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Solid State Kinetics

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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276 views13 pages

Solid State Kinetics

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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Hudi Nurwendi
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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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