Quick Business Items

• Quiz #1 complete
• Next quiz is Week 5
– Cover kinetics Weeks 3-5
– Timeline: 6 PM, July 2nd – 11:55 PM, July 5th
Steady State Approximation
• Steady state approximation assumes that
ka after an induction period where
intermediates are formed, the subsequent
A + B ⎯⎯→

I ⎯⎯→
kb
P concentration of intermediate is unchanged
k a – Rate of intermediate formation and consumption
is zero
– Used for any and all intermediate formation in a
mechanism
– The assumption of the pre-equilibrium case
does not hold
• Namely kb is not much smaller than the
reverse reaction

d I 
0 = k a AB  − k a I  − kb I 
dt
I   ka AB  = d P = k I 
k a + kb b
dt
d P  k a kb AB 

dt k a + kb
d P  k a kb
 k app AB  k app =
dt k a + kb
Competing Reactions
Thermodynamic or Kinetic Control

B (kinetic product)
• Now, consider the same
A reactions, but both are
reversible
C (thermodynamic product) • As we increase T we
increase k for BOTH
reactions
– But, the larger Ea is the
greater the temperature
dependence
– So k changes more for
the thermodynamic
reaction
Gkinetic
• Higher T and longer
Gthermo reaction times drive the
reaction to the
thermodynamic product
Langmuir Isotherms
• Consider:
– A (g) + M (surface) ↔ AM For X2 (g) + ↔ 2X (Surface)
(surface) (Gas dissociation)
– ka for adsorption, kd for
desorption 𝑑𝜃 2
= 𝑘𝑎 𝑝 𝑁 1 − 𝜃 𝐾𝑝
𝑑𝑡
𝜃=
• Then: 𝑑𝜃 1 + 𝐾𝑝
= −𝑘𝑑 𝑁𝜃 2
𝑑𝜃 𝑑𝜃 𝑑𝑡
= 𝑘𝑎 𝑝𝑁 1 − 𝜃 = −𝑘𝑑 𝑁𝜃
𝑑𝑡 𝑑𝑡
• where N → # of sites

• @ equilibrium (equal
absorption & desorption):

𝐾𝑝 𝑘𝑎
𝜃= 𝐾=
1 + 𝐾𝑝 𝑘𝑑
Langmuir Isothermal
Heterogenous Catalysis Mechanisms
• Langmuir-Hinshelwood
Mechanism • Eley-Rideal Mechanism
– Reactions between adsorbed A & B – Reactions between already adsorbed A &
take place on a catalytic surface inbound B
– A+B→P – A+B→P

– 𝑟𝑎𝑡𝑒 = 𝑘𝜃𝐴 𝜃𝐵 – 𝑟𝑎𝑡𝑒 = 𝑘𝜃𝐴 𝑝𝐵

𝑘𝐾𝐴 𝑝𝐴 𝑝𝐵
– L-H Mechanism assumes Langmuir – 𝑟𝑎𝑡𝑒 = , if Langmuir behaviour is
1+𝐾𝑝𝐴
behaviour. If gasses don’t dissociate maintained and no dissociation
𝐾𝐴 𝑝𝐴 𝐾𝐵 𝑝𝐵
– 𝜃𝐴 = 𝜃𝐵 = 𝐾𝐴 𝑝𝐴
1+𝐾𝐴 𝑝𝐴 +𝐾𝐵 𝑝𝐵 1+𝐾𝐴 𝑝𝐴 +𝐾𝐵 𝑝𝐵 – 𝑟𝑎𝑡𝑒 = 𝑘𝑝𝐵 , if Langmuir behaviour
1+ 𝐾𝐴 𝑝𝐴
𝑘𝐾𝐴 𝐾𝐵 𝑝𝐴 𝑝𝐵
– 𝑟𝑎𝑡𝑒 = and dissociation occurs
1+𝐾𝐴 𝑝𝐴 +𝐾𝐵 𝑝𝐵 2
– Example: CO oxidation to CO2 – Example: Most (if not all) hydrogenation
(removal of carbon monoxide) reactions are E-R-”like”

Dissociated H2 provides
structural change on
catalyst to geometrically
enable reaction