A B
C D
0
=
n n
v
i i
i
0
X
n n
n
i i
i
=
0
0
CHG 3127: Reaction Engineering E.J. Anthony 2012 26
Mole Balances and
Stoichiometry
relationship between and X
=
Xn
v
lim,
lim
0
CHG 3127: Reaction Engineering E.J. Anthony 2012 27
Mole Balances and
Stoichiometry
Mole balance on species j in system of
volume V
wellmixed system
not wellmixed
F F G
dN
dt
j j j
j
0
+ =
G r V
j j
=
G r V r dV
j ji i
i
m
j
V
~ =
=
}
A
1
CHG 3127: Reaction Engineering E.J. Anthony 2012 28
Mole Balances and
Stoichiometry
General integral mole balance on
species j in system of volume V
F F r dV
dN
dt
j j j
V
j
0
+ =
}
CHG 3127: Reaction Engineering E.J. Anthony 2012 29
Stoichiometric Tables
Objective: to find expressions for r
j
and
N
j
Consider the reaction
A as basis:
Rate of formation of C:
In general:
aA bB cC dD + +
A
b
a
B
c
a
C
d
a
D + +
( )
A A C
r
a
c
r
a
c
r = =
= = =
r
a
r
b
r
c
r
d
A B C D
CHG 3127: Reaction Engineering E.J. Anthony 2012 30
Stoichiometric Tables
Consider the previous reaction with a batch
system
Moles A reacted at time t:
Moles A remaining at time t:
A
b
a
B
c
a
C
d
a
D + +
N X
A0
( ) ( )
N t N N X N X
A A A A
= =
0 0 0
1
CHG 3127: Reaction Engineering E.J. Anthony 2012 31
Stoichiometric Tables
Consider further the batch system with reaction
Moles B reacted at time t:
Moles B remaining at time t:
A
b
a
B
c
a
C
d
a
D + +
moles reacted
moles reacted
moles reacted =
B
A
A
b
a
N X
A
0
( )
N t N
b
a
N X
B B A
=
0 0
CHG 3127: Reaction Engineering E.J. Anthony 2012 32
Stoichiometric Tables
!"#$%#& '(%)%*+ ,*(.# /#0*%(%(.
1
N
A0
N X
A0
N N X
A A 0 0
2 N
B0
b
a
N X
A0
N
b
a
N X
B A 0 0
, N
C0
c
a
N X
A0
N
c
a
N X
C A 0 0
+
3 N
D0
d
a
N X
A0
N
d
a
N X
D A 0 0
+
' N
I 0
N
I 0
45)*+ N
T0 ( ) ( )
N d c b a N X
T A 0 0
1 + +
CHG 3127: Reaction Engineering E.J. Anthony 2012 33
Stoichiometric Tables
Total change in number of moles:
Define parameter
represents change in total number of
moles per mole of A converted
o
N N
d
a
c
a
b
a
N X
T T A
= + +

\

.

0 0
1
o = +
d
a
c
a
b
a
1
o
CHG 3127: Reaction Engineering E.J. Anthony 2012 34
Stoichiometric Tables
Concentration of species j given by
For species B, for example,
C
N
V
j
j
=
C
N
b
a
N X
V
B
B A
=
0 0
CHG 3127: Reaction Engineering E.J. Anthony 2012 35
Stoichiometric Tables
Define new variable to represent the inlet
molar flow rate of species i relative to the inlet
flow rate of the reference (limiting) reactant
For species B, for example
O
i
i
A
N
N
=
0
0
C
N
b
a
X
V
B
A B
=

\

.

0
O
CHG 3127: Reaction Engineering E.J. Anthony 2012 36
Stoichiometric Tables
For a constant volume process
Cases of constant volume process:
dilute liquid phase reactions
organic liquid phase reactions (except
polymerization reactions)
gas phase reactions where number of reacting
molecules equals number of product ones,
operating at constant T, P
C
N
b
a
X
V
N
b
a
X
V
C
b
a
X
B
A B A B
A B
=

\

.

=

\

.

=

\

.

0 0
0
0
O O
O
CHG 3127: Reaction Engineering E.J. Anthony 2012 37
Stoichiometric Tables
For flow problems, replace
with
N N
j j
and
0
F F
j j
and
0
CHG 3127: Reaction Engineering E.J. Anthony 2012 38
Stoichiometric Tables
!"#$%#& '(%)%*+ ,*(.# /#0*%(%(.
1
F
A0
F X
A0
( )
F X
A0
1
2 F
B0
b
a
F X
A0
F
b
a
X
A B 0
O

\

.

, F
C0
c
a
F X
A0
F
c
a
X
A C 0
O +

\

.

3 F
D0
d
a
F X
A0
F
d
a
X
A D 0
O +

\

.

' F
I 0
F
A I 0
O
45)*+ F
T0
o F X
A0
F F X
T A 0 0
+o
CHG 3127: Reaction Engineering E.J. Anthony 2012 39
Stoichiometric Tables
Local concentrations calculated from
local molar flow rates and total
volumetric flowrate
C
F
v
i
i
=
CHG 3127: Reaction Engineering E.J. Anthony 2012 40
Stoichiometric Tables
In the case of negligible volume
changes (most liquid phase reactions)
( )
( )
C
F
v
F
v
F X
v
C X
A
A A
A
A
= = =
=
0
0
0
0
1
1
CHG 3127: Reaction Engineering E.J. Anthony 2012 41
Stoichiometric Tables
In the case of significant volume
changes (most gas phase reactions)
or
Define a new symbol
N N N X
T T A
= +
0 0
o
N
N
y X
T
T
A
0
0
1 = +o
c o = y
A0
c
CHG 3127: Reaction Engineering E.J. Anthony 2012 42
Stoichiometric Tables
Calculate the volume (volumetric flow
rate) using the gas law:
or, in terms of fractional conversion
V V
P
P
T
T
z
z
N
N
T
T
=

\

.


\

.


\

.

0
0
0 0 0
 
V V
P
P
T
T
z
z
X =

\

.


\

.


\

.

+
0
0
0 0
1 c
CHG 3127: Reaction Engineering E.J. Anthony 2012 43
Stoichiometric Tables
Concentration given by
or, neglecting compressibility effects
( )
 


.

\


.

\

c +
+ O
=
0
0
0
1
/
P
P
T
T
X
X a v
C C
j j
A j
( ) ( )
( )( )  X z z P P T T V
X a v N
V
X a v N
V
N
C
j j A j j A j
j
c +
+ O
=
+ O
= =
1
/ /
0 0 0 0
0 0
CHG 3127: Reaction Engineering E.J. Anthony 44
Stoichiometric Tables
For a flow system
Concentration given by
or, neglecting compressibility effects
  v v
P
P
T
T
z
z
X =

\

.


\

.


\

.
 +
0
0
0 0
1 c
( )
 
C C
v a X
X
T
T
P
P
j A
j j
=
+
+

\

.


\

.

0
0
0
1
O
c
( ) ( )
( )( )
 
C
F
v
F v a X
v
F v a X
v T T P P z z X
j
j
A j j A j j
= =
+
=
+
+
0 0
0 0 0 0
1
O O
c
Stoichiometric Tables
In summary
For a batch system:
For a flow system:
For both:
CHG 3127: Reaction Engineering E.J, Anthony 2012 45
 
V V
P
P
T
T
z
z
X =

\

.


\

.


\

.

+
0
0
0 0
1 c
 
v v
P
P
T
T
z
z
X =

\

.


\

.


\

.

+
0
0
0 0
1 c
( )
 
C C
v a X
X
T
T
z
z
P
P
j A
j j
=
+
+

\

.


\

.


\

.

0
0 0
0
1
O
c
CHG 3127: Reaction Engineering E.J. Anthony 2012 46
Alternatives to X
Fractional conversion not
appropriate for following situations:
membrane reactions
gas phase multiple reactions
unsteadystate flow reactors
CHG 3127: Reaction Engineering E.J. Anthony 2012 47
Alternatives to X
Express concentrations in terms of
molar flows in these cases


.

\


.

\

=
0
0
0
P
P
T
T
F
F
C C
T
j
T j
0 0
0
0
0
0
RT Z
P
v
F
C
T
T
= =
0
0
0
0
0
0
0
0
T
T
P
P
C
F
z
z
T
T
P
P
F
F
v
v
T
T
T
T
= =
(z=z
0
=1)
CHG 3127: Reaction Engineering E.J. Anthony 2012 48
Analysis of Reactions with
Phase Change
Consider the reaction
Condensation occurs when
beyond this point each mole of D produced in
the reaction condenses
( ) ( ) ( ) ( )
A g B g C g D g l + + 2 ,
y
P
P
D e
v
T
,
=
CHG 3127: Reaction Engineering E.J. Anthony 2012 49
Analysis of Reactions with
Phase Change
Create additional column in the stoichiometric
table to account for balances after
condensation begins
Let X
C
represent the conversion of A at which
condensation begins
Use definition of mole fraction of D at
condensation along with expressions for total
molar flow rate to calculate X
C
CHG 3127: Reaction Engineering E.J. Anthony 2012 50
Consider the example
Assume reactants only are introduced
into a flow reactor according to their
stoichiometric ratios:
( ) ( ) ( ) ( )
A g B g C g D g l + + 2 ,
F F
F F
B A
C D
0 0
0 0
2
0
=
= =
Analysis of Reactions with
Phase Change
CHG 3127: Reaction Engineering E.J. Anthony 2012 51
Analysis of Reactions with
Phase Change
!"#$%#& /#0*%(%(.
62#758# ,5(:;<
/#0*%(%(.
617)#8 ,5(:;<
1
( )
F X
A0
1
( )
F X
A0
1
2
( )
F X
A0
2 2
( )
F X
A0
2 2
,
F X
A0
F X
A0
3
F X
A0
y F
D e T ,
45)*+
( )
F F X
T A
=
0
3
( )
( )
F y F F F X
F F X y
T D e T A A
T A D e
= +
=
,
,
. /
3 2
2 15 1
0 0
0
CHG 4127: Reaction Engineering David G. Taylor, 2000 52
Calculate y
D,e
from operating conditions:
Equate total molar flow rates from two
columns at point of condensation and solve
for y
D,e
in terms of X
C
:
or
y
X
X
D e
C
C
,
=
3
y
P
P
D e
vD
T
,
=
( )
( )
( )
F X F
X
y
A C A
C
D e
0 0
3 2
15
1
=
.
,
Analysis of Reactions with
Phase Change
CHG 3127: Reaction Engineering E.J. Anthony 2012 53
Analysis of Reactions with
Phase Change
to calculate the concentrations after
condensation we note that, at constant
pressure and temperature
C C
T T
=
0
C
C
F
v
F
v
v
F
F
v
T
T
T
T
T
T 0
0
0
0
0
= =
CHG 3127: Reaction Engineering E.J. Anthony 2012 54
Analysis of Reactions with
Phase Change
Knowing F
T0
and F
T
, we can calculate
concentrations:
where
( )
T
T A A
A
F
F
X
v
F
v
F
C
0
0
0
1 = =
( )
( )
F F
X
y
F F
T A
D e
T A
=
= 2
15
1
3
0 0 0
.
,
,
CHG3127: Reaction Engineering E.J. Anthony 2012 55
Reversible Elementary
Reactions
Consider the reaction
assume rate constants written in terms of
benzene
rate of disappearance of benzene by forward
reaction:
rate of appearance due to reverse reaction:
2
6 6 12 10 2
1 2
C H C H H
k k ,
+
= r k C
B forward B , 1
2
r k C C
B reverse D H ,
=
2
CHG 3127: Reaction Engineering E.J. Anthony 2012 56
Reversible Elementary
Reactions
net rate of formation of benzene given by
net rate of consumption of benzene then
equilibrium constant :
r r r r
r k C k C C
B B net B forward B reverse
B B D H
= +
= +
, , ,
1
2
2


.

\

= =
H D B H D B B
C C
k
k
C k C C k C k r
1
2
2
1 2
2
1
K
k
k
c
=
1
2
CHG 3127: Reaction Engineering E.J. Anthony 2012 57
Summarizing So Far...
Basic definitions:
chemical species, and reaction; types of reactions
(e.g., decomposition, combination, etc.); reaction rate;
elementary and nonelementary reactions; molecularity
and reaction order; Arrhenius law
Characterizing industrial Reactors:
by operation
batch, continuous, and semibatch
by design
tank , tubular, tower, fluidized bed, slurry
CHG 3127: Reaction Engineering E.J. Anthony 2012 58
Summarizing So Far...
generalized stoichiometric equation, extent of
reaction, and fractional conversion
generalized mole balance equation
wellmixed
not wellmixed
CHG 3127: Reaction Engineering E.J. Anthony 2012 59
Summarizing So Far...
relationships between reaction rates
stoichiometric tables for batch systems
tables for continuous (flow) systems
definitions for and
defining inlet moles (molar flow rates) in
terms of limiting reactant
constant and variable volume processes
c
o
CHG 3127: Reaction Engineering E.J. Anthony 2012 60
Summarizing So Far...
Use stoichiometric table to analyze phase
change
Calculate critical mole fraction from vapour
pressure and operating pressure
Add column for after condensation
Use two expressions for total moles (or proper
ratio of molar flows) to determine critical X
Expressions for reversible, elementary
reactions
Acknowledgement
Slides taken and modified from David
Taylor
CHG 3127: Reaction Engineering E.J. Anthony 2012 61