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    CRE II Heterogeneous Catalysis L11: Prof. K.K.Pant Department of Chemical Engineering IIT Delhi

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    Mehul Varshney
    This document discusses the Langmuir adsorption isotherm model, which describes adsorption of gas molecules onto solid surfaces. The key assumptions of the Langmuir model are that the surface is homogeneous, with a fixed number of equivalent adsorption sites, and that adsorption occurs through a dynamic equilibrium between gas molecules and occupied sites. The document also outlines how the Langmuir isotherm can be used to develop kinetic rate expressions for surface catalyzed reactions.

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    CRE II Heterogeneous Catalysis L11: Prof. K.K.Pant Department of Chemical Engineering IIT Delhi

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    Mehul Varshney
    161 views17 pages
    This document discusses the Langmuir adsorption isotherm model, which describes adsorption of gas molecules onto solid surfaces. The key assumptions of the Langmuir model are that the surface is homogeneous, with a fixed number of equivalent adsorption sites, and that adsorption occurs through a dynamic equilibrium between gas molecules and occupied sites. The document also outlines how the Langmuir isotherm can be used to develop kinetic rate expressions for surface catalyzed reactions.

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    CRE II L 11

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    This document discusses the Langmuir adsorption isotherm model, which describes adsorption of gas molecules onto solid surfaces. The key assumptions of the Langmuir model are that the surface is homogeneous, with a fixed number of equivalent adsorption sites, and that adsorption occurs through a dynamic equilibrium between gas molecules and occupied sites. The document also outlines how the Langmuir isotherm can be used to develop kinetic rate expressions for surface catalyzed reactions.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    161 views17 pages

    CRE II Heterogeneous Catalysis L11: Prof. K.K.Pant Department of Chemical Engineering IIT Delhi

    Uploaded by

    Mehul Varshney
    This document discusses the Langmuir adsorption isotherm model, which describes adsorption of gas molecules onto solid surfaces. The key assumptions of the Langmuir model are that the surface is homogeneous, with a fixed number of equivalent adsorption sites, and that adsorption occurs through a dynamic equilibrium between gas molecules and occupied sites. The document also outlines how the Langmuir isotherm can be used to develop kinetic rate expressions for surface catalyzed reactions.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    of 17

    CRE II Heterogeneous Catalysis

    L 11
    Prof. K.K.Pant Department of Chemical Engineering IIT Delhi. [email protected]

    Langmuir Adsorption Isotherm


    Simple approach to quantitatively describe an adsorption process at the gas/solid interface

    N = N +N number of vacant sites V S


    Assumptions:

    Solids surface is homogeneous and contain a number of equivalent sites,each of which is occupied by a single adsorbate molecule.
    2

    A dynamic equilibrium exist between gas phase reactant and adsorbed species. No interactions between adsorbed species. Adsorbed species localised,Hads is independent of coverage ..

    Chemisorption rates:

    Adsorption data is reported in the form of isotherms


    Chemisorption may be considered as a reaction between a reactant molecule and an active site resulting in an adsorbed molecule A + A (or) A + S AS Turnover Frequency (N): defined as the number of molecules reacting per active site per second at the conditions of the experiment a measure for the activity of the catalyst
    4

    Langmuir Isotherm - Assumptions:

    Surface is uniformly active


    All sites are identical

    Amounts of adsorbed molecules will not interfere with further adsorption


    Uniform layer of adsorption Site balance:
    No. of vacant sites v v Fraction of vacant sites total sites t No. of occupied sites A A Fraction of sites occupied by A total sites t v A 1

    Alternately:
    Ct Molar conc. of activesites Cv Molar conc. of vacant sites C AS Molar conc. of sites by A
    Cv C AS Ct

    No. of active sites / unit mass Avogadro' s number No. of vacant sites / unit mass Avogadro' s number No. of sites by A / unit mass Avogadro' s number

    Though other isotherms account for non-uniform surfaces, they have primarily been developed for single adsorbing components. Thus, the extensions to interactions in multi-component systems is not yet possible, as with the Langmuir isotherm. Langmuir isotherms are only used for developing kinetic rate expressions.
    6

    Effect of increasing reactant concentration:

    Increasing the reactant concentration increases both the driving force and adsorption inhibition terms.

    rate

    CA

    Volcano shape results from a competition between kinetic driving force and adsorption inhibition terms.
    13

    15

    Remarks:
    For a given mechanism, the driving force is unique, irrespective of RDS.
    The product of equilibrium constant of all steps in the mechanism yield the overall eq. constant In the kinetic term, the rate constant of RDS will appear. If adsorption of A is not RDS, then KApA will appear in the adsorption term. If desorption of B is not rate limiting, then pB/KD will appear in the adsorption term.

    If SR is RDS, then the adsorption term will be raised to the power equal to the number of sites involved in the SR step.
    16

    Simplified rate laws: Over limited pressure range, the Langmuir isotherm = Kp/(1+Kp) can be replaced by an approximation = kpn

    In such cases the rate law assumes the form:


    r = k pAm pBn pCo Such rate laws may be reasonably accurate Example: CO + Cl2 COCl2 (Over charcoal)
    rCOCl2 kKCO K Cl 2 pCO pCl 2 (1 K Cl 2 pCl 2 K COCl 2 pCOCl 2 ) 2

    L-H approach

    1/ 2 rCOCl2 kpCO pCl 2

    Simplified equation
    17

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