Calcium carbonate and its hydrates

Abstract

This paper is concerned with observations on the preparation of phases which may exist in the system CaCO 3 -H 2 0 in the presence o f ‘additives’, with a qualitative explanation of the appearance of unstable phases under such conditions. It has been found that the tendency for metastable phases of calcium carbonate to be precipitated from aqueous solutions is increased not only by raising the rate of precipitation but also by increasing the concentration of certain added substances. Thus in the presence of small amounts of Calgon* or magnesium-ion, and in saturated sodium chloride solution in the presence of magnesium-ion, a range of products is obtained according to the conditions of precipitation, particularly the stirring and the temperature. Calcite (the stable phase), aragonite, vaterite (/^-calcium carbonate) and calcium carbonate hexahydrate have been prepared In this way together with a new hydrate, CaCO 3 .H 2 O . By allowing reaction mixtures containing additive to stand until the first-formed gel has crystallized, metastable phases may be produced with considerable regularity. Metastable phase diagrams can be constructed which show the dependence of the phases on conditions of precipitation, e.g. sodium carbonate concentration and concentration of additive. By exploration using such diagrams, all the previously mentioned phases except vaterite have been prepared in the presence of magnesium-ion, and in the presence of Calgon all but aragonite have been identified. This suggests that to some extent the action of the additives is specific. In stirred conditions of reaction, calcium carbonate may be grown, without fresh nucleation, on seed crystals of calcite and vaterite at a much faster rate in the presence of limited amounts of Calgon than in its absence. At relatively high concentrations other phases may appear and growth of the calcite and vaterite ceases in spite of the presence of seed crystals. Compounds containing calcium carbonate formed in the presence of magnesium-ion or Calgon have been shown by analytical methods to contain magnesium or phosphorus in appreciable quantities. The presence of the additive leads to modification in the crystal habit of calcite and of the hexahydrate. It has also been noted that distortion of X-ray patterns of the crystalline species is common. This is consistent with absorption of the additive in the distorted phase. Absorption of additive seems, therefore, to be important in influencing nucleation and the formation of metastable phases. These observations are explained on the grounds that germs of the crystalline phases are subject to varying degrees of distortion depending on the constitution of the solution. The growth is therefore hindered to different degrees in different cases. In the limit the effect of distortion may be such that growth of nuclei of certain types may be inhibited, and there is a corresponding change in the conditions for the spontaneous crystallization from solution of the various phases.