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