A thermodynamic solution model for calcium carbonate: Towards an understanding of multiequilibria precipitation pathways
Article
English
OPEN
Donnet, Marcel
;
Bowen, Paul
;
Lemaître, Jacques
(2009)
 Publisher: Elsevier

Subject:
Calcium carbonate  Solubility  Interfacial energy  Surface potential  Crystal size  Reaction pathway  Electrokinetic Properties  InterfacialTensions  AqueousSolutions  System  Surface  25DegreesC  Nucleation  Inhibition  Aragonite
Thermodynamic solubility calculations are normally only related to thermodynamic equilibria in solution. In this paper, we extend the use of such solubility calculations to help elucidate possible precipitation reaction pathways during the entire reaction. We also estimate the interfacial energy of particles using only solubility data by a modification of Mersmann’s approach. We have carried this out by considering precipitation reactions as a succession of small quasiequilibrium states. Thus possible equilibrium precipitation pathways can be evaluated by calculating the evolution of surface charge, particle size and/or interfacial energy during the ongoing reaction. The approach includes the use of the Kelvin’s law to express the influence of particle size on the solubility constant of precipitates, the use of Nernst’s law to calculate surface potentials from solubility calculations and relate this to experimentally measured zeta potentials. Calcium carbonate precipitation and zeta potential measurements of well characterised high purity calcite have been used as a model system to validate the calculated values. The clarification of the change in zeta potential on titration illustrates the power of this approach as a tool for reaction pathway prediction and hence knowledge based tailoring of precipitation reactions.