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    Solid State Kinetics

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    Hudi Nurwendi
    Thermodynamics describes how favorable a reaction is, while kinetics describes how fast a reaction occurs. Solid state reactions involve the diffusion of reactants to reactive interfaces, adsorption and reaction at the interface, and diffusion of products away. Transport phenomena like diffusion are involved, and reaction kinetics do not follow homogeneous reaction models. Methods to measure extent of reaction include thermogravimetric analysis and differential thermal analysis. Kinetics models are based on assumptions about rate-limiting steps like nucleation, geometrical contraction, or diffusion. Parameters can be determined through isothermal or non-isothermal model fitting or model-free isoconversional methods.

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    Solid State Kinetics

    Uploaded by

    Hudi Nurwendi
    157 views13 pages
    Thermodynamics describes how favorable a reaction is, while kinetics describes how fast a reaction occurs. Solid state reactions involve the diffusion of reactants to reactive interfaces, adsorption and reaction at the interface, and diffusion of products away. Transport phenomena like diffusion are involved, and reaction kinetics do not follow homogeneous reaction models. Methods to measure extent of reaction include thermogravimetric analysis and differential thermal analysis. Kinetics models are based on assumptions about rate-limiting steps like nucleation, geometrical contraction, or diffusion. Parameters can be determined through isothermal or non-isothermal model fitting or model-free isoconversional methods.

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    Thermodynamics describes how favorable a reaction is, while kinetics describes how fast a reaction occurs. Solid state reactions involve the diffusion of reactants to reactive interfaces, adsorption and reaction at the interface, and diffusion of products away. Transport phenomena like diffusion are involved, and reaction kinetics do not follow homogeneous reaction models. Methods to measure extent of reaction include thermogravimetric analysis and differential thermal analysis. Kinetics models are based on assumptions about rate-limiting steps like nucleation, geometrical contraction, or diffusion. Parameters can be determined through isothermal or non-isothermal model fitting or model-free isoconversional methods.

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    © All Rights Reserved
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    157 views13 pages

    Solid State Kinetics

    Uploaded by

    Hudi Nurwendi
    Thermodynamics describes how favorable a reaction is, while kinetics describes how fast a reaction occurs. Solid state reactions involve the diffusion of reactants to reactive interfaces, adsorption and reaction at the interface, and diffusion of products away. Transport phenomena like diffusion are involved, and reaction kinetics do not follow homogeneous reaction models. Methods to measure extent of reaction include thermogravimetric analysis and differential thermal analysis. Kinetics models are based on assumptions about rate-limiting steps like nucleation, geometrical contraction, or diffusion. Parameters can be determined through isothermal or non-isothermal model fitting or model-free isoconversional methods.

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    SOLID STATE KINETICS

    Thermodynamics vs Kinetics
    • Thermodynamics: How favorable is a reaction? (ΔG <
    0)
    – Diamond  Graphite is favored at ambient pressure
    • Kinetics: How fast is a reaction?
    – Diamond  graphite is kinetically extremely slow, even
    not observable at room temperature
    Solids: The crystal lattice
    • “Immobility” of atoms in solids
    • General reaction steps of
    heterogeneous reactions:
    – Diffusion of reactant to reactive interface
    – Adsorption at interface (Desorption for
    decomposition)
    – Reaction on atomic scale at the interface
    – Nucleation of product and growth
    – Diffusion of products away from the
    reactive interface
    • Transport phenomena (diffusion, heat) involved
    • Reaction zone confined: average concentration of reactant is
    NOT applicable in solid state reactions  homogeneous
    reaction kinetics DO NOT apply
    Methods in solid state kinetics
    Measurement of the extent of
    reaction α (conversion) as a

    isothermal
    function of time and
    temperature under either
    isothermal or temperature-
    controlled conditions.

    (constant heating)
    Non isothermal
    Methods in solid state
    kinetics
    Several observables suitable (any
    experimental method probing product
    formation at sufficient accuracy and
    time resolution):
    - loss of mass (TGA)
    - Heat flow (DTA / DSC)
    - Change of dimension (dilatometer)
    - Time-resolved features (FTIR, XRD,
    Raman, etc)
    Calculation of α for TGA:
    Kinetics Evaluation
    • Formal kinetic (gas phase) for unimolecular
    elementary reaction (n=1):
    dC C
    r  kC  ln  kt
    dt C0
    • For solid state reactions:

    • Several models for solid state reactions exist.


    Kinetics MODELS
    The existing models are classified by the following assumptions:
    • Nucleation: Formation and growth of nuclei are considered to
    be rate-limiting. Nucleation rate is different from the growth
    rate and the model accounts for both
    • Geometrical contraction: The progress of the product layer
    from the surface to the inner crystal is considered to be rate-
    limiting. It is different for various crystal morphologies (cubic,
    cylindrical, spherical, …)
    • Diffusion: Diffusion of reactant or product is considered to be
    rate-limiting.
    • Reaction order: The rate law is based on considerations for
    homogeneous kinetics
    Kinetics MODELS

    General model:
    (Sestak and Berggren)
    Determination of Kinetics Parameter
    • Isothermal model-fitting method
     Determination of k by fitting
    the best model to
    experimental data at each
    temperature
    g ( )  kt
     Determine A and E using
    Arrhenius correlation
    E1

    k  Ae RT
    Determination of Kinetics
    Parameter
    • Isothermal model-free fitting
    method (iso-conversional method)

    If the value of action energies (E) at different


    temperatures remain constant, the reaction
    follows single step reaction.
    Determination of Kinetics
    Parameter
    • Non-isothermal case
    – Model fitting method
    – Model-free fitting method

    d d dt 1 d
     
    dT dt dT  dt

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