Scribd Logo
Upload

Welcome to Scribd!

  • 14 views

    CRE-II Lecture 3

    Uploaded by

    Rashmi
    This document discusses various models of adsorption and surface reactions on heterogeneous catalysts: 1) Adsorption is the first step in heterogeneous chemical reactions, where molecules attach to the surface of a catalyst. 2) The Langmuir model describes adsorption of gas molecules onto well-defined sites on a surface, assuming each site holds one molecule and molecules do not interact. 3) The Langmuir-Hinshelwood model describes bimolecular surface reactions, where two reactants adsorb on the surface before reacting together. 4) The Eley-Rideal model involves one gas reactant directly colliding with an adsorbed reactant without adsorbing itself

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd

    CRE-II Lecture 3

    Uploaded by

    Rashmi
    14 views15 pages
    This document discusses various models of adsorption and surface reactions on heterogeneous catalysts: 1) Adsorption is the first step in heterogeneous chemical reactions, where molecules attach to the surface of a catalyst. 2) The Langmuir model describes adsorption of gas molecules onto well-defined sites on a surface, assuming each site holds one molecule and molecules do not interact. 3) The Langmuir-Hinshelwood model describes bimolecular surface reactions, where two reactants adsorb on the surface before reacting together. 4) The Eley-Rideal model involves one gas reactant directly colliding with an adsorbed reactant without adsorbing itself

    Copyright

    © © All Rights Reserved

    Available Formats

    PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    This document discusses various models of adsorption and surface reactions on heterogeneous catalysts: 1) Adsorption is the first step in heterogeneous chemical reactions, where molecules attach to the surface of a catalyst. 2) The Langmuir model describes adsorption of gas molecules onto well-defined sites on a surface, assuming each site holds one molecule and molecules do not interact. 3) The Langmuir-Hinshelwood model describes bimolecular surface reactions, where two reactants adsorb on the surface before reacting together. 4) The Eley-Rideal model involves one gas reactant directly colliding with an adsorbed reactant without adsorbing itself

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    14 views15 pages

    CRE-II Lecture 3

    Uploaded by

    Rashmi
    This document discusses various models of adsorption and surface reactions on heterogeneous catalysts: 1) Adsorption is the first step in heterogeneous chemical reactions, where molecules attach to the surface of a catalyst. 2) The Langmuir model describes adsorption of gas molecules onto well-defined sites on a surface, assuming each site holds one molecule and molecules do not interact. 3) The Langmuir-Hinshelwood model describes bimolecular surface reactions, where two reactants adsorb on the surface before reacting together. 4) The Eley-Rideal model involves one gas reactant directly colliding with an adsorbed reactant without adsorbing itself

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    You are on page 1of 15

    Lecture 3

    CHO 203

    Chemical Reaction Engineering


    (CRE-II)
    Adsorption
    • Adsorption is the first step of a heterogeneous chemical reaction process

    • Chemical reactions catalysed by heterogeneous catalysts can be viewed as a


    sequence of three elementary steps: adsorption, desorption and surface reaction

    Reaction
    2

    3
    Adsorption Desorption
    Surface of Catalyst
    Adsorption-Desorption Models
    Langmuir Model

    Langmuir Hinshelwood Model

    Eley Rideal Model


    Langmuir Model
    Assumptions

     The solid surface needs definite no. of sites for the adsorption of gases

     Each site can adsorb only one molecule

     All sites are energetically equivalents

     The adsorption is independent on the neighboring adsorbed specie

     At equilibrium, the rate of adsorption is equal to rate of desorption

     At equilibrium and for constant temperature and pressure, there are nA


    moles adsorbed molecules on the surface

     The adsorption rate of a molecule A depends on the partial pressure pA


    and of the number of free sites at a constant temperature and the
    desorption rate on the number of occupied sites
    Langmuir Model (Unimolecular Reaction)

    rads = kapA ( 1-θA)


    A

    rdes = kdθA

    At equilibrium, rads = rdes


    𝒌𝒂𝒑𝑨
    θA=
    𝒌𝒅+𝒌𝒂𝒑𝑨

    Two Cases:
    𝑲𝑨𝒑𝑨
    θA= (i) If 𝑲𝑨𝒑𝑨≈ 0
    𝟏+𝑲𝑨𝒑𝑨
    (ii)If 𝑲𝑨𝒑𝑨>> 0
    Symmetric Dissociative Adsorption
    Consider the dissociation and adsorption of a molecule A2 on two sites *

    A2 (g) + 2*(s) ↔ 2A* (ads)


    Adsorption rate
    rads = ka pA (1-θA)2

    Desorption rate
    rdes = kd θ2A

    Langmuir equation of adsorption for dissociative molecules


    Adsorption of n-molecules
    When the adsorption and desorption of different molecules occur
    simultaneously, either reactants or products
    Agas 1-θA-θB-θR
    θA θB θR

    𝐾𝑖 𝑝𝑖
    𝜃𝑖 =
    1 + 𝐾𝑖 𝑝𝑖

    If A is dissociative:
    𝐾𝐴 𝑝𝐴
    𝜃𝐴 =
    1 + 𝐾𝐴 𝑝𝐴 + 𝐾𝐵 𝑝𝐵 + 𝐾𝑅 𝑝𝑅
    Langmuir Hinshelwood Model (Bimolecular Reaction)
    A (g)  A (ads)
    B (g)  B (ads)
    A (ads)  B (ads) 
    rds
    AB (ads) 
    fast
    AB (g)
    pA B
    pB AB Rate = k q A q B
    A
    QB
    QA

    kKA p A K B p B
    Rate 
    1  K A p A  K B pB 2
    Langmuir Hinshelwood Model (Bimolecular Reaction)

    kKA p A K B p B
    Rate 
    1  K A p A  K B pB 2

    Two cases:

    (i) When both starting materials are weakly adsorbed


    reff = k’ pA pB and k’ = k K A K B

    → Reaction is first order in both reactants and second overall

    (ii) When A is weakly and B is strongly adsorbed, then rate equation


    reduces to
    reff = k’’pA/pB and k’’ = k KA/K B
    → Reaction order is one with respect to A and minus with respect to B
    Langmuir Hinshelwood Model (Bimolecular Reaction)

    rate
    Rate limited by
    surface concentration of A Rate limited by
    surface concentration
    of B

    PA
    Q B >> Q A
    Q B << Q A
    Examples of L-H Mechanism

    (i) Oxidation of CO on Pt catalysts


    2CO + O2 → 2CO2
    CO (g) → CO (ads)
    O2 (g) → 2O (ads)
    CO (ads) + O (ads) → CO 2 (ads) → CO2(g)

    (ii) Methanol synthesis on ZnO catalysts


    CO + 2H2 → CH3OH

    (iii) Hydrogenation of ethylene on Cu catalysts


    C2H4 + H2 → C2H6
    Eley-Rideal

    Bimolecular Surface Reactions


    A
    AB
    B

    fast

    An adsorbed molecule may react directly with an impinging


    gas molecule by a collision mechanism
    Bimolecular Gas Phase Reaction

    Examples:

    (i) Reduction of CO2 with H2


    CO2,G +H2*→ H2O + CO

    (ii) Oxidation of ammonia on Pt catalysts


    2NH3+3/2 O2* → N2 + 3H2O
    BET Model (Brunauer, Emmet and Teller)
    Assumptions:

    • Heat of adsorption of first monolayer is constant


    • The lateral interaction of adsorbed molecules is negligible
    • The adsorbed molecules can act as new adsorption surface and the
    process can repeat itself
    • The heat of adsorption of all monolayers but the first is equal to
    the heat of condensation
    𝑷𝑨 𝟏 𝑪 − 𝟏 𝑷𝑨
    = +
    𝑽 𝑷𝟎 − 𝑷𝑨 𝑪𝑽𝒎 𝑪𝑽𝒎 𝑷𝟎
    Thank You

    You might also like

    pFad - Phonifier reborn

    Pfad - The Proxy pFad of © 2024 Garber Painting. All rights reserved.

    Note: This service is not intended for secure transactions such as banking, social media, email, or purchasing. Use at your own risk. We assume no liability whatsoever for broken pages.


    Alternative Proxies:

    Alternative Proxy

    pFad Proxy

    pFad v3 Proxy

    pFad v4 Proxy