Silicate surfaces

In the presence of mineral phases containing anions that would form sparingly soluble compounds (e.g. POt - and F for the lower oxidation states) an enhanced plutonium uptake due to chemisorption can be expected (57). For plutonium in the higher oxidation states the formation of anionic carbonate complexes would drastically reduce the sorption on e.g oxide and silicate surfaces. 

Clay may promote hydrolysis of the metal at low pFI, but also inhibit hydrolysis at high pH (McBride, 1991). At a higher pH, clay prevents complete hydrolysis of the metal due to the affinity of the charged polymeric metal ions for the silicate surface. This keeps the metal from becoming a separate hydroxide phase. 

Both organic and inorganic ligands such as Cl and dissolved organic carbon (fulvie acid and carboxylic acids) decrease metal adsorption. In the arid soils with higher pH, folic acids increase the solubility of metals such as Cu and Zn. The interaction between the transition of heavy metals and silicate surfaces was reviewed by McBride (1991). 

The primary process initiating dust surface chemistry is the collision of a molecule from the ISM with the surface. The sticking probability is a measure of how often molecules will stick to the dust surface but this depends on the collision energy, the temperature of the grain surface and the nature of the chemical surface itself. The silicate surface is highly polar, at least for a grain of sand on Earth, and should attract polar molecules as well as atoms. The adsorption process can also be reversed, resulting in thermal desorption, both as the reverse of adsorption and by new molecules as the product of surface reactions. 

The volatile materials would have vaporised from the surface of the planetesimals once the temperature reached 160 K below this temperature water sticks to silicate surfaces and condenses, ultimately freezing into ice. The new gaseous material is swept away from the planetesimals by the solar wind of particles, leaving bare planetesimals too small to acquire and maintain an atmosphere. The temperature gradient and location within the solar nebula are then important to the ultimate nature and composition of the planets themselves and interplanetary debris. 

The adsorption of ligands (anions and weak acids) on metal oxide (and silicate) surfaces can also be compared with complex formation reactions in solution, e.g.,... 

The relationship given in Fig. 2.7 illustrates the affinities of cations and anions to the Lewis bases and Lewis acids of oxide and silicate surfaces. For alkali and earth... 

White, A. F. (1990), "Heterogeneous Electrochemical Reactions Associated with Oxidation of Ferrous Oxide and Silicate Surfaces", Reviews in Mineralogy 23,467-509. 

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. 

In view of the problems associated with the expanding 2 1 clays, the smectites and vermiculites, it seemed desirable to use a different clay mineral system, one in which the interactions of surface adsorbed water are more easily studied. An obvious candidate is the hydrated form of halloysite, but studies of this mineral have shown that halloysites also suffer from an equally intractable set of difficulties (JO.). These are principally the poor crystallinity, the necessity to maintain the clay in liquid water in order to prevent loss of the surface adsorbed (intercalated) water, and the highly variable morphology of the crystallites. It seemed to us preferable to start with a chemically pure, well-crystallized, and well-known clay mineral (kaolinite) and to increase the normally small surface area by inserting water molecules between the layers through chemical treatment. Thus, the water would be in contact with both surfaces of every clay layer in the crystallites resulting in an effective surface area for water adsorption of approximately 1000 tor g. The synthetic kaolinite hydrates that resulted from this work are nearly ideal materials for studies of water adsorbed on silicate surfaces. 

Subsequent work showed that a modification of the synthesis procedure produced a 10A hydrate which> if dried carefully, would maintain the interlayer water in the absence of excess water (27). This material is optimal for adsorbed water studies for a number of reasons the parent clay is a well-crystallized kaolinite with a negligible layer charge, there are few if any interlayer cations, there is no interference from pore water since the amount is minimal, and the interlayer water molecules lie between uniform layers of known structure. Thus, the hydrate provides a useful model for studying the effects of a silicate surface on interlayer water. 

An understanding of much of aqueous geochemistry requires an accurate description of the water-mineral interface. Water molecules in contact with> or close to, the silicate surface are in a different environment than molecules in bulk water, and it is generally agreed that these adsorbed water molecules have different properties than bulk water. Because this interfacial contact is so important, the adsorbed water has been extensively studied. Specifically, two major questions have been examined 1) how do the properties of surface adsorbed water differ from bulk water, and 2) to what distance is water perturbed by the silicate surface These are difficult questions to answer because the interfacial region normally is a very small portion of the water-mineral system. To increase the proportion of surface to bulk, the expanding clay minerals, with their large specific surface areas, have proved to be useful experimental materials. 

Based on the study of expanding clay minerals, two models of water adsorbed on silicate surfaces have been proposed. One states that only a few layers (<5) of water are perturbed by the silicate surface, the other concludes that many layers (perhaps 10 times that number) are involved. The complexity of the interactions which occur between water molecules, surface adsorbed ions, and the atoms of the silicate mineral make it very difficult to unequivocally determine which is the correct view. Both models agree that the first few water layers are most perturbed, yet neither has presented a clear picture of the structure of the adsorbed water, nor is much known about the bonding of the water molecules to the silicate surface and to each other. 

MCBRIDE Paramagnetic Probes of Layer Silicate Surfaces... 

Figure 8. Several orientations of TEMPAMINE at the layer silicate surface with a. maximum CHj-surface interaction (0 45°), b. minimum CHj-surface interaction (0 > 45°), c. minimum mobility (0 M)°). 0 is defined in Figure 7.

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