L12-1

Review: Thermochemistry for

Nonisothermal Reactor Design
FA0 FA XA = 0.7

Consider an exothermic, liquid-phase reaction operated adiabatically in a

PFR (adiabatic operation- temperature increases down length of PFR):
k
A B E 1 1
dX A rA
E
exp 1
R T T
Mole balance: k Ae RT k k1
dV FA0
Arrhenius Equation
E 1 1
dX A kCA0 (1 X A ) dX A (1 X A )
Rate law: rA kCA exp 1
R T T
k1
dV CA00 dV 0

Stoichiometry: FA CA v 0 Need relationships: X T V

0 The energy balance provides this
CA CA0 (1 X A ) relationship
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L12-2

Review: Terms in Energy Balance

dE sys n n
Q W FiEi in
FiEi out
dt i1 i1
Rate of accum Rate of energy added
Heat energy leaving syst
of energy in = work done + to syst by -
in - by mass flow out
system by syst mass flow in
n n
W FPV
i i in
FPV
i i out
Ws P : pressure WS: shaft work
i1 i1 Vi specific volume
Flow work
Ei Ui Internal energy is major contributor to energy term
dE sys n n
Q - Ws Fi (Ui PVi ) in - Fi (Ui PVi ) out
dt i1 i1
Hi Ui PVi
n n
Steady state: 0 Q Ws Fi0Hi0 FHi i
i1 i1
Energy &
Accum of energy =0= Heat shaft Energy & work
- + work added -
in system in work removed by flow out
by flow in
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L12-3

Review: Relate T to Conversion

n n
Steady state: 0 Q Ws Fi0Hi0 FiHi
i1 i1
F
Fi Fi0 iFA0 X A Fi FA0 i i X A where i i0
FA0
dE sys n n
If XA0=0, then: Q Ws Hi0 iFA0 HiFA0 i i X A
dt i1 i1
Multiply dEsys n n
Q Ws Hi0 iFA0 HiFA0 i HiFA0 i X A
out: dt i1 i1

Total energy dE sys n n

balance (TEB) dt Q Ws FA0 Hi0 Hi i iHi FA0 X A
i1 i1 i
0 at steady state HRX T heat of reaction
n n
0 Q Ws FA0 Hi0 Hi i HRX T FA0 XA
i1 i1
Energy & Energy & work
Accum of energy = Heat - shaft + work added - removed by
in system in work
by flow in flow out
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L12-4

Review: Q in a CSTR
CSTR with a heat exchanger, perfectly mixed inside and outside of reactor

FA0

Q UA(Ta T) Ta
T, X Ta

T, X
The heat flow to the reactor is in terms of:
Overall heat-transfer coefficient, U
Heat-exchange area, A
Difference between the ambient temperature in the heat jacket, Ta, and
rxn temperature, T

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L12-5

Review: Tubular Reactors (PFR/PBR):

Integrate the heat flux equation along the length of the
reactor to obtain the total heat added to the reactor :

Q A U(Ta T)dA V Ua(Ta T)dV

a: heat-exchange area per unit volume of reactor

A
a
V

dQ Heat transfer to a perfectly mixed PFR in a jacket

Ua(Ta - T)
dV For a tubular reactor of diameter D, a = 4 / D

For a jacketed PBR (perfectly mixed in jacket):

1 dQ dQ Ua
(Ta T) Heat transfer to a PBR
b dV dW b
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L12-6

L12: Nonisothermal Reactor Design

Goal: Use TEB to design nonisothermal steady-state reactors
Steadystate total energy balance (TEB):
dE sys n n
0 Q Ws FA0 Hi0 Hi i HRX T FA0 X A
dt i1 i1
Needs to be simplified before we can apply it to reactor design
At a particular temperature: Hi Hi (TR ) TT CpidT
R
no phase change
Hi Hi0 Hi (TR ) TT CpidT Hi (TR ) Ti0 CpidT Ti0 CpidT
T T
R R
(Hi Hi0) = - (Hi Hi0) dE sys n T
Substitute Q Ws FA0 iCp,idT HRX T FA0 X A
dt i1T i0
For a SS nonisotherm n T
0 Q Ws FA0 iCp,idT HRX T FA0 X A
flow reactor: i1T i0
Constant (average) n
0 Q Ws FA0 iCp,i T Ti0 HRX (T)FA0 XA
heat capacities : i1

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 Relating HRX(T) to HRX(TR) and
L12-7

Overall Change in Heat Capacity

n T
0 Q Ws FA0 iCp,idT HRX T FA0 XA
i1Ti0
T
n n
HRX T iHi (TR ) TR i pi dT
C HRX T H RX (TR ) TT CP dT
R
i1 i1
n
overall heat capacity: CP iCpi
i1 n
overall heat of reaction at reference temp: H RX TR iHi TR
i1

n T
0 Q Ws FA0 iCp,idT H RX (TR ) TT CP dT FA0 X A
i1Ti0 R

Only considering constant (average) heat capacities:

n
0 Q Ws FA0 iCp,i T Ti0 H RX (TR ) CP T TR FA0 X A
i1

T = reaction temp Ti0 = initial (feed) temp TR= reference temp
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L12-8

Solving TEB for Conversion

Always start with this TEB:
n
0 Q Ws FA0 iCp,i T Ti0 H RX (TR ) C
T T F X
i1
P R A0 A

Rearrange to isolate terms with XA on one side of eq:

n
FA0 iCp,i T Ti0 Ws Q H RX (TR ) C
T T F X
i1
P R A0 A

n
FA0 iCp,i T Ti0 Ws Q
Solve for XA:
i1 XA
T T F
H RX (TR ) C
P R A0

Plug in Q for the specific type of reactor, and

solve this eq simultaneously with design equation

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L12-9

Solving TEB for XA for an Adiabatic Rxn

n
0 Q Ws FA0 iCp,i T Ti0 H RX (TR ) C
T T F X
i1
P R A0 A

Rearrange:
n
FA0 iCp,i T Ti0 Q Ws H RX (TR ) C
T T F X
i1
P R A0 A

Which term in this equation is zero because were solving for an adiabatic
reaction?
a) dEsys/dt d) FA0
b) Q e) None of the above
c)
When the reaction is adiabatic (Q=0):
n
FA0 iCp,i T Ti0 Q Ws H RX (TR ) C
T T F X
i1
P R A0 A

n
FA0 iCp,i T Ti0 0 Ws H RX (TR ) C
T T F X
i1
P R A0 A

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L12-10

Solving TEB for XA for an Adiabatic Rxn

n
0 Q Ws FA0 iCp,i T Ti0 H RX (TR ) C
T T F X
i1
P R A0 A

Rearrange:
n
FA0 iCp,i T Ti0 Q Ws H RX (TR ) C
T T F X
i1
P R A0 A

When shaft work can be neglected (=0) and the reaction is adiabatic (Q=0):
n
FA0 iCp,i T Ti0 0 0 H RX (TR ) C
T T F X
i1
P R A0 A

n
Solve for XA: FA0 iCp,i T Ti0
i1 XA
H RX (TR ) C T T F
P R A0
n Solve this eq simultaneously
iCp,i T Ti0 with design equation
i 1 X A Design eqs do not change,
H RX (TR ) C T T
P R except k will be a function of T
T = reaction temp Ti0 = initial (feed) temperature TR= reference temp
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L12-11

Nonisothermal Adiabatic Operation

Constant or mean heat capacities

n
Q Ws FA 0 iC pi( T Ti0 ) FA 0 X HR X( TR ) C p( T TR ) 0
i1

For a system with no shaft work ( W s 0 ) & adiabatic operation (Q 0 ):

n
iCpi (T Ti0 ) Q 0
X i1
W 0
HRX (TR ) C
(T T ) Xenergy balance s
p R

CSTR, PFR, PBR, Batch

Usually, C p( T TR ) HR X( TR ) Temperature
Adiabatic exothermic reactions

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L12-12

Nonisothermal CSTR
FA0 X
Design equation (From mass balance) : V
rA
Energy balance: Coupled
n
Q Ws FA0 iCpi (T Ti0 ) FA0 X HRX (TR ) C
(T T ) 0
i1
p R

With the exception of processes involving highly viscous materials,

the work done by the stirrer can be neglected (i.e. W s 0 )
With heat exchanger: Q UA(Ta T)
n
UA(Ta T) 0 FA0 iCpi (T Ti0 ) FA0 X HRX (TR ) C
(T T ) 0
i1
p R
n
UA(Ta T) FA0 iCpi (T Ti0 ) FA0 X HRX (TR ) C p (T TR )
i1

UA(Ta T) n
iCpi (T Ti0 ) X HRX (TR ) C
(T T )
FA0 i1
p R

UA(Ta T)
n
X HRX (TR ) Cp ( T TR ) iCpi (T Ti0 )
FA0 i1
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L12-13

Application to CSTR
Case 1: Given FA0, CA0, A, E, Cpi, HI, and XA, calculate T & V

a) Solve TEB for T at the exit (Texit = Tinside reactor)

b) Calculate k = Ae-E/RT where T was calculated in step a
c) Plug the k calculated in step b into the design equation to calculate VCSTR

Case 2: Given FA0, CA0, A, E, Cpi, HI, and V, calculate T & XA

a) Solve TEB for T as a function of XA
b) Solve CSTR design equation for XA as a function of T (plug in k = Ae-E/RT )
c) Plot XA,EB vs T & XA,MB vs T on the same graph. The intersection of these 2
lines is the conditions (T and XA) that satisfies the energy & mass balance
XA,EB = conversion determined from the TEB equation
XA,MB = conversion determined using the design equation
XA,exit
XA,MB Intersection is T and XA that
XA satisfies both equations
XA,EB

T Texit
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L12-14

Application to a Steady-State PFR

FA0 FA

XA
T

distance
Negligible shaft work (S=0) and adiabatic (Q=0)

a) Use TEB to construct a table of T as a function of XA

b) Use k = Ae-E/RT to obtain k as a function of XA
c) Use stoichiometry to obtain rA as a function of XA
d) Calculate: XA
dX A
V FA0
X rA X A ,T
A0
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
A first order reaction A(l) B(l) is to be carried out adiabatically in a CSTR. L12-15
Given A, E, T0, 0, CA0, and FA0, find the reactor volume that produces a
conversion XA. The heat capacities of A & B are approximately equal, & S=0.
a) Solve TEB for T:
n
0 Q Ws FA0 iCp,i T Ti0 H RX (TR ) CP T TR FA0 X A


n 0 0 i 1
FA0 iCp,i T Ti0 H RX (TR ) CP T TR FA0 X A
i1

n
iCp,i T Ti0 H RX (TR ) CP T TR X A Multiply out
i1

n
iCp,iT iCp,iTi0 H RX (TR )X A CPTX A CPTR X A Isolate T
i1
n n
iCp,iT CPTX A H RX (TR )X A CPTR X A iCp,iTi0
i1 i1
n
Factor out T T iCp,i CP X A H RX (TR )X A CPTR X A Cp,A TA0
i1
Temp when n Plug in values (Cp,
specified H RX (TR )X A CPTR X A iCp,iTi0 H (T ), C ) given
RX R p,i
XA is T i 1
in problem statement
reached n
iCp,i CP X A (look them up if
i1 necessary) & solve
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
A first order reaction A(l) B(l) is to be carried out adiabatically in a CSTR. L12-16
Given A, E, T0, 0, CA0, and FA0, find the reactor volume that produces a
conversion XA. The heat capacities of A & B are approximately equal, & S=0.
a) Solve TEB for T of reaction when the specified XA is reached:
n
H RX (TR )X A CPTR X A iCp,iTi0
T i1
n
iCp,i CP XA
i1
b) Calculate k = Ae-E/RT where T was calculated in step (a)
Look up E in a thermo book
c) Plug the k calculated for the reactions temperature when the specified XA
is reached (in step b) into the design equation to calculate VCSTR
FA0 X A FA0 X A FA0 X A CA00 X A
V V V V
rA kC A kC A0 1 X A kC A0 1 X A

0 X A
V
k 1 X A

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L12-17
Now, the first order reaction A(l) B(l) is carried out adiabatically with and
inlet temp of 300 K, CPA = 50 cal/molK, and the heat of reaction = -20,000
cal/mol. Assume S=0. The energy balance is:
n 0 0
FA0 iCp,i T Ti0 Ws Q
XA i 1 HRX T H RX (TR ) C T T
P R
H RX (TR ) C T T F
P R A0
n
iCpi T T0 n
T T0
i1 iCpi 1 Cp A CP
XEB i1 XEB A
HRX T HRX T
From thermodynamics
XEB 50 T 300
XEB
20000

From energy balance

T
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
The irreversible, elementary liquid-phase reaction 2A B is carried out adiabatically L12-18

in a flow reactor with S=0 and without a pressure drop. The feed contains equal molar
amounts of A and an inert liquid (I). The feed enters the reactor at 294 K with 0 = 5
dm3/s and CA0= 1 mol/dm3. What would be the temperature inside of a steady-state
CSTR that achieved XA= 0.8? Extra info:
E = 10,000 cal/mol CpA= 15 cal/molK CpB= 30 cal/molK CpI = 15 cal/molK
HA(TR) = -20 kcal/mol HB(TR) = -50 kcal/mol HI(TR) = -15 kcal/mol
k = 0.02 dm3/mols at 350 K
n
Start with SS EB & solve for T: 0 Q Ws FA0 iCp,i T Ti0 HRX (T)FA0 X A
i1
n
0 0 0 FA0 iCp,i T Ti0 HRX (T)FA0 X A
i1
n
FA0 iCp,i T Ti0 H RX TR CP T TR FA 0 X A
i1

n
iCp,i T Ti0 H RX (TR ) CP T TR X A
Multiply out brackets & bring
i1
terms containing T to 1 side
n n
iCp,iT CP TX A H RX (TR )X A CP TR X A iCp,iTi0
i1 i1
n
H RX (TR )X A CP TR X A iCp,iTi0
T i1
n
iCp,i CP X A
i1
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
The irreversible, elementary liquid-phase reaction 2A B is carried out adiabatically L12-19

in a flow reactor with S=0 and without a pressure drop. The feed contains equal molar
amounts of A and an inert liquid (I). The feed enters the reactor at 294 K with 0 = 5
dm3/s and CA0= 1 mol/dm3. What would be the temperature inside of a steady-state
CSTR that achieved XA= 0.8? Extra info:
E = 10,000 cal/mol CpA= 15 cal/molK CpB= 30 cal/molK CpI = 15 cal/molK
HA(TR) = -20 kcal/mol HB(TR) = -50 kcal/mol HI(TR) = -15 kcal/mol
k = 0.02 dm3/mols at 350 K
n
H RX (TR )X A CP TR X A iCp,iTi0
T i1
Start with SS EB & solve for T: n
iCp,i CP X A
i1
b 1 cal cal C 0
Cp Cp Cp Cp 30 15 p
a B A 2 mol K mol K
n cal cal cal
A 1 B 0 I 1 iCp,i = 1 15 + 1 15 30
i1 mo l K mo l K m ol K

d
a
c

H RX TR H D TR H C TR H B TR H A TR
a
b
a

1 cal cal

H RX TR 50,000
2
20,000
mol

m ol
H T
RX R 5000
cal
mol

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
The irreversible, elementary liquid-phase reaction 2A B is carried out adiabatically L12-20

in a flow reactor with S=0 and without a pressure drop. The feed contains equal molar
amounts of A and an inert liquid (I). The feed enters the reactor at 294 K with 0 = 5
dm3/s and CA0= 1 mol/dm3. What would be the temperature inside of a steady-state
CSTR that achieved XA= 0.8? Extra info:
E = 10,000 cal/mol CpA= 15 cal/molK CpB= 30 cal/molK CpI = 15 cal/molK
HA(TR) = -20 kcal/mol HB(TR) = -50 kcal/mol HI(TR) = -15 kcal/mol
k = 0.02 dm3/mols at 350 K n
H RX (TR )X A CP TR X A iCp,iTi0
Start with SS EB & solve for T: T i1
n
iCp,i CP X A
i1
n

Cp 0 cal cal
iCp,i 30 H RX TR 5000
i1 mol K mol

cal cal cal cal

5000 X 0 30 294K 5000 X 8820
mol A mol K mol A
mol
T T
cal cal
30 0 30
mol K mol K

TX 0.8 166.67K 0.8 294K TXA 0.8 427.3K

A

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
The irreversible, elementary liquid-phase reaction 2A B is carried out adiabatically L12-21

in a flow reactor with S=0 and without a pressure drop. The feed contains equal molar
amounts of A and an inert liquid (I). The feed enters the reactor at 294 K with 0 = 5
dm3/s and CA0= 1 mol/dm3. What would be volume of the steady-state CSTR that
achieves XA= 0.8? Extra info:
E = 10,000 cal/mol CpA= 15 cal/molK CpB= 30 cal/molK CpI = 15 cal/molK
HA(TR) = -20 kcal/mol HB(TR) = -50 kcal/mol HI(TR) = -15 kcal/mol
k = 0.02 dm3/mols at 350 K
FA 0 X A
Solve the CSTR design eq for V at XA = 0.8 & T = 427.3K: VCSTR
-rA
CA0 0 X A
rA kCA Stoichiometry : C A C A0 1 X A Combine : VCSTR
2

k CA0 2 1 X A
2

dm3 10,000cal mol 1 1

Need k at 427.3K: k 0.02 exp
mol s 1.987cal mol K 350K 427.3
dm3 dm3
k 0.02 exp 2.60124 k 0.2696
mol s mol s
dm3
5 0.8
VCSTR s V 370.9dm 3
CSTR
dm3 mol
1 3 1 0.8
2
0.2696
mol s dm
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
The irreversible, elementary liquid-phase reaction 2A B is carried out adiabatically L12-22

in a flow reactor with S=0 and without a pressure drop. The feed contains equal molar
amounts of A and an inert liquid (I). The feed enters the reactor at 294 K with 0 = 5
dm3/s and CA0= 1 mol/dm3. Use the 2-point rule to numerically calculate the PFR
volume required to achieve XA=0.8? Extra info:
E = 10,000 cal/mol CpA= 15 cal/molK CpB= 30 cal/molK CpI = 15 cal/molK
HA(TR) = -20 kcal/mol HB(TR) = -50 kcal/mol HI(TR) = -15 kcal/mol
k = 0.02 dm3/mols at 350 K
Use the energy balance to construct table of T as a function of XA
For each XA , calculate k, -rA and FA0/-rA
Use numeric evaluation to calculate VPFR
XA T(K) k(dm3/mols) -rA(mol/dm3s) FA0/-rA(dm3)
0 294* 0.00129 0.00129
0.8 427.3* 0.2696* 0.010784
*Calculated in CSTR portion of this problem

dm3 1 1 dm3
k 0.02 exp 5032.7126K k 0.00129
mol s 350K 294 mol s
dm3 mol2 mol
rA k C A0 1 X A rA XA 0 0.00129
2 2
2
1 1 0 r 0.00129
mol s dm6
A X A 0
dm3 s
dm3 mol2 mol

2
rA X 0.8 0.2696 1 1 0.8 r 0.010784
mol s dm6
A XA 0.8
A
dm3 s
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
The irreversible, elementary liquid-phase reaction 2A B is carried out adiabatically L12-23

in a flow reactor with S=0 and without a pressure drop. The feed contains equal molar
amounts of A and an inert liquid (I). The feed enters the reactor at 294 K with 0 = 5
dm3/s and CA0= 1 mol/dm3. Use the 2-point rule to numerically calculate the PFR
volume required to achieve XA=0.8? Extra info:
E = 10,000 cal/mol CpA= 15 cal/molK CpB= 30 cal/molK CpI = 15 cal/molK
HA(TR) = -20 kcal/mol HB(TR) = -50 kcal/mol HI(TR) = -15 kcal/mol
k = 0.02 dm3/mols at 350 K
Use the energy balance to construct table of T as a function of XA
For each XA , calculate k, -rA and FA0/-rA
Use numeric evaluation to calculate VPFR
XA T(K) k(dm3/mols) -rA(mol/dm3s) FA0/-rA(dm3)
0 294 0.00129 0.00129 3876
0.8 427.3 0.2696 0.010784 463.6

mol dm
3
mol
FA0 CA0 0 FA0 1 3 5 5
dm s s

mol mol
FA0 5 FA0 5
s 3876 dm3 s 463.6 dm3


A XA 0
r 0.00129
mol rA XA 0.8 0.010784 mol
dm3 s dm3 s

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
The irreversible, elementary liquid-phase reaction 2A B is carried out adiabatically L12-24

in a flow reactor with S=0 and without a pressure drop. The feed contains equal molar
amounts of A and an inert liquid (I). The feed enters the reactor at 294 K with 0 = 5
dm3/s and CA0= 1 mol/dm3. Use the 2-point rule to numerically calculate the PFR
volume required to achieve XA=0.8? Extra info:
E = 10,000 cal/mol CpA= 15 cal/molK CpB= 30 cal/molK CpI = 15 cal/molK
HA(TR) = -20 kcal/mol HB(TR) = -50 kcal/mol HI(TR) = -15 kcal/mol
k = 0.02 dm3/mols at 350 K
Use the energy balance to construct table of T as a function of XA
For each XA , calculate k, -rA and FA0/-rA
Use numeric evaluation to calculate VPFR
XA T(K) k(dm3/mols) -rA(mol/dm3s) FA0/-rA(dm3)
0 294 0.00129 0.00129 3876
0.8 427.3 0.2696 0.010784 463.6

X1
h

2-point rule: f x dx f X 0 f X 1 where h X 1 X 0 h 0. 8 0 h 0. 8
2
X0
0. 8
VPF R 3876dm3 463. 6dm3
2

VP F R 1736 dm3

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.