Kaolinite hydrogen bonds

Sulfoxides DMSO/kaolinite Hydrogen bonding Olejniket al. (261)... 

Clays consist of parallel silicate layers in kaolinite, two unsymmetrical types of layers are linked by hydrogen bonds. One consists of aluminium ions and hydroxyl groups, the other of silicon and oxygen ions. Cairns-Smith does not postulate a detailed mechanism, but only describes the main thrust of his argument. Critics complain that clear experimental results are not available (however, other proponents of new hypotheses often provide no evidence to back up their suggestions ). 

Study of hydrated kaolinites shows that water molecules adsorbed on a phyllosilicate surface occupy two different structural sites. One type of water, "hole" water, is keyed into the ditrigonal holes of the silicate layer, while the other type of water, "associated" water, is situated between and is hydrogen bonded to the hole water molecules. In contrast, hole water is hydrogen bonded to the silicate layer and is less mobile than associated water. At low temperatures, all water molecules form an ordered structure reminiscent of ice as the temperature increases, the associated water disorders progressively, culminating in a rapid change in heat capacity near 270 K. To the extent that the kao-linite surfaces resemble other silicate surfaces, hydrated kaolinites are useful models for water adsorbed on silicate minerals. 

The marked difference in the relaxation times for the kaolinite and silica may be attributed to the nature of the surface. Intuitively, the hydrogen bonding which influences the increased structure at the kaolinite surface would be expected to give shorter values for the relaxation time. However this is not observed in the simulations. Instead, shorter values are seen for the silica surface which is a result of water molecules becoming trapped in the cage-like amorphous silica surface. This reflects experimental results where precipitated silica surfaces are microporous and water inclusion in the surface is common. 

The number and exact composition of the sheets is used to classify the phyllosilicates. The most important classification for our purposes is the distinction between 1 1 and 2 1-type minerals (Figure 2.1). In 1 1 minerals such as kaolinite, the basal oxygens of the tetrahedral sheet are free to interact with octahedral OH groups forming hydrogen bonds. In contrast, 2 1 minerals such as pyrophyllite or talc contain two tetrahedral sheets sandwiched around an octahedral sheet. These minerals have only basal oxygens exposed on the faces of the tetrahedral sheets and are linked by weak van der Waals forces. The weaker interaction of one 2 1 layer with a second 2 1 layer results in interlayer spaces which, depending on the particular mineral, may be available for contaminant intercalation. 

The above results are related to the structural properties of the clay minerals. In the case of kaolinite, the tetrahedral layers of adjacent clay sheets are held tightly by hydrogen bonds. Therefore, only readily available planar external surface sites exist for exchange. With smectite, the inner peripheral space is not held together by hydrogen bonds, but instead it is able to swell with adequate hydration and thus allow for rapid passage of ions into the interlayer. 

The value of the reaction enthalpy of decomposition of the kaolinite-DMSO intercalate is -12 kcal/mol [142] and the enthalpy of formation of hydrogen bonds is about -10 kcal/mol [143]. 

---