SOAL

The dehydrogenation of methylcyclohexane (M) to produce toluene (T) was

carried out over a 0.3% Pt/Al2O3 catalyst in a differential catalytic reactor.
The reaction is carried out in the presence of hydrogen (H2) to avoid coking.
a) Determine the model parameters for each of the following rate laws
𝛼 𝛽
1 − 𝑟 ′ 𝑀 = 𝑘𝑃𝑀 𝑃𝐻2
′
𝑘𝑃𝑀
2 −𝑟 𝑀 =
1 + 𝐾𝑀 𝑃𝑀
′
𝑘𝑃𝑀 𝑃𝐻2
3 −𝑟 𝑀 =
(1 + 𝐾𝑀 𝑃𝑀 )2
′
𝑘𝑃𝑀 𝑃𝐻2
4 −𝑟 𝑀 =
1 + 𝐾𝑀 𝑃𝑀 + 𝐾𝐻2 𝑃𝐻2
SOAL(2)
• Use the data in Table P10-15.
b) Which rate law best describes the data?
c) Where would you place additional data
points?
A(1)
• Determine the model parameters for each of the following rate laws:

𝛼 𝛽
1 − 𝑟′ 𝑀 = 𝑘𝑃𝑀 𝑃𝐻2
JAWABAN A(1)
Pada reaksi (1) reaksi yang terjadi merupakan reaksi elementer.
Elementary reaction: a chemical reaction in which one or more of
the chemical species react directly to form products in a single reaction
step and with a single transition state.

A  Products Unimolecular reaction

A  B  Products Bimolecular reaction

 𝑀 → 𝑇 + 3𝐻2
• Adsorpsi : M + S → M. S
• Reaksi Permukaan : M. S + H2 → T. S + H2
• Desorpsi : T. S → T + S

Berdasarkan persamaan diatas, laju reaksi dapat diekspresikan dengan

𝛽
−𝑟 = 𝑘 𝐶𝑀 𝛼 𝐶𝐻2
Atau 𝛽
−𝑟 = 𝑘 𝑃𝑀 𝛼 𝑃𝐻2
Dimana,
𝛼=1
𝛽=3
A(2)
• Determine the model parameters for each of the following rate laws:

𝑘𝑃𝑀
2 − 𝑟′ 𝑀 =
1 + 𝐾𝑀 𝑃𝑀
MEKANISME REAKSI
Asumsi:
1. -Single Site
2. -TPL: Reaksi Permukaan
3. -H2 sekitar tidak mempengaruhi reaksi permukaan.

• Adsorption
M+S→M∙S
• Surface Reaction
M ∙ S → T ∙ S + H2 (g)
• Desorption
T∙S→T+S
Reaksi Permukaan Single-Site

𝑀 ∙ 𝑆 → 𝑇 ∙ 𝑆 + 𝐻2 (𝑔)

𝐶𝑇∙𝑆 𝑃𝐻2
−𝑟 = 𝑘𝑠 𝐶𝑀.𝑆 −
𝐾𝑠
Absorpsi
𝑀+𝑆 →𝑀∙𝑆

𝐶𝑀∙𝑆
−𝑟 = 𝑘𝑀 𝑃𝑀 𝐶𝑉 −
𝐾𝑀

Karena reaksi permukaan adalah limiting rate, sehingga nilai kM>>r

𝑟
− ≈0
𝑘𝑀
Sehingga diperoleh:

𝐶𝑀∙𝑆 = 𝑃𝑀 𝐶𝑉 𝐾𝑀
Desorpsi
𝑀+𝑆 →𝑀∙𝑆

𝐶𝑀∙𝑆
−𝑟 = 𝑘𝑀 𝑃𝑀 𝐶𝑉 −
𝐾𝑀

Karena reaksi permukaan adalah limiting rate, sehingga nilai kM>>r

𝑟
− ≈0
𝑘𝑀
Sehingga diperoleh:
𝑃𝑇 𝐶𝑉
𝐶𝑇∙𝑆 =
𝐾𝑇
Total Site
Total Site (CT) = vacant site + occupied site
𝐶𝑇 = 𝐶𝑉 +𝐶𝑀∙𝑆 +𝐶𝑇∙𝑆

𝑃𝑇 𝐶𝑉
𝐶𝑇 = 𝐶𝑉 + 𝑃𝑀 𝐶𝑉 𝐾𝑀 +
𝐾𝑇

𝑃𝑇
𝐶𝑇 = 1 + 𝑃𝑀 𝐾𝑀 + 𝐶
𝐾𝑇 𝑉

Diperoleh:

𝐶𝑇
𝐶𝑉 =
𝑃
1 + 𝑃𝑀 𝐾𝑀 + 𝐾𝑇
𝑇
Laju Dekomposisi Cumen
𝐶𝑇∙𝑆 𝑃𝐻2
−𝑟 = 𝑘𝑠 𝐶𝑀∙𝑆 −
𝐾𝑆
𝑃𝑇 𝐶𝑉
𝐾𝑇 𝑃𝐻2
−𝑟 = 𝑘𝑠 𝑃𝑀 𝐶𝑉 𝐾𝑀 −
𝐾𝑆
𝑃𝑇
𝐾𝑇 𝑃𝐻2
−𝑟 = 𝑘𝑠 𝑃𝑀 𝐾𝑀 − 𝐶𝑣
𝐾𝑆
𝑃𝑇
𝐾𝑇 𝑃𝐻2 𝐶𝑇
−𝑟 = 𝑘𝑠 𝑃𝑀 𝐾𝑀 − .
𝐾𝑆 𝑃
1 + 𝑃𝑀 𝐾𝑀 + 𝐾𝑇
𝑇

Menggunakan metode initial rate, nilai P belum terbentuk diawal reaksi jadi nilai PT= 0
• Diperoleh laju dekomposisi Cumen:

𝒌𝑷𝑴
−𝒓𝒎 = ; 𝑘 = 𝐾𝑀 𝐶𝑇 𝑘𝑠
𝟏 + 𝑲𝑴 𝑷𝑴