Catalytic Reaction:

Transport and Kinetics Mechanism

F Kurniawansyah
Institut Teknologi Sepuluh Nopember
Surabaya
Step in Heterogeneous Catalytic
Reaction
Kinetika, Transport : Reaksi Heterogen
Faktor Penting
A. Reaction and Diffusion in Pores
Reaksi dan Difusi
Reaksi – Difusi: Shell Balance
Reaksi – Difusi : Solusi Matematik
Effectiveness Factor
Thiele Modulus vs Effectiveness factor
Regim Reaksi : Pengaruh Ukuran
Partikel
Ernest Thiele 1895 - 1993
 B. Kinetics :
Adsorption – Reaction -Desorption
 Adsorption
• Gas A to the active site S
 Adsorption
• Non – dissociative

• Dissociative
 Adsorption: Non - Dissociative
• Reaction
 Adsorption: Non - Dissociative
• Net Rate of adsorption is defined as rate of
attachment vs rate of detachment
 Adsorption: Non - Dissociative
• Site Balance

• Substitute C-CO.S (r-ad = 0)

 Adsorption: Non - Dissociative
• Langmuir Isotherm
 Adsorption: Dissociative
• Reaction

• Net rate of adsorption:

 Adsorption: Dissociative
• At equilibrium, net rate = 0

• Site Balance:
 Adsorption: Dissociative
• After substitution

• and a bit of arrangement…..

 Adsorption: Dissociative
• Graph plot
 Surface Reaction
• Single-Site mechanism

• Rate equation
 Surface Reaction
• Dual site mechanism: interaction with
neighboring site

• Rate equation
 Surface Reaction
• Dual-site mechanism

• Rate equation
 Surface Reaction
• Dual-site mechanism: on different sites

• Rate equation
The aforementioned single
and dual site mechanisms:
 Surface Reaction
• Dual-site mechanism: a molecule is adsorbed
on another molecule

• Rate equation
 Desorption
• Product desorption to the gas phase

• Rate equation
 Rate – Limiting - Step
• Reaction:
 When adsorption is the limiting step
• Rate of surface reaction and desorption are
fast, ks and kd are large

• Site balance:
 When adsorption is the limiting step
• Rate equation

• Graph
(initial rate method)
 When surface reaction is
the limiting step
• Rate of adsorption and rate of desorption are
fast
 When surface reaction is limiting
• Rate equation

• Graph
 When desorption is the limiting step
• Surface reaction and Adsorption are fast
 When desorption is limiting
• Rate equation

• Graph
 Summary
• Basic mechanism in catalytic reaction:
transport and kinetic aspect)
• Adsorption, Surface Reaction, Desorption
• Overall rate is determined from the rate
limiting step hypothesis
• Revisit of Langmuir adsorption isotherm and
its development
 Irving Langmuir (1881 – 1957)
• Fields : Chemistry, Physics
• Alma-mater:
University of Columbia (BSc)
University of Gottingen (PhD)
- Nobel Laureate 1932 :
Surface Chemistry
- Contribution: surface chemistry,
light bulbs, triode, theory of atom, welding
 Quotes
“Science, almost from its beginnings, has been
truly international in character. National
prejudices disappear completely in the scientist's
search for truth”
(Irving Langmuir)
 Cyril Norman Hinshelwood
(1897-1967)
• Fields: Physical Chemistry
• Nobel Laureate: 1956
• Institutions:
University of Oxford
Imperial College London

Contribution:
molecular kinetics, antibiotics, chain reaction
 Hougen - Watson

Andreas Olaf Hougen (1893-1986) Kenneth M Watson (1921 - )

Professor of Chemical Engineering Professor of Physics
University of Wisconsin, Madison University of California at San Diego
 Quotes
“ We should not be ashamed to recognize truth and
assimilate it, from whatever quarter it may reach us,
even though it may come from earlier generations and
foreign people. For the seeker after truth there is
nothing of more value than truth itself, it never
cheapens or debases the seeker, but ennobles and
elevates him”
(Yaqub Ibn Ishaq Al – Kindi: 801 – 873)