Lecture 19

Chemical Reaction Engineering (CRE) is the

field that studies the rates and mechanisms of
chemical reactions and the design of the reactors in
which they take place.
 Web Lecture 19
Class Lecture 17Tuesday 3/19/2013
Energy Balance Fundamentals
Adiabatic reactors

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 Todays Lecture
Energy Balance, Rationale and Overview
Lets calculate the volume necessary to achieve a
conversion, X, in a PFR for a first-order, exothermic and
adiabatic reaction.
The temperature profile might look something like this:

T k X

3 V V V
 Energy Balance, Rationale and Overview
Mole Balance: dX rA
=
dV FA0
E 1 1
Rate Law: rA = ki exp C A
R T1 T
Stoichiometry: C A = C A0 (1 X )
E 1 1
ki exp
Combine: dX R T1 T
= C A0 (1 X )
dV FA0
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 Energy Balance, Rationale and Overview
E 1 1
ki exp
dX R T1 T
= C A0 (1 X )
dV FA0

We cannot solve this equation because we dont

have X either as a function of V or T.

We need another equation. That equation is:

The Energy Balance

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 User Friendly Equations Relate T and X or Fi

1. Adiabatic CSTR, PFR, Batch or PBR

W!S = 0 C P = 0

X EB =
C (T T )
i Pi 0
o
H Rx

X=
C (T T )
i Pi 0

H Rx

T = T0 +
( Rx )X EB
H o

6 C i Pi
 Adiabatic
Exothermic Endothermic

T0

T T

T0
0 XEB 0 XEB

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 User Friendly Equations Relate T and X or Fi

2. CSTR with heat exchange: UA(Ta-T) and a

large coolant flow rate
! UA $
# (T T a )& + iCPi (T T 0 )
" FA0 %
X EB = o
H Rx
Fi0

m! C
T
Ta
8
X
 User Friendly Equations Relate T and X or Fi

3. PFR/PBR with heat exchange

Ta Coolant
FA0
T0

3A. PFR in terms of conversion

Qg Qr
!#"#$ !#"#$
dT
=
( )
rAH Rx T Ua T Ta ( )= Qg Qr

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dV FA0 ( C i Pi
+ C p X ) FA0 ( C
i Pi
+ C p X )
 User Friendly Equations Relate T and X or Fi

3B. PBR in terms of conversion

Ua
dT
rA H Rx (T )
b
(T Ta )
=
dW FA 0 ( Ci Pi + C p X )
3C. PBR in terms of molar flow rates

Ua
dT
rA H Rx (T )
b
(T Ta )
=
dW FiCPi
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 User Friendly Equations Relate T and X or Fi
3D. PFR in terms of molar flow rates

dT rA H Rx (T ) Ua(T Ta ) Qg Qr
= =
dV FiCP i
FiCP i

4. Batch

dT (rAV )(H Rx ) UA(T Ta )

=
dt N iC P i

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 User Friendly Equations Relate T and X or Fi
5. For Semibatch or unsteady CSTR
n
Q! W!S Fi0 C P T Ti0 + #$H Rx T %& rAV
( ( ) ( )( ))
dT i
i=1
= n
dt
N C i Pi
i=1

6. For multiple reactions in a PFR (q reactions and m species)

q

dT
r Hij Rx ij Ua(T Ta )
i=1
= m
dV
FC i Pj
j =1
12 Lets look where these User Friendly Equations came from.
Energy Balance
Reactor with no Spatial Variations

Reactor
Energy Balance
Reactor with no Spatial Variations
Q!

Reactor

Rate of flow of
heat to the
system from
the
surroundings

Q!
(J/s)
Energy Balance
Reactor with no Spatial Variations
Q! W!

Reactor

Rate of flow of
Rate of work
heat to the
system from - done by the
system on the
the
surroundings
surroundings

Q! - W!
(J/s) (J/s)
Energy Balance
Reactor with no Spatial Variations
Q! W!

Fin
Reactor
E in

Rate of flow of Rate of energy

Rate of work
heat to the added to the
system from - done by the
system on the
+ system by mass
the flow into the
surroundings
surroundings system

Q! - W! + Fin Ein
(J/s) (J/s) (J/s)
Energy Balance
Reactor with no Spatial Variations
Q! W!

Fin Fout
Reactor
E in Eout

Rate of flow of Rate of energy Rate of energy

Rate of work
heat to the added to the leaving system
system from - done by the
system on the
+ system by mass - by mass flow
the flow into the out of the
surroundings
surroundings system system

Q! - W! + Fin Ein - Fout Eout

(J/s) (J/s) (J/s) (J/s)
Energy Balance
Reactor with no Spatial Variations
Q! W!

Fin Fout
Reactor
E in Eout

Rate of Rate of flow of Rate of energy Rate of energy

Rate of work
accumulation heat to the added to the leaving system
of energy = system from - done by the
system on the
+ system by mass - by mass flow
within the the flow into the out of the
surroundings
system surroundings system system

dE sys
dt = Q! - W! + Fin Ein - Fout Eout
(J/s) (J/s) (J/s) (J/s) (J/s)
 Energy Balance
!
Q
Fi in Fi out

(e.g., FA 0 ) (e.g., FA )

H i in H i out
!
W
(e.g., H A 0 ) S (e.g., H )
A

Energy Balance on an open system: schematic.

! W
! + F E FE = dE system
Q S i 0 i 0 in i i out (1)
dt
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 OK folks, here is what we are going to do to put the
above equation into a usable form.
1. Replace Ui by Ui=Hi-PVi
2. Express Hi in terms of heat capacities
3. Express Fi in terms of either conversion or rates
of reaction
4. Define HRx
5. Define CP
6. Manipulate so that the overall energy balance
is in terms of the User Friendly Equations.

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 Intro to Heat Effects
Assumptions:
=0 =0
E i = U i + PE i + KE i Other energies small compared to internal
W! = flow work + shaft work
~ ~ ~ m 3
flow work = Fi 0 P0 Vi 0 + Fi PVi V =
mol

Recall:
H i = Ui + PV!i

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 Intro to Heat Effects
Substituting for W!
dEsys
F U FU + ! # F P V! + F PV! + W! % =
Q
i0 i0 i i $ i0 0 i0 i i S&
dt
Hi 0 Hi
"$# $% "$# $
% dEsys
Fi0 !"U i0 + P0V!i0 #$ Fi #$U i + PV!i %& + Q& W&S = dt
dEsys
F H F H + ! W! =
Q
i0 i0 i i S
dt

Steady State: ! W
Q ! + F H F H = 0
22 S i0 i0 i i
 Intro to Heat Effects
General Energy Balance :

! W
! + F H F H = dE system
Q S i0 i0 i i
dt

For Steady State Operation:

! W
Q ! + F H F H = 0
S i0 i0 i i

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 Intro to Heat Effects
F H i0 i0 = FA 0 i H i0

!"
# # $
H Rx

F H
i i
= FA0 ( )
i + i X H i = FA0 i H i + FA0 X i H i

Q! W!S + FA0 ( ( H i i0 ) )
H i + FA0 X H Rx = 0

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 Intro to Heat Effects
For No Phase Changes
T
Hi (T ) = H (TR )+
0
i TR
CPidT
Enthalpy of formation at temperature TR
Constant Heat Capacities
H i (T ) = H i0 (TR )+ CPi (T TR )

H i0 H i = CPi (T T0 )
i i i i + iCPi (T TR )
H = H 0

Heat of reaction at temperature T

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 Intro to Heat Effects
H = H + C (T T )
i i i
0
i i Pi R

H R (T ) = H R (TR ) + CP (T TR )
d c b
iCPi = CP = a CPD + a CPC a CPB C PA

Substituting back into the Energy Balance

Q! W!S FA0 X #$H R TR + C P T TR %& FA0 iC" Pi T Ti0 = 0

( ) ( ) ( )

Adiabatic (Q=0) and no Work (WS = 0)
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 Intro to Heat Effects

d c b
H Rx = HD + HC HB HA
a a a

d c b
C P = C PD + C PC C PB C PA
a a a

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 Intro to Heat Effects

Q! W!S + FA0 ( ( H
i i0 ) )
H i + FA0 X H Rx = 0

Substituting back into the Energy Balance

Q! W!S FA0 X #$H R TR + C P T TR %& FA0 iC" Pi T Ti0 = 0

( ) ( ) ( )

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 Adiabatic Energy Balance

Adiabatic (Q=0) and no Work (WS = 0)

T = T0
[ ~
]
X H R (TR ) + C P (T TR )
= T0
X [H R (T )]
~
C X
C C X C
i Pi
+ P i Pi
+ P
T

Exothermic

T0

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X
 Example: Adiabatic PFR
AB
1) Mole Balance: dX rA
=
dV FA 0

C B E 1 1
2) Rate Laws: rA = k C A k = k1 exp
k C R T1 T
H 0X 1 1
C P = 0 k C = k C 2 exp
k T2 T

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 Example: Adiabatic PFR
AB
3) Stoichiometry:
C A = C A 0 (1 X )

CB = CA0X
4) Energy Balance
H 0X X
T = T0 +
i C Pi
First need to calculate the maximum conversion
31 which is at the adiabatic equilibrium conversion.
Example: Adiabatic PFR
 Example: Adiabatic PFR
AB H X0 X
T = T0 +
iCPi
Xe Adiabatic equilibrium conversion
and temperature

T
KC
X eq =
33 1+ KC
 Example: Adiabatic PFR
We can now form a table. Set X, then calculate T, -VA,
and FA0/-rA, increment X, then plot FA0/-rA vs. X:

FA0/-rA

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X
 End of Web Lecture 19
Class Lecture 17

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