Professional Documents
Culture Documents
Lecture 4 - Rate Law and Stoichiometry
Lecture 4 - Rate Law and Stoichiometry
Elementary Reaction
Reversible Reaction
3 Rate laws and stoichiometry It is expected that students are able to:
Part 1: Part 1:
• Stoichiometric Table • Write rate law, define reaction order and
activation energy for elementary reactions
Part 2
• Expressing concentrations • Construct a stoichiometry table for batch
in terms other than and flow systems and express
conversions concentration as a function of conversion
Part 2
• Calculate the equilibrium conversion for gas
and liquid phase reactions
Equilibrium position
• Irreversible reaction
A B C D (one direction)
• Reversible reaction
A B C D (forward or backward)
Rate Law and Order of Reaction
rA k A C C
m
A
n
B
2NO O2
2NO2
rNO kNOC C O2
2
NO
Order of Reaction
Zero-order First-order
Second-order Third-order
rA k A T fnconcentration
k A(T) Ae E/RT
Slope = – E/R
ln kA
E 1
lnk A lnA
R T 1/T (K–)
Elementary Reaction
A reaction has an elementary rate law if the
stoichiometry coefficients are the same as the
individual reaction order of each species.
For the reaction
A 2B C D
A 2B C D rA kC 2A C B3
Non-Elementary (Example)
Free-radical mechanism
k1C H2 C 1/2
H2 Br2 2HBr rHBr
Br
k 2 C HBr /CBr 2
Vapor-phase decomposition
aA bB cC dD
k A C aA C Bb k A C Cc C Dd
Reversible Reactions (Cont.)
At equilibrium, rA, net = 0
Thus,
kA
k A C A C k A C C
a b
B
c
C
d
D
K equilibriu m
k A
C Ce
c
C De
d
K equlibrium Kc a b
Thermodynamic
C AeC Be equilibrium relationship
example
Note: Kc = (mol/dm3)d + c – b – a
Reversible Reactions
All rate law for reversible reactions must satisfy
thermodynamic relationship relating the reacting species
concentrations at equilibrium,
dX X dX
NA rA V t NA0
Batch
dt 0 rA V
FA0 X out X in
V
rA out
CSTR
dX X out dX
PFR FA0 rA V FA0
dV X in rA
dX X out dX
PBR FA0 rA' W FA0
dW
X in - rA'
• It was shown that the rate law can be expressed as a
function of concentration.
ex:
rA kC 2A C B3
• Now we need to express concentration as a function of
conversion in order to carry out calculations similar to
those presented in Chapter 2 to size reactors.
aA bB
cC dD
b c d
A B
C D
a a a
moles of A reacted
XA
moles of A fed
Relatives Rates of Reaction
rA rB rC rD
a b c d
b
NBreacted NA0 X
a
NB NB0 NA0
b
X NB NB0 b/aNA0 X
CB
a V V
NA0 Θ b/aX
V
Stoichiometry Table for Batch System
For every component in the reactor we can write after conversion X is achieved:
b b
B NB0 NA0 X NB NB0 NA0 X
a a
c c
C NC0 NA0 X NC NC0 NA0 X
a a
d d
D ND0 NA0 X ND ND0 NA0 X
a a
__ d c b
Totals NT0 NT NT 0 1NA0 X
a a a
Stoichiometry Table for Batch System
d c b
-1 δ
a a a
δ - the total molar increase per mole A reacted
NT NT0 δNA0 X
The total number of moles
Batch Reactor
Now, if we know the number of moles of every component we
can calculate concentration as function of conversion.
NA NA0 1 X
CA
V V
N N b/aNA0 X NA0 Θ b/aX
C B B B0
V V V
N N Θ c/aX
C C C A0
V V
N N Θ d/aX
C D D A0
V V
Batch System
Species Symbol Initial (mol) Change (mol) Remaining (mol)
b b
B B NB0 NA0ΘB NA0 X NB NA0 ΘB X
a a
c c
C C NC0 NA0 ΘC NA0 X NC NA0 ΘC X
a a
d d
D D ND0 NA0 ΘD NA0 X ND NA0 ΘD X
a a
Ni0 C y
Θi i0 i0
NA0 C A0 y A0
Constant volume-system, (V = Vo)
NA NA0 1 X
CA C A0 1 X
V V0
Entering Leaving
F A0 FA
FB0 b c d FB
A B
C D
FC0 a a a FC
FD0 FD
FI0 FI
Stoichiometry Table for Flow System
Feed rate to Change within Effluent rate from
Species
reactor (mol/time) reactor (mol/time) reactor (mol/time)
b b
B FB0 FA0 ΘB FA0 X FB FA0 ΘB X
a
a
c c
C FC0 FA0ΘC FA0 X FC FA0 ΘC X
a a
d d
D FD0 FA0 ΘD FA0 X FD FA0 ΘD X
a a
FAmoles/time
CA
liter/time
FA b
CA C A0 1 X C B C A0 Θ X
a