Lecture 12

𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡
Ex. 1. 2𝐶𝑂 + 𝑂2 → 2𝐶𝑂2 (non-elementary! All catalytic reactions are
non-elementary.)

Propose a L-H_type reaction mechanism

Elementary steps:

(1) 𝐶𝑂 + 𝑋 ⇌ 𝐶𝑂𝑋 (molecules just sit on the surface; physical adsorption)

𝑂2 + 2𝑋 ⇌ 2𝑂𝑋 (chemisorption; 𝑂2 dissociates occupying two sites)

(𝑂2 + 𝑋 ⇌ 𝑂2 . 𝑋) ← it can also happen, which is physisorption)

𝑂𝑋 + 𝐶𝑂𝑋 ⇌ 𝐶𝑂2 𝑋 + 𝑋 (surface re-arrangement but ‘𝑋’ is conserved)

𝐶𝑂2 𝑋 ⇌ 𝐶𝑂2 + 𝑋 (desorption)

1 ′𝑋′
𝐶𝑂 + 𝑂2 → 𝐶𝑂2 (overall reaction)
2

How? by multiplying the 2nd step by ′ 1⁄2 ′ and adding to eliminate all
1
intermediates; stoichiometry/mass balance must hold good : (𝑂2 + 2𝑋 ⇌ 2𝑂𝑋)
2

(2) Assume that surface-re-arrangement/reaction controls, implying that the

other steps are at equilibrium (𝑟 = 0)

𝑟 = 𝑘3 (𝐶𝑂𝑋)(𝑂𝑋) − 𝑘−3 (𝐶𝑂2 𝑋)(𝑋)

≈ 𝑘3 (𝐶𝑂𝑋)(𝑂𝑋) (The reaction under consideration clearly indicates an

approximately irreversible reaction/situation)

(𝐶𝑂𝑋) (𝑂𝑋)2 (𝐶𝑂 𝑋)

(3) 𝐾1 = (𝐶𝑂)(𝑋) ; 𝐾2 = (𝑂 )(𝑋)2
; 𝐾4 = (𝐶𝑂 2)(𝑋)
2 2
𝑘3
(Note 𝐾3 𝑖𝑠 also defined as , because the step describes an elementary
𝑘−3
reaction, even if the step is assumed to be irreversible with a non-zero rate.)

1
 (4) (𝑋)𝑜 = (𝑋) + (𝐶𝑂𝑋) + (𝑂𝑋) + (𝐶𝑂2 𝑋) (sites are either free or occupied)
1
𝑋𝑜 2 𝑘3 𝐾1 √𝐾2 (𝑂2 )2 (𝐶𝑂)
𝑟= 1 2
[1+√𝐾2 (𝑂2 )2 +𝐾1 (𝐶𝑂)+𝐾4 (𝐶𝑂2 )]

Special Cases:
(1) 𝑂2 is in excess
(2) weak 𝐶𝑂2 adsorption (𝐾4 is a small quantity; [𝐶𝑂2 𝑋] is small)

𝛼𝐶𝑂
𝑟 = (𝛽
+ 𝐶𝑂)2
𝐶𝑂 1 1⁄√𝛼
√ = √ (𝛽 + 𝐶𝑂) √
𝐶𝑂
𝑟 𝛼
𝑟
𝛽⁄√𝛼
Data: 𝐶𝑂
𝑂2 𝐶𝑂 𝐶𝑂2 𝑟
   
   
Ex. 2. The following reaction between NO and CO is important in controlling the
emission of these air pollutants from IC engines:
𝑃𝑡⁄𝑅ℎ
2𝑁𝑂 + 2𝐶𝑂 → 𝐶𝑂2 + 𝑁2

- The reaction takes place on the Pt⁄Rh supported catalyst and follows the L-H
mechanism. NO, CO and CO2 adsorb on the catalyst non-dissociatively; N2 adsorbs
dissociatively.

- Derive the rate expression for the forward reaction

- What is the rate expression for the reverse reaction?
𝐶𝑂2 + 𝑁2 → 2𝑁𝑂 + 2𝐶𝑂

2
Ans: As per the L-H model, the surface re-arrangement or reaction rate is
controlling:

k1
NO + X ⇌ NOX
k −1
k2
CO + X ⇌ COX
k −2 [NOX] = K1 [NO][X]
ks [COX] = K 2 [CO][X]
NOX + COX ⇌ CO2 X + NX
k −s [CO2 X] = K 3 [CO2 ][X]
k3 [NX]2 = K 4 [N2 ][X]2
CO2 X ⇌ CO2 + X
k −3
k4
2NX ⇌ N2 + 2X
k −4 }

Site conservation equation:

1⁄ 1
[𝑋𝑜 ] = [𝑋] + 𝐾1 [𝑁𝑂][𝑋] + 𝐾2 [𝐶𝑂][𝑋] + 𝐾3 [𝐶𝑂2 ][𝑋] + 𝐾4 2 [𝑁 ] ⁄2 [𝑋]
2

[𝑋𝑜 ]
→ [𝑋] = 1 1
1+𝐾1 [𝑁𝑂]+𝐾2 [𝐶𝑂]+𝐾3 [𝐶𝑂2 ]+𝐾4 ⁄2 [𝑁2 ] ⁄2

Re-read the question “Determine the rate of the forward reaction: 2𝑁𝑂 + 2𝐶𝑂
→ 𝐶𝑂2 + 𝑁2 . The overall reaction is controlled by the surface arrangement step;
the other steps are at equilibrium and do not contribute to the rate of reaction.
Therefore,

𝑟𝑓𝑜𝑟𝑤𝑎𝑟𝑑 = 𝑘𝑠 [𝑁𝑂𝑋][𝐶𝑂𝑋] = 𝑘𝑠 𝐾2 𝐾1 [𝑁𝑂][𝐶𝑂][𝑋]2

𝐾1 𝐾2 𝑘𝑠 [𝑁𝑂][𝐶𝑂][𝑋𝑜 ]2
= 1 1 2
[1+𝐾1 [𝑁𝑂]+𝐾2 [𝐶𝑂]+𝐾3 [𝐶𝑂2 ]+𝐾4 ⁄2 [𝑁2 ] ⁄2 ]

1⁄ 1
𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑒 = 𝑘−𝑠 [𝐶𝑂2 𝑋][𝑁𝑋] = 𝑘−𝑠 𝐾3 𝐾4 2 [𝑁 ] ⁄2 [𝐶𝑂 ][𝑋]2
2 2
1 1
𝑘−𝑠 𝐾3 𝐾4 ⁄2 [𝑁2 ] ⁄2 [𝐶𝑂2 ][𝑋𝑜 ]2
= 1 1 2 (Note that the denominator has not
[1+𝐾1 [𝑁𝑂]+𝐾2 [𝐶𝑂]+𝐾3 [𝐶𝑂2 ]+𝐾4 ⁄2 [𝑁2 ] ⁄2 ]

changed)

3
What are the approximations you can make?

⇒ 𝐶𝑂2 adsorbs weakly: 𝐾3 ≪ 𝐾1 , 𝐾2 , 𝐾4

K1 K2 ks [NO][CO][Xo ]2
rforward = 1 1 2 (Similarly for rreverse )
[1+K1 [NO]+K2 [CO]+K4 ⁄2 [N2 ] ⁄2 ]

⇒ 𝑁2 adsorbs weakly? No. This may not be a good approximation.

⇒ 𝑁2 adsorbs physically without dissociation. This is a possibility. Therefore,

𝑘4
[𝑁 𝑋]
𝑁2 𝑋 ⇌ 𝑁2 + 𝑋 𝐾4 = [𝑁 2][𝑋]
2
𝑘−4

In this case, re-do the calculation for [𝑋𝑜 ] = ⋯ ⋯

[𝑋𝑜 ]
𝑠𝑢𝑏𝑠𝑡𝑖𝑡𝑢𝑒 𝑡𝑜 𝑔𝑒𝑡 [𝑋] =
1+⋯⋯

Thus, obtain a new rate expression for the reaction

⇒ Initial rates? These are often useful. Product concentrations (𝑁2 ), (𝐶𝑂2 ) ≪
(𝐶𝑂), (𝑂2 ). In such case, 𝑟𝑓𝑜𝑟𝑤𝑎𝑟𝑑 𝑜𝑟 𝑟𝑒𝑣𝑒𝑟𝑠𝑒 can be approximated by neglecting the
product terms in the denominator.

H.W. (F-B 2nd ed.): 2.1, 2.2(a), 2.3(a), 2.4, 2.7(a-b)