CHME 314 Lecture 08 Rate Laws and Stoichiometry 3

Previous Lecture
Reaction rate
Stoichiometry table for batch system

Todays Lecture
Review stoichiometry for batch system
Example on batch system stoichiometry
Stoichiometry for flow system
Examples on stoichiometry
Stoichiometric table (Batch system)
Stoichiometric relationships between reacting molecules
for a single reaction.
aA bB cC d D
t=t
NA N A N A 0 N A0 X
NB
t=0 b
N B N B 0 N A0 X
a
NA0 NC
c
NB0 Batch reactor N C N C 0 N A0 X
NC0 ND a
ND0
NI0 NI N N d N X
D D0 A0
a
b c d NI NI 0
A B C D
a a a
Initia Remaining Concentration*
Specie Change
l mole (volume change or
s mole
mole not)
A NA0 N A0 X N A N A 0 N A0 X C A0 (1 X )
b
N A0 X
b
N B N B 0 N A0 X b
B NB0 C A0 B X
a a a
c
N A0 X
c
N C N C 0 N A0 X c
C NC0 C A0 C X
a a a
d
N A0 X
d
N D N D 0 N A0 X d
D ND0 C A0 D X
a a a
I NI0 -- NI NI 0 CI 0
d c b *constant volume
Total NT0 NT NT 0 1 N A0 X
a a a here
d c b N i 0 Ci 0 yi 0
1 NT NT 0 N A0 X i
a a a N A0 C A0 y A0
The change in the total number of moles per mole of A reacted.
Example 3-2: Soap consists of the sodium and potassium salts of
various fatty acids such as oleic, stearic, palmitic, lauric, and
myristic acids. The liquid phase saponification process for the
formation of soap from aqueous caustic soda and glyceryl stearate
is
Letting X represent the conversion of sodium hydroxide, set up a
stoichiometric table expressing the concentration of each species in
terms of its initial concentration and the conversion X.
liquid phase reaction:
Example 3-3: Having set up the stoichiometric table in Example 3-2,
one can now readily use it to calculate the concentrations at a given
conversion. If the initial mixture consists solely of sodium hydroxide
at a concentration of 10 mol/dm3 (i.e., 10 mol/L or 10 kmol/m3) and
of glyceryl stearate at a concentration of 2 mol/dm3, what is the
concentration of glycerine when the conversion of sodium
hydroxide is (a) 20% and (b) 90% ?
Only the reactants NaOH and (C17H35COO)3C3H5 are initially present:
C=D=0.
X = 20%
X = 90%
Stoichiometric table (flow system)
aA bB cC d D
entering Leaving
FA
FA0
FB
FB0
FC
FC0
FD
FD0
Continuous-flow reactor FI
FI0
Feeding rate Change Effluent rate
Species
mole/t mole/t mole/t
A FA0 FA0 X FA FA0 (1 X )
b b
B FB0=BFA0 FA0 X FB FA0 B X
a a
c c
C FC0=CFA0 FA0 X FC FA0 C X
a a
d d
D FD0=DFA0 FA0 X FD FA0 D X
a a
I FI0=IFA0 -- FI FA0 I
d c b
Total FT0 FT FT 0 1 FA0 X
a a a
Fi 0 Ci 0v0 Ci 0 yi 0 FT FT 0 FA0 X
i
FA0 C A0v0 C A0 y A0
Stoichiometric Table for Flow Reactors
Reaction: b c d
A B C D
a a a
Species Feed Flow Rate Change within Effluent Rate from

(mol/s) Reactor Reactor
(mol/s) (mol/s)
A F AO - ( F AO X ) F A F AO (1 X )
B FBO B F AO b b
- ( FAO X ) FB FAO ( B X)
a a
C FCO C F AO c c
( F AO X ) FC FAO ( c X)
a a
FDO D F AO d d
D ( FAO X ) FD FAO ( D X )
a a
FIO I F AO FI FIO
I -
FTO FT FTO FAO X
Total
I hope you see the similarity between flow and batch reactor
stoichiometric tables
Speci Feeding rate Change Effluent rate
es mole/t mole/t mole/t
A FA0 FA0 X FA FA0 (1 X )
b
FA0 X b
B FB0=BFA0 FB FA0 B X
a a
c c
C FC0=CFA0 FA0 X FC FA0 C X
a a
d d
D FD0=DFA0 FA0 X FD FA0 D X
a a
I FI0=IFA0 -- FI FA0 I
d c b
Total FT0 FT FT 0 1 FA0 X
a a a
Why stoichiometric tables?! FT FT 0 FA0 X
F C rA f (X )
Variable volume - Batch
Equation of state
PV ZNT RT
t=0
P0 T Z NT
P0V0 Z 0 NT 0 RT0 V V0
P T0 Z 0 NT 0
from stoichiometry table NT NT 0 N A0 X
NT N A0
1 X 1 y A0X 1 X
NT 0 NT 0
1
y A0
P0 T Z
V V0 1 X
P T0 Z 0
Variable volumetric flow rate
FT P
entering CT 1
v ZRT
FT 0 P0 FT P0 T Z
CT 0 v v0
v0 Z 0 RT0 FT 0 P T0 Z 0
From stoichiometry FT FT 0 FA0X
table
P0 T
v v0 1 y A0X
P T0
C A0 ( j v j X ) P T0
Cj
y A0 1 X P0 T
Stoichiometric P0 T
coefficient v v0 1 X FA0 ( j v j X )
P T0 Cj
Fj P0 T
v0 1 X
For
Cj
species j v Fj Fj 0 v j ( FA0 X ) FA0 ( j v j X ) P T0
Figure 3-6
Example 3-5: A mixture of 28% SO2 and 72% air is charged to a flow
reactor in which SO2 is oxidized:
First, set up a stoichiometric table using only the symbols (i.e., i, Fi)
and then prepare a second stoichiometric table evaluating numerically
as many symbols as possible for the case when the total pressure is
1485 kPa (14.7 atm) and the temperature is constant at 227 C.
Taking SO2 as the basis of calculation:
Change
concentration!!
If the rate law for this reaction were first order in SO2 (i.e., A) and
in O2 (i.e., B) with k=200 dm3/mol.s:
Example 3-6: The reversible gas-phase decomposition of nitrogen
tetroxide, N2O4, to nitrogen dioxide, NO2, is to be carried out at
constant temperature. The feed consists of pure N2O4 at 340 K and
202.6 kPa (2 tam). The concentration equilibrium constant, Kc, at
340 K is 0.1 mol/dm3.
A 2B
concentration equilibrium constant: at equilibrium !!

(a) Calculate the equilibrium conversion of N2O4 in a constant-volume batch
reactor.
at equilibrium !!
(b) Calculate the equilibrium conversion of N2O4 in a flow reactor.
at equilibrium !!
(c) Assuming the reaction is elementary, express the rate of reaction solely as a
function of conversion for a flow system and for a batch system.
Elementary reaction:
A 2B
for flow system
for batch system
(d) Determine the CSTR volume necessary to achieve 80% of the equilibrium
conversion.
CSTR design
equation

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Previous Lecture

Stoichiometry table for batch system

A FA0 FA0 X FA FA0 (1 X )

Species Feed Flow Rate Change within Effluent Rate from

from stoichiometry table NT NT 0 N A0 X

concentration equilibrium constant: at equilibrium !!

for flow system

for batch system

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