A theoretical approach to the kinetics of calcite ⇌ aragonite transition: application to laboratory experiments

Details A theoretical approach to the kinetics of calcite ⇌ aragonite transition: application to laboratory experiments A theoretical approach to the kinetics of calcite ⇌ aragonite transition: application to laboratory experiments

Mar 1984

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1984e%26psl..67..400m&link_type=abstract

Earth and Planetary Science Letters, Volume 67, Issue 3, p. 400-414.

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Scientific paper

A theoretical approach to the calcite ⇌ aragonite transformation is presented for the case of a dislocation glide mechanism obeying first-order kinetics. The kinetic parameters are determined from recent experimental data from the literature; the sensitivity of the model to these and other parameters like the grain size and the deviatoric stresses are discussed.
The model results in the definition of what could be the actual transformation domains of the CaCO3 polymorphs in the (P,T) plane. These domains are different from the classical ones, i.e. different from the stability fields defined with respect to Clapeyron's curve; they can evolve in the (P,T) plane when a deviatoric stress is applied to the system. In this case, we can define a domain in which the two senses of the calcite ⇌ aragonite transition are activated simultaneously.
The application of the model to laboratory experiments needs the integration of the kinetic differential equation (K varying with P and T). Using this method, we demonstrate the role of (P,T,t) path on reaction rate and the role of experimental uncertainties on the reaction parameters K and n.
Finally, we discuss the problem of the synthesis of polymorphs out of their stability field and of their formation by grinding; these problems, difficult to tackle in terms of diffusion, can be approached with the proposed dislocation transformation kinetic model.

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