Chapter 4

Multiple Reactions
 Objectives

 Define different types of selectivity and yield

 Choose a reaction system that would maximize the selectivity of the
desired product given the rate laws for all the reactions occurring in the
system.
 Determine the species concentrations in a batch reactor, semi-batch
reactor, CSTR, PFR, and PBR, systems.
8.1 Definition of Multiple Reaction

 Parallel rxns (competing rxns)

k1 B
A
k2 C
 Series rxns (consecutive rxns)
k1 k2
A B C

 Complex rxns (Parallel + Series rxns)

k1
A+B C+D
k2
A+C E

 Independent rxns
k1
A B+C
k2
D E+F
 8.1.1 Examples of Multiple Reaction
 Parallel rxns (Oxidation of ethylene to ethylene oxide)
k1 2CO2 + 2H2O
CH2=CH2 +O2
k2
CH2-CH2
 Series rxns (rxn of EO with NH3) O
Monoethanolamine
O
CH2-CH2 + NH3 HOCH2CH2NH2
EO EO
(HOCH 2CH2)2NH
Diethanolamine (HOCH 2CH2)3N
Triethanolamine

 Complex rxns (formation of butadiene from ethanol)

C2H5OH C2 H4 + H 2 O
C2H5OH CH3CHO + H2
C2H4 + CH3CHO C4 H6 + H 2 O

 Independent rxns (The cracking of crude oil to form gasoline)

C15H32 C12H26 + C3H6
 8.1.2 Desired and Undesired Reaction

kD The economic incentive

D (Desired Product)
A
kU Maximize the formation of D
U (Undesired
Product) Minimize the formation of U

D Total cost

cost
Reaction cost
A separation

Separation cost
reaction

A, U Low High

Rxn-separation system producing both D & U Efficiency of a reactor system

 8.1.2 Instantaneous Selectivity, SDU

kD D (Desired Product)
A
kU U (Undesired Product)
Selectivity tells us
how one product is
The rate laws are favored over another
 rA  k D C A1  kU C A 2 when we have
multiple reactions.
rD  k D C A1
rU  kU C A 2

r k Rate of formation of D
S D /U  D  D C A1  2 =
rU kU Rate of formation of U
 Overall Selectivity, ~SDU

For Flow Reactor

~ FD Exit molar flow rate of desired product

SD/U = =
FU Exit molar flow rate of undesired product

For Batch Reactor

~ ND No. of moles of desired product at the end of rxn time

SD/U = =
NU No. of moles of undesired product at the end of rxn time
 ~
Comparison between SD/U and SD/U for a CSTR

~
Mission: Develop a relationship between SD/U and SD/U in a CSTR

Solution rD
SD/U =
kD D (Desired Product) rU
A
kU U (Undesired Product) ~ FD
SD/U =
FU
Mole balance of D and U yields FD=rDV and FU=rUV, respectively

~ FD rDV rD
SD/U = = = = SD/U
FU rUV rU
~
SD/U = SD/U
 8.1.3 Yields
).

Instantaneous Yield (Basis: Reaction Rate)

rD
YD = -r
A

Overall Yield (Basis: Mole or Molar Flow Rate)

~ ND Mole of desired product

formed at the end of reaction
For a batch system: YD = N -N = Number of moles of
Ao A key reactant consumed

~ FD
For a flow system: YD = F -F
Ao A
 8.3 Parallel Reactions

kD D (Desired Product)
A
kU U (Undesired Product)

The rate laws are rD  k D C A1 (8-6)

rU  kU C A 2 (8-7)
 rA  rD  rU (8-8)
We want to
 rA  k D C A1  kU C A 2 (8-9)
maximize
SD/U.
rD k D 1  2 Rate of formation of D
S D /U   CA =
rU kU Rate of formation of U
(8-10)
1 and 2 are positive reaction orders
 8.3.2 Maximizing the Desired Product for One Reactant

kD D (Desired Product) rD k D 1  2
S D /U   CA
A rU kU
kU U (Undesired Product)

 Case 1: 1 > 2 , a = 1- 2

rD k D a
S D/U   CA (8-11)
rU kU

Maximize SD/U
- keeping the concentration of reactant A as high as possible during the rxn
- in gas phase rxn, we should run it with inert and at high pressures to keep CA high
- in liquid phase rxn, the use of diluents should be keep to a minimum.
- use a batch or plug-flow reactor
 8.3.2 Maximizing the Desired Product for One Reactant

kD D (Desired Product) rD k D 1  2
SDU   CA
A rU k U
kU U (Undesired Product)

 Case 2: 2 > 1 , b = 2- 1

rD k D 1
SD/U   (8-12)
rU k U C bA

Maximize SD/U
- keeping the concentration of reactant A as low as possible during the rxn
- in gas phase rxn, we should run it with inerts and at low pressures to keep CA low
- in liquid phase rxn, the use of diluents should be keep to a maximum
- use a CSTR or recycle reactor (product stream act as a diluent)
 Maximizing SDU for one reactant
Whether the reaction should be run at high or low T?

rD k D 1  2
SDU   CA
E D  EU rU k U
k D AD 
S D /U ~  e RT
kU AU
ED  EU

 Case 3: ED > EU S D /U
- kD (rD) increases more rapidly with increasing temp. than does the kU.

- keeping the temperature as high as possible to maximize SDU.

T

ED  EU
 Case 4: EU > ED
S D /U
- keeping the temperature as low as possible to maximize SDU

- not so low that the desired rxn does not proceed to any significant extent.
T
 Ex 8-1: Maximizing SB/XY for the Trambouze Reaction

Reactant A decomposes by three simultaneous reactions to form three

products, B (desired), X (undesired), and Y (undesired). These liquid phase
reactions, along with the appropriate rate laws, are called the Trambouze
reactions.
mol
k1 X  r1A  rX  k 1  0. 0001 (0)
dm 3  s
k2
A B  r2A  rB  k 2 C A  (0.0015s 1 )C A (1)
k3
dm 3 2
Y  r3A  rY  k 3C  0.008
2
A CA (2)
mol  s

How and under what conditions (e.g., reactor types, temperature,

concentrations) should the reaction be carried out to maximize the selectivity of
B?

 The specific reaction rates are given @ 300K

 E1C=10,000, E2=15,000,
A0  0.4 mol/dm
3
and E3=20,000 kcal/mole
, v0=2.0 rB k 2CA
SB/(Xdm /s
3
  Y)  
rX  rY k1  k 3C 2A
 Maximizing SB/XY for the Trambouze Reaction

CA SB/(X+Y) rB k 2C A
SB/(X  Y)  
0 0
rX  rY k1  k 3C 2A
0.025 0.357143
0.05 0.625
0.075 0.775862
SB/(X+Y)=(0.0015*CA)/(0.0001+0.008*CA2)
0.1 0.833333
0.125 0.833333
1
rB k 2C A
0.15 0.803571
0.84 SB/(X  Y)  
rX  rY k1  k 3C 2A
0.175 0.76087
0.8
0.2 0.714286
0.225 0.668317
0.6
0.25 0.625
SB/(X+Y)
0.275 0.585106
0.3 0.54878
0.4
0.325 0.515873
0.35 0.486111 0.2
0.375 0.459184
0.4 0.434783 0 0.112
0.425 0.412621
0 0.1 0.2 0.3 0.4 0.5
0.45 0.392442
0.475 0.374016
0.5 0.357143 CA (mol/dm3)
 Maximizing SB/XY for the Trambouze Reaction

As we see, the selectivity reaches a maximum at a concentration C*A. Because the

concentration changes down the length of a PFR, we cannot operate at this
maximum. Consequently, we will use a CSTR and design it to operate at this
maximum. To find the maximum C*A, we differentiate SB/(X+Y) w.r.t. CA, set the
derivative to zero, and solve for C*A. That is, rB k 2CA
SB/(X  Y)  
rX  rY k1  k 3C 2A
dSB/(X  Y)
0

k 2 k1  k 3C*2
A - k C
2 A
*
2k C
3 A
*
 
dC A k 1  k 3C *2 2
A 
k1 0.0001(mol/dm 3  s)
C 
*
A   0.1118mol/ dm 3

k3 0.008(dm 3 /mol  s)

k1 k1
k2 k2
rB k 2C A* k3 k3 k2
SB/XY       0.8385
r X  rY k1  k 3C A*2
 k1 
2
2k1 2 k1k 3
k1  k 3  

 k3 
 Maximizing SB/XY for the Trambouze Reaction

We now calculate this CSTR volume and conversion. The net rate of formation of
A from reactions (1), (2), and (3) is

rX  k1
- rA  k1  k 2C A  k 3C 2
A rB  k 2 C A
rY  k 3C 2A

CSTR volume for this liquid-phase reaction,    0

0 [C A0  C*A ] 0 [C A0  C*A ]
V   1567.6 dm 3 CSTR volume for
maximum selectivity
 rA [k1  k 2 C*A  k 3C*A2 ]

k1  0.0001 mol/dm 3  s
V CA0  C *
C A0  C *
   A
 783.8s
A
k 2  0.0015 s 1
0  rA
*
k1  k 2C A  k 3C A
* *2
k 3  0.008 dm 3 /mol  s
0  2.0 dm 3 /s
C A0  0.4 mol/dm 3
C A*  0.112 mol/dm 3
 Maximizing SB/XY for the Trambouze Reaction

What is the conversion of A in the CSTR?

C A0 - C A* 0.4 - 0.112
X 
*
  0.72
C A0 0.4

If greater than 72% conversion of A is required, then the CSTR operated with a
reactor concentration of 0.112 mol/dm3 should be followed by a PFR because the
concentration and selectivity will decrease continuously from C*A as we move down
the PFR to an exit concentration CAf. Hence the system

CSTR  PFR CAf 

 C *A C *A 

Would be the highest selectivity while forming more the desired product B,
beyond what was formed at C*A in a CSTR.
How can we increase the conversion and still have a high selectivity SB/(X+Y)?
 Maximizing SB/XY for the Trambouze Reaction

Optimum CSTR followed by a PFR.

The exit concentration of X, Y, and B can be found from the CSTR mole balances

υ0 C X υ0 C X
Species X: V   C X  k1τ  (0.0001)(783)  0.0783mol / dm 3
rX k1
υ0 C B υ0 C B
Species B: V  *
 C B  k 2 τC *A  (0.0015)(0.112 )(783)  0.132mol / dm 3
rB k2 C A
υ0 CY υC
Species Y: V  0 *Y2  CY  k3 τC *A2  (0.008)(0.112 ) 2 (783)  0.0786mol / dm 3
rY k3 C A

FX  0 C X  0.156 mol / s, FB   0 C B  0.264 mol / s, FY  0 C Y  0.157 mol / s

Let’s check to make sure the sum of all the species in solution equals the initial
concentration CA0 = 0.4.

CA+CX+CB+CY=0.112+0.0783+0.132+0.0786=0.4
 8.3.3 Reactor Selection and Operating Conditions

Two simultaneous reactions with two reactants

k1 D (Desired Product)
A+B
k2 U (Unwanted Product)

The rate laws are

 rA  k1CA1 C B1  k 2 CA2 C B 2

rD  k1CA1 C B1
rU  k 2 CA2 C B 2

Rate selectivity rD k1 1  2 1   2
SD / U   CA CB
parameter rU k 2

Rate selectivity parameter (= Instantaneous selectivity) is to maximized by

choosing reactor schemes.
 Reactor Selection Criteria

 Selectivity
 Yield
 Temperature control
 Safety
 Cost
 Figure 8-2
Different reactors and schemes for maximizing the desired product
A B A
B
A
B A
B A B

(a) CSTR (b) tubular reactor (c ) batch (d) semi-batch 1 (e) semi-batch 2

A A
B B

(f) Tubular reactor with side streams (g) Tubular reactor with side streams

B
A

(h) Series of small CSTRs

 Figure 8-2
Different reactors and schemes for maximizing the desired product

The two reactors with recycle shown in (i) and (j) can be used for highly
exothermic reactions. Here recycle stream is cooled and returned to the
reactor to dilute and cool the inlet stream thereby avoiding hot spots and
run-away reactions. The PFR with recycle is used for gas-phase
reactions, and the CSTR is used for liquid-phase reactions.

A
B

A
B

(i) Tubular reactor with recycle (j) CSTR with recycle

 Figure 8-2
Different reactors and schemes for maximizing the desired product
The last two reactors, (k) and (l), are used for thermodynamically limited
reactions where the equilibrium lies far to the left (reactant side)
←
A+B ← C+D
And one of the products must be removed (e,g., C) for the reaction to
continue to completion. The membrane reactor (k) is used for
thermodynamically limited gas-phase reactions, while reactive distillation
(l) is used for liquid-phase reaction when one of the products has a high
volatility (e.g., C) than the other species in the reactor.
C
C A+B
A
D
B

D
(k) Membrane reactor
(l) Reactive distillation
 Example 8-2: Minimizing unwanted products for two reactants

For the parallel reactions, consider all possible combinations of reaction orders and select
the reaction scheme that will maximize SD/U.

k1
D (Desired Product)
A+B
k2
U (Undesired Product)

Case I : 1 > 2, 1 > 2, a = 1-2 > 0, b = 1-2 > 0

rD k1 a b
the rate selectivity parameter
S DU   C AC B
rU k 2

To maximize the SDU, maintain the concentration of both A and B as high as possible
 a tubular reactor (Figure 8-2 (b))
 a batch reactor (Figure 8-2 (c))
 high pressures (if gas phase), and reduce inerts
 Example 8-2: Minimizing unwanted products for two reactants

for the parallel reactions

k1 D (Desired Product)
A+B
k2
U (Undesired Product)

Case II : 1 > 2, 1 < 2, a = 1-2 > 0, b = 2-1 > 0

rD k1C Aa
S DU  
the rate selectivity parameter rU k 2C Bb

To maximize the SDU, maintain CA high and CB low.

 a semi batch reactor in which B is fed slowly into A. (Figure 8-2(d))
 a tubular reactor with side stream of B continually (Figure 8-2(f))
 a series of small CSTRs with A fed only to the first reactor and small B fed
to each reactor. (Figure 8-2(h))
 Example 8-2: Minimizing unwanted products for two reactants

for the parallel reaction

k1 D (Desired Product)
A+B
k2 U (Undesired Product)

Case III : 1 < 2, 1 < 2, a = 2-1 > 0, b = 2-1 > 0

rD k1
S DU  
the rate selectivity parameter
rU k 2C Aa C Bb

To maximize the SDU, maintain the concentration of both A and B as low as possible
 a CSTR (Figure 8-2(a))
 a tubular reactor in which there is a large recycle ratio (Figure 8-2(i))
 a feed diluted with inert material
 low pressures (if gas phase)
 Example 8-2: Minimizing unwanted products for two reactants

for the parallel reaction

k1 D (Desired Product)
A+B
k2
U (Undesired Product)

Case IV : 1 < 2, 1 > 2, a = 2-1 > 0, b = 1-2 > 0

rD k1C Bb
S DU  
the rate selectivity parameter rU k 2C Aa

To maximize the SDU, maintain the concentration of both A and B as high as possible
 a semibatch reactor in which A is slowly fed to a large amount of B (Figure 8-2(e))
 a membrane reactor or tubular reactor with side stream of A (Figure 8-2(g))
 a series of small CSTRs with fresh A fed to each reactor
8.4 Maximizing the desired product in series reaction

k1 k2
A B C

 In parallel rxns, maximize the desired product

 by adjusting the reaction conditions (e.g. CA, CB)
 by choosing the proper reactor

 In series rxns, maximize the desired product

 by adjusting the space-time for a flow reactor
 by choosing real-time for a batch reactor
 Maximizing the desired product in series reaction

k1 k2
A B C
Desired Product

 If the first reaction is slow and second reaction is fast, it will be

extremely difficult to produce species B.

 If the first reaction (formation of B) is fast and the reaction to form C is

slow, a large yield of B can be achieved.

 However, if the reaction is allowed to proceed for a long time in a

batch reactor or if the tubular flow reactor is too long, the desired product
B will be converted to C.
 Example 8-3: Maximizing the yield of the intermediate product

k1 k2
A→ B→ C
Determine the concentration of desired product as a function of space-
time in packed bed reactor?
Solution
 
kk11ττ
C  C e
CAA  CAA00 e
  eekk11ττ  eekk22ττ 
CAA00
CBB  kk11C
C 
 kk22  kk11 
Reaction paths for different ks in series reaction
k1 k2
A B C

For k1/k2>1, a
B k1
1
Large quantity of B
Can be obtained k2

k1
~1
k2
For k1/k2<1, a
Little quantity of B  2'
Can be obtained  3' k1
1 1st rxn is slow
 '
1 k2 2nd rxn is fast

A C
Long rxn time in batch or long tubular reactor
 B will be converted to C
 Relationship for Multiple Rxns Occuring in a PFR
For equations for species j and reaction i that are to be combined when we have q reactions and n species

dF j
Mole Balance:  rj
dV
Rate laws: rij  kij f i (C1 , C j , Cn )
q
rj   rij
i 1

riA r r r
 iB  iC  iD
 ai  bi ci di
n
Stoichiometry: FT   F j
j 1

F j P T0
(gas-phase) C j  CT 0
FT P0 T

(liquid-phase)
Fj
Cj 
0
 Multiple reactions
Reaction 1: 4NH3 + 6NO  5N2 + 6H2O  r1NO  k1NO C NH 3 C 1NO
.5

Reaction 2: 2NO  N2 + O2  r2 N 2  k 2 N 2 C NO
2

Reaction 3: N2 + 2O2  2NO2  r3O2  k 3O2 C N 2 C O22

The rates for rxns 1, 2 and 3 are given in terms of species NO, N 2, and O2, respectively.
Consequently, to relate each reacting species in each rxn to its rate law more clearly, we divide
each rxn through by the stoichiometric coefficient of the species for which the rate law is given.

 r1NO  k1NO C NH 3 C 1NO

.5

1: NO + 2/3NH3  5/6N2 + H2O

 r2 N 2  k 2 N 2 C NO
2

2: 2NO  N2 + O2
 r3O2  k 3O2 C N 2 C O22
3: O2 + 1/2N2  NO2

The corresponding rate laws are related by:

riA riB riC riD
  
 ai  bi ci di
Reaction 1:
1 The rate law w.r.t. NO is
 r1NO  k1NO C NH 3 C 1NO
.5

The relative rates are

r1NO r1NH 3 r1N 2 r1H O
   2
(1) (2 / 3) (5 / 6) (1)
Then the rate of NH3, N2, and H2O
2 2
 r1NH 3  ( r1NO )  k1NO C NH 3 C 1NO.5

3 3
5 5
r1N 2  (r1NO )  k1NO C NH 3 C 1NO .5

6 6
r1H 2O  (r1NO )  k1NO C NH 3 C 1NO
.5

Reaction 2:
2
 r2 N 2  k 2 N 2 C NO
2
 r2 NO  2r2 N 2  2k 2 N 2 C NO
2

r2O2  r2 N 2  k 2 N 2 C NO
2

Reaction 3:
3
1 1
 r3O2  k3O2 C N 2 CO22  r3 N 2  (r3O2 )  k3O2 C N 2 CO22
2 2
r3 NO2  r3O2  k3O2 C N 2 CO22
 3
0
Net rate of formation NO: rNO   riNO  r1NO  r2 NO  r3 NO
i 1

rNO  k1NO C NH 3 C 1NO

.5
 2k 2 N 2 C NO
2

Net rate of formation N2: rN 2   riN 2  r1N 2  r2 N 2  r3 N 2

i 1

5 1
rN 2  k1NO C NH 3 C 1NO
.5
 k 2 N 2 C NO
2
 k3O2 C N 2 CO22
6 2

3
0
Net rate of formation O2: rO2   riO2  r1O2  r2O2  r3O2
i 1

rO2  2k 2 N 2 C NO
2
 k3O2 C N 2 CO22
 Multiple reactions in a PFR
For gas-phase rxns, concentration of species j is

Fj FT 0  F j  P T0  Fj  P T0  Fj 
Cj      CT 0   T=P=0 C j  CT 0  
0  0  FT  P0 T  FT  P0 T  FT 
For gas-phase rxns, concentration of species j is
n
FT   F j  FNO  FNH 3  FN 2  FH 2O  FO2  FNO2
j 1

(1) Mole balance on NO:

dFNO
 rNO   k1NO C NH 3 C 1NO
.5
 2k 2 N 2 C NO
2

dV

1.5 2
2.5  NH 3  FNO
dFNO F  2  FNO 
  k1NO CTO  
 F   2k 2 N 2 CTO  
dV  FT  T   FT 
(2) Mole balance on NH3:

dFNH 3 2 2
 rNH 3   r1NH 3  r1NO   k1NOC NH 3 C 1NO
.5

dV 3 3

1.5
2.5  NH 3  FNO 
dFNH 3 2 F
  k1NOCTO   
dV 3  FT  FT 

(3) Mole balance on H2O:

dFH 2O
 rH 2O   r1H 2O   r1NO  k1NO C NH 3 C 1NO
.5

dV

1.5
2.5  NH 3  FNO 
dFH 2O F
 k1NO CTO   
dV  FT  FT 
(4) Mole balance on N2:
dFN 2 5 1
 rN 2  k1NO C NH 3 C 1NO
.5
 k 2 N 2 C NO
2
 k3O2 C N 2 CO22
dV 6 2

1.5 2 2
2.5  NH 3  FNO  2  FNO  3  N2  FO2 
dFN 2
5 F 1 F
 k1NOCTO     k 2 N 2 CTO    k3O2 CTO   
dV 6  FT  FT   FT  2  FT  FT 

(5) Mole balance on O2:

dFO2
 rO2  r2O2  r3O2  r2 N 2  r3O2
dV

2 2
2  FNO  3  N2  FO2 
dFO2 F
 k 2 N 2 CTO    k3O2 CTO   
dV  FT   FT  FT 

(6) Mole balance on NO2:

2
3  N2  FO2 
dFNO2 F
 rNO2  r3 NO2   r3O2  k3O2 CTO   
dV  FT  FT 
 Hydrodealkylation of Mesitylene in a PFR
1,3,5-trimethylbenzene
CH3 CH3
k1
+ H2 + CH 4
CH3 CH3 CH3

CH3 CH3
k2
+ H2 + CH 4
CH3

The hydrodealkylation of mesitylene is to be carried out isothermally at 1500 R and 35 atm in

a packed-bed reactor in which the feed is 66.7 mol% hydrogen and 33.3 mol% mesitylene.
The volumetric feed rate is 476 ft3/h and the reactor volume (i.e. V=W/b) is 238 ft3.

 r1M  k1CM C H0.5 k1  55.20 (ft 3 /lb mol)0.5 /h @1500R

r2T  k 2C X C H0.5 k 2  30.20 (ft 3 /lb mol)0.5 /h @1500R
M=mesitylene, X=xylene, T=toluene, Me=methane, H=hydrogen

The bulk density of the catalyst has been included in the specific reaction rate (i.e., k 1=k1’ b)

Plot the concentrations of hydrogen, mesitylene, and xylene as a function of space-time.

Calculate the space-time where the production of xylene is a maximum (i.e., opt) .
 Reaction 1: M+H  X + Me
Reaction 2: X+H  T + Me

1. Mole balances:

dFH
Hydrogen
 r1H  r2 H
dV
dFM
Mesitylene  r1M
dV
dFX
Xylene  r1 X  r2 X
dV
dFT
Toluene  r2T
dV
dFMe
Methane  r1Me  r2 Me
dV
2. Rate laws:  r1H  k1C H0.5CM
r2T  k 2C H0.5C X
 Relative Reaction rates:
Reaction 1: -r1H = -r1M = r1X = r1Me
Reaction 2: -r2H = -r2X = r2T = r2Me

3. Stoichiometry: (no volume change with reaction, v=v0)

Flow rates: FH   0 C H
FM   0 C M
FX   0 C X
FMe   0 C Me  FH 0  FH   0 (C H 0  C H )
FT  FM 0  FM  FX   0 (C M 0  C M  C X )
V

0
4. Combining and substituting in terms of the space-time ( )
If we know CM, CH, and CX, then CMe and CT can be calculated from the reaction
stoichiometry. Consequently, we need only to solve the following three equations:
dC H
 k1C H0.5 C M  k 2 C H0.5 C X
d
dC M
 k1C H0.5 C M
d
dC X
 k1C H0.5 C M  k 2 C H0.5 C X
d
5. Parameter evaluation:
y H 0 P0 (0.667)(35 atm)
CH 0   3
 0.021 lb mol/ft 3
RT (0.73 ft atm/lb mol R)(1500 R)
1
C M 0  C H 0  0.0105 lb mol/ft 3
2
C X0  0
V 238 ft 3
   0.5 h
 0 476 ft / h
3

2.0

1.5 CH
Ci 1.0 H2
opt
CM CX
0.5

0.0  (hr)
0.0 0.1 0.2 0.3 0.4 0.5
 Multiple reactions in a CSTR
For a CSTR, a coupled set of algebraic eqns analogous to PFR differential eqns must be solved.
Fj0  Fj
V 
 rj
q

Rearranging yields F j 0  F j   r jV where  r j   rij  f j (C1 , C 2 ,..., C N )

i 1

After writing a mole balance on each species in the reaction set, we substitute for concentrations
in the respective rate laws.

If there is no volume change with reaction, we use concentrations, C j, as variables.

If the reactions are gas-phase and there is volume change, we use molar flow rates, F j as
variables.
q reactions in gas-phase with N different species to be solved
q
F F 
F10  F1   r1V  V   ri1  V  f 1  1 CT 0 ,  , N CT 0 
i 1  FT FT 
F F 
F j 0  F j  r jV  V  f j  1 CT 0 ,  , N CT 0 
 FT FT 
F F 
FN 0  FN   rN V  V  f N  1 CT 0 ,  , N CT 0 
 FT FT 
 Hydrodealkylation of Mesitylene in a CSTR
Calculate the conversion of hydrogen and mesitylene along with the exiting concentrations of
mesitylene, hydrogen, and xylene in a CSTR.

1. Mole Balances: 3. Stoichiometry:

FH 0  FH  ( r1H  r2 H )V   0
FM 0  FM  r1M V FH   0 C H
FX  (r1 X  r2 X )V FM   0 C M
FT  r2T V FX   0 C X
FMe  (r1Me  r2 Me )V FT   0 CT  ( FM 0  FM )  FX
FMe   0 C Me   0 (C H 0  C H )
2. Rate laws:
4. Combining and letting   V /  0 yields:
 r1H   r1M  r1 X  r1Me  k1C H1 / 2 C M
 r2 H  r2 X  r2T  r2 Me  k 2 C 1/ 2
CX C H 0  C H  (k1C H1 / 2 C M  k 2 C H1 / 2 C X )
H
C M 0  C M  (k1C H1 / 2 C M )
C X  (k1C H1 / 2 C M  k 2 C H1 / 2 C X )
 Ex 6-7: Hydrodealkylation of Mesitylene in a CSTR
We put these equations in a form such that they can be readily solved using .
f (C H )  0  C H  C H 0  (k1C H1/ 2C M  k 2C H1/ 2C X )
f (CM )  0  C M  CM 0  (k1C H1/ 2CM )
f (C X )  0  (k1C H1/ 2C M  k 2C H1/ 2C X )  C X

For =0.5, the exiting concentrations are CH=0.0089, CM=0.0029 and CX=0.0033.
The overall conversion is
FH 0  FH C H 0  C H 0.021  0.0089
Hydrogen : XH     0.58
FH 0 CH 0 0.021
FM 0  FM CM 0  CM 0.0105  0.0029
Mesitylene : XM     0.72
FM 0 CM 0 0.0105
0.020

0.015 CH
Ci 0.010

0.005 CX
0.000
CM
0.0 1.0 2.0
CSTR
 Hydrodealkylation of Mesitylene in a CSTR
The moles of hydrogen consumed in reaction 1 are equal to the moles of mesitylene consumed.
Therefore, the conversion of hydrogen in reaction 1 is
C M 0  C M 0.0105  0.0029
X 1H    0.36
CH 0 0.021
The conversion of hydrogen in reaction 2 is

X 2 H  X H  X 1H  0.58  0.36  0.22

The yield of xylene from mesitylene based on molar flow rates exiting the CSTR for =0.5 is

~ FX CX 0.00313 mole xylene produced

YMX     0.41
FM 0  FM C M 0  C M 0.0105  0.0029 mole mesitylene reacted

The overall selectivity of xylene relative to toluene is

~ F C CX 0.00313
S XT  X  X  
FT CT C M 0  C M  C X 0.0105  0.0029  0.00313
mole xylene produced
 0.7
mole toluene produced