FiCpi
i 1
o
i
T Tref
pi
dT
dT
Ua(Ta T ) 0 0 i (rA ) H i Fi Cpi
0
dV
i 1
i 1
dT
dV
U a (Ta T ) i ( rA ) H i (T )
i 1
F Cp (T )
i 1
dT
dV
U a (Ta T ) i (rA ) H i (T )
i 1
F Cp (T )
i 1
dFi
i ( rA )
dV
or
g( X ,T )
dX
FA0
(rA )
dV
f ( X ,T )
dT
dV
U a (Ta T ) i ( rA ) H i (T )
i 1
F Cp (T )
i 1
n
dV
Fi Cpi (T )
n
increase in T
dV
FA0 [ i Cpi (T ) X Cp ]
i 1
Class Problem #7
It is proposed to design pilot plant for the production of Allyl
Chloride. The feed stream comprises 4 moles propylene/mole
chlorine. The reactor will be vertical tube of 2 inch ID. The
combined feed molar flow rate is 0.6 g-mol/h. The inlet pressure is
2 atmospheres. The feed stream temperature is 275 C. Calculate
Allyl Chloride production as a function of tube length for the
following 2 cases:
Case-1: PFR jacketed with heat exchange fluid circulated at 275 C
Case-2: Adiabatic operation of PFR
(cP )Cl2
36 J / mol K
(c P ) C3 H 6
107 J / mol K
(cP ) AllylChloride
117 J / mol K
(cP ) HCl
30 J / mol K