REEN 3001

Solution to HomeWork (week of 27 Jan)

EXERCISE 1

1-Butyl alcohol (TBA) is an important octane enhancer that is used to replace lead additives in
gasoline [Ind. Eng. Chem. Res., 27. 2224 (1988)]. t-Bu alcohol was produced by the liquid-phase
hydration (W) of isobutene (I) and an Amberlyst- 15 catalyst. The system is normally a
multiphase mixture of hydrocarbon, water and solid catalysts. However, the use of co solvents
and excess TBA can achieve reasonable miscibility.

The reaction mechanism is believed to be:

I+S ↔ I.S

W + S ↔ W.S

W.S + I. S → TBA.S + S

TBA.S ↔ TBA + S

Part I:

Derive a rate law assuming:

The surface reaction is rate-limiting.

Generic Rate Laws

Absorption of I
𝐶𝐼·𝑆
𝑟𝐴𝐷𝐼 = 𝑘𝐴𝐼 (𝐶𝐼 𝐶𝑉 − )
𝐾𝐼

Absorption of W
𝐶𝑊·𝑆
𝑟𝐴𝐷𝑊 = 𝑘𝐴𝑊 (𝐶𝑊 𝐶𝑉 − )
𝐾𝑊

Surface Reaction
𝐶𝑉 𝐶𝑇𝐵𝐴·𝑆
𝑟𝑆 = 𝑘𝑆 (𝐶𝑊·𝑆 𝐶𝐼·𝑆 − )
𝐾𝑆

Desorption Reaction

𝐶𝑉 𝐶𝑇𝐵𝐴
𝑟𝐷 = 𝑘𝐷 (𝐶𝑇𝐵𝐴·𝑆 − )
𝐾𝐷
𝑟𝐴𝐷𝐼
=0
𝑘𝐴𝐼

𝐶𝐼·𝑆
𝑟𝐴𝐷𝐼 = 𝑘𝐴𝐼 (𝐶𝐼 𝐶𝑉 − )
𝐾𝐼
𝑟𝐴𝐷𝐼 𝐶𝐼·𝑆
= 𝐶𝐼 𝐶𝑉 =
𝑘𝐴𝐼 𝐾𝐼

𝐶𝐼·𝑆
0 = 𝐶𝐼 𝐶𝑉 = 𝐾𝐼
𝐶𝐼·𝑆
= 𝐶𝐼 𝐶𝑉
𝐾𝐼

𝐶𝐼·𝑆 = 𝐾𝐼 𝐶𝐼 𝐶𝑉

For W adsorption
𝑟𝐴𝐷𝑊
=0
𝑘𝐴𝑊

𝐶𝑊·𝑆
𝑟𝐴𝐷𝑊 = 𝑘𝐴𝑊 (𝐶𝑊 𝐶𝑉 − )
𝐾𝑊
𝑟𝐴𝐷𝑊 𝐶𝑊·𝑆
= 𝐶𝑊 𝐶𝑉 −
𝑘𝐴𝑊 𝐾𝑊

𝐶𝑊·𝑆
0 = 𝐶𝑊 𝐶𝑉 − 𝐾𝑊
𝐶𝑊·𝑆
= 𝐶𝑊 𝐶𝑉
𝐾𝑊

𝐶𝑊·𝑆 = 𝐾𝑊 𝐶𝑊 𝐶𝑉
Desorption
𝑟𝐷
=0
𝑘𝐷
𝐶𝑇𝐵𝐴 𝐶𝑉
0 = 𝐶𝑇𝐵𝐴·𝑆 − 𝐾𝐷
𝐶𝑇𝐵𝐴 𝐶𝑉
= 𝐶𝑇𝐵𝐴·𝑆
𝐾𝐷

Since desorption is reverse of adsorption, KD (desorption constant) is the reciprocal of

adsorption constant for TBA (KTBA).
1
= 𝐾𝑇𝐵𝐴
𝐾𝐷
𝐶𝑇𝐵𝐴 𝐶𝑉
Therefore if 𝐶𝑇𝐵𝐴·𝑆 = 𝐾𝐷

Then 𝐶𝑇𝐵𝐴·𝑆 = 𝐶𝑇𝐵𝐴 𝐶𝑉 𝐾𝑇𝐵𝐴

Now, must eliminate Cv
𝐶𝑇 = 𝐶𝑉 + 𝐶𝐼·𝑆 + 𝐶𝑊·𝑆 + 𝐶𝑇𝐵𝐴·𝑆
 = 𝐶𝑉 + (𝐾𝐼 𝐶𝐼 𝐶𝑉 ) + (𝐾𝑊 𝐶𝑊 𝐶𝑉 ) + (𝐾𝑇𝐵𝐴 𝐶𝑇𝐵𝐴 𝐶𝑉 )
= 𝐶𝑉 (1 + 𝐾𝐼 𝐶𝐼 + 𝐾𝑊 𝐶𝑊 + 𝐾𝑇𝐵𝐴 𝐶𝑇𝐵𝐴 )
𝐶𝑇
𝐶𝑉 = 1+ 𝐾 𝐶 + 𝐾
𝐼 𝐼 𝑊 𝐶𝑊 +𝐾𝑇𝐵𝐴 𝐶𝑇𝐵𝐴

𝐾𝑇𝐵𝐴 𝐶𝑇𝐵𝐴
𝑟𝑆 = 𝐶𝑉2 [𝑘𝑆 (𝐾𝑊 𝐶𝑊 )(𝐾𝐼 𝐶𝐼 ) − ]
𝐾𝑆

𝐾 𝐶
𝐶𝑇2 𝑘𝑆 𝐾𝑊 𝐶𝑊 𝐾𝐼 𝐶𝐼 − ( 𝑇𝐵𝐴 𝑇𝐵𝐴 )
𝐾𝑆
𝑟𝑆 = (1+ 𝐾 𝐶 + 𝐾 2
𝐼 𝐼 𝑊 𝐶𝑊 +𝐾𝑇𝐵𝐴 𝐶𝑇𝐵𝐴 )

Part II:

Derive a rate law assuming:

The reaction follows Eley-Rideal kinetics.

I + S ← → I·S
I·S + W ← → TBA·S
TBA·S ← → TBA + S
𝐶𝐼·𝑆
𝑟𝐴𝐷𝐼 = 𝑘𝐴𝐼 (𝐶𝐼 𝐶𝑉 − )
𝐾𝐼
𝐶𝑇𝐵𝐴·𝑆
𝑟𝐸𝑅 = 𝑘𝐸𝑅 (𝐶𝐼·𝑆 𝐶𝑊 − )
𝐾𝐸𝑅
𝐶𝑉 𝐶𝑇𝐵𝐴
𝑟𝐷 = 𝑘𝐷 (𝐶𝑇𝐵𝐴·𝑆 − )
𝐾𝐷

𝐶𝐼·𝑆 = 𝐾𝐼 𝐶𝐼 𝐶𝑉
𝐶𝑇𝐵𝐴·𝑆 = 𝐾𝑇𝐵𝐴 𝐶𝑇𝐵𝐴 𝐶𝑉
Therefore
𝐾𝑇𝐵𝐴 𝐶𝑇𝐵𝐴 𝐶𝑉
𝑟𝐸𝑅 = 𝑘𝐸𝑅 (𝐾𝐼 𝐶𝐼 𝐶𝑉 )𝐶𝑊 − 𝐾𝐸𝑅
𝐾𝑇𝐵𝐴 𝐶𝑇𝐵𝐴
𝑟𝐸𝑅 = 𝐶𝑉 [𝑘𝐸𝑅 𝐾𝐼 𝐶𝐼 𝐶𝑉 − ]
𝐾𝐸𝑅

Solve for Cv
𝐶𝑇 = 𝐶𝑉 + 𝐶𝐼·𝑆 + 𝐶𝑊·𝑆 + 𝐶𝑇𝐵𝐴·𝑆
𝐶𝑇 = 𝐶𝑉 + 𝐾𝐼 𝐶𝐼 𝐶𝑉 + 𝐾𝑇𝐵𝐴 𝐶𝑇𝐵𝐴 𝐶𝑉
 𝐶𝑇 = 𝐶𝑉 (1 + 𝐾𝐼 𝐶𝐼 + 𝐾𝑇𝐵𝐴 𝐶𝑇𝐵𝐴 )
𝐶𝑇
𝐶𝑉 = 1+𝐾𝐼 𝐶𝐼 + 𝐾𝑇𝐵𝐴 𝐶𝑇𝐵𝐴

Plug it in

𝐶𝑇 𝐾𝑇𝐵𝐴 𝐶𝑇𝐵𝐴
𝑟𝐸𝑅 = [𝑘𝐸𝑅 𝐾𝐼 𝐶𝐼 𝐶𝑉 − ]
1+𝐾𝐼 𝐶𝐼 + 𝐾𝑇𝐵𝐴 𝐶𝑇𝐵𝐴 𝐾𝐸𝑅

Part III:

Derive a rate law assuming:

Isobutene (I) and water (W) are adsorbed on different sites:

I + S1 ↔ I.S1

W + S2 ↔ W.S2

and TBA is not on the surface, and the surface reaction is rate-limiting.

W·S2 + I·S2 ↔ TBA + S2 + S1

𝐶𝑇𝐵𝐴 𝐶𝑉1 𝐶𝑉2
𝑟𝑆 = 𝑘𝑆 [𝐶𝑊.𝑆2 𝐶𝐼.𝑆1 − ]
𝐾𝑆

𝐶𝑇1 = 𝐶𝑉1 + 𝐶𝐼.𝑆1

𝐶𝑇2 = 𝐶𝑉2 + 𝐶𝑊.𝑆2

𝐶𝐼.𝑆1 = 𝐾𝐼 𝐶𝐼 𝐶𝑉1
𝐶𝑇1 = 𝐶𝑉1 (1 + 𝐾𝐼 𝐶𝐼 )

𝐶𝑊.𝑆2 = 𝐾𝑊 𝐶𝑊 𝐶𝑉2
𝐶𝑇2 = 𝐶𝑉2 (1 + 𝐾𝑊 𝐶𝑊 )

𝐶
𝑘𝑆 𝐾𝑊 𝐾𝐼 𝐶𝑇1 𝐶𝑇2 [𝐶𝐼 𝐶𝑊 − 𝑇𝐵𝐴]
𝐾𝑆
𝑟𝐼 = (1+ 𝐾𝐼 𝐶𝐼 )(1+ 𝐾𝑊 𝐶𝑊 )
 EXERCISE 2

The formation of proponal on a catalytic surface is believed to proceed by the following

mechanism.

O2 +2S ↔ 2O·S

C3H6 + O·S → C3H5OH·S

C3H6OH·S ↔ C3H5OH + S

Suggest a rate-limiting step and derive a rate law.

A2 + 2S ↔ 2A·S
B + A·S → C·S
C·S → C + S
Assumed surface reaction is the RLS:
2
𝐶𝐴.𝑆
𝑟𝐴𝐷 = 𝑘𝐴 [𝑃𝐴2 𝐶𝑉2 − ]
𝐾𝐴

𝑟𝑆 = 𝑘𝑆 𝑃𝐵 𝐶𝐴.𝑆
𝑟𝐷 = 𝑘𝐷 𝐶𝐶.𝑆
𝑟𝐴𝐷
=0
𝑘𝐴

𝐶𝐴.𝑆 = 𝐶𝑉 √𝐾𝐴 𝑃𝐴
𝐶𝑇 = 𝐶𝑉 + 𝐶𝐴.𝑆 + 𝐶𝐶.𝑆
To define CC.S, must treat it as reversible:
𝑃𝐶 𝐶𝑉
𝑟𝐷 = 𝑘𝐷 [𝐶𝐶.𝑆 − ]
𝐾𝐷

Considering desorption as the opposite of adsorption:

𝑃𝐶 𝐶𝑉
𝑟𝐷 = 𝑘𝐷 [𝐶𝐶.𝑆 − ] = 𝑘𝐷 [𝐶𝐶.𝑆 − 𝐾𝐶 𝑃𝐶 𝐶𝑉 ]
𝐾𝐷
𝑟𝐷
=0
𝑘𝐷

𝐶𝐶.𝑆 = 𝐾𝐶 𝑃𝐶 𝐶𝑉

𝐶𝑇 = 𝐶𝑉 + 𝐶𝐴.𝑆 + 𝐶𝐶.𝑆 = 𝐶𝑉 [1 + √𝐾𝐴 𝑃𝐴 + 𝐾𝐶 𝑃𝐶 ]

Plug everything in:
𝑘𝑆 𝐶𝑇 𝑃𝐵 √𝐾𝐴 𝑃𝐴
𝑟𝑆 = 1+√𝐾𝐴 𝑃𝐴 + 𝐾𝐶 𝑃𝐶