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Calcium carbonate (CaCO3) nucleation kinetics suggest prenucleation clusters are not involved. The transition state is a small, unstable cluster, challenging classical nucleation theories.

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Area of Science:

  • Geochemistry
  • Materials Science
  • Chemical Physics

Background:

  • Classical nucleation theory posits a critical cluster size for nucleation.
  • Nonclassical nucleation involves prenucleation clusters (PNCs) that restructure.
  • The exact nucleation pathway for calcium carbonate (CaCO3) remains debated.

Purpose of the Study:

  • To investigate the nucleation mechanism of CaCO3.
  • To determine the size of the transition state during CaCO3 nucleation.
  • To assess the role of prenucleation clusters (PNCs) in CaCO3 nucleation.

Main Methods:

  • Analysis of CaCO3 nucleation kinetics.
  • Experimental characterization of prenucleation cluster (PNC) size.
  • Thermodynamic and kinetic modeling of nucleation pathways.

Main Results:

  • The transition state for CaCO3 nucleation comprises approximately 10 formula units.
  • This transition state size is independent of supersaturation.
  • The transition state is significantly smaller than experimentally observed PNCs.

Conclusions:

  • Prenucleation clusters (PNCs) are likely not involved in the nucleation of CaCO3.
  • The nucleation kinetics suggest that if CaCO3 nucleates classically, the transition state is an unusually unstable cluster.
  • This finding challenges existing models of CaCO3 formation.