Clay surface reactions

The alkyl ammonium used to render the clay organophilic is known to decompose with the Hofmann elimination or with an SN2 nucleophilic substitution reaction at a temperature as low as 155°C." As result a protonic site is created on the clay surface (Reaction 10.1). 

Secondary minerals. As weathering of primary minerals proceeds, ions are released into solution, and new minerals are formed. These new minerals, called secondary minerals, include layer silicate clay minerals, carbonates, phosphates, sulfates and sulfides, different hydroxides and oxyhydroxides of Al, Fe, Mn, Ti, and Si, and non-crystalline minerals such as allophane and imogolite. Secondary minerals, such as the clay minerals, may have a specific surface area in the range of 20-800 m /g and up to 1000 m /g in the case of imogolite (Wada, 1985). Surface area is very important because most chemical reactions in soil are surface reactions occurring at the interface of solids and the soil solution. Layer-silicate clays, oxides, and carbonates are the most widespread secondary minerals. 

An explanation was suggested for these solvent and support effects and this is represented in Fig. 19. Thus, in solvents with greater dielectric permittivity, e, the cationic complex is situated further from the clay surface and the stereoselectivities are therefore more similar to those obtained in homogeneous phase. On the other hand, in solvents with low e, close ion pairs are formed and the surface has a larger effect on the reaction. 

Racemisation is a chemical reaction, and its rate is different for each type of amino acid. An important fact is that this process is affected by many factors that influence the rate of change of the amino acids stereochemistry [106]. The main parameters affecting the racemisation process include the amino acid structure, the sequence of amino acids in peptides, the bound state versus the free state of the amino acids, the pH in the environment, the concentration of buffer compounds, the contact of the sample with clay surfaces... 

Table III summarizes the parameters that affect Brrfnsted acid-catalyzed surface reactions. The range of reaction conditions investigated varies widely, from extreme dehydration at high temperatures in studies on the use of clay minerals as industrial catalysts, to fully saturated at ambient temperatures. Table IV lists reactions that have been shown or suggested to be promoted by Br nsted acidity of clay mineral surfaces along with representative examples. Studies have been concerned with the hydrolysis of organophosphate pesticides (70-72), triazines (73), or chemicals which specifically probe neutral, acid-, and base-catalyzed hydrolysis (74). Other reactions have been studied in the context of diagenesis or catagenesis of biological markers (22-24) or of chemical synthesis using clays as the catalysts (34, 36). Mechanistic interpretations of such reactions can be found in the comprehensive review by Solomon and Hawthorne (37).

Both acid- and base-promoted reactions may be affected by acidic surfaces and, hence, by the factors which influence the surface acidity. Kinetic evidence for increased Br nsted acidity at clay surfaces has been presented by McAuliffe and Coleman (80) who studied the hydrolysis of ethylacetate and the inversion of sucrose. They noted that potentionmetrie pH measurements did not explain the catalytically effective H+-concentration at the clay surface. 

Rate data for hydrolysis reactions in homogeneous aqueous solutions have been reviewed (79), but application of these data to environmental conditions involving mineral surfaces remains difficult due to the unknown effects sorption may have. Several studies have demonstrated that acid-catalyzed reactions are promoted if the substrate is sorbed at clay surfaces (70-74 and other works reviewed by Theng, 8), but inhibition may also occur if substrate hydrolysis is base-promoted (74). 

The dissociation of water coordinated to exchangeable cations of clays results in Brtfnsted acidity. At low moisture content, the Brrfnsted sites may produce extreme acidities at the clay surface-As a result, acid-catalyzed reactions, such as hydrolysis, addition, elimination, and hydrogen exchange, are promoted. Base-catalyzed reactions are inhibited and neutral reactions are not influenced. Metal oxides and primary minerals can promote the oxidative polymerization of some substituted phenols to humic acid-like products, probably through OH radicals formed from the reaction between dissolved oxygen and Fe + sites in silicates. In general, clay minerals promote many of the reactions that also occur in homogenous acid or oxidant solutions. However, rates and selectivity may be different and difficult to predict under environmental conditions. This problem merits further study. 

The chemistry of an important group of naturally occurring materials is characterized by surface reactions many clay minerals possess what can be considered surface at its extreme. All clay minerals capable of intracrystalline swelling with separation of the silicate layers are—to overstate it—surface with a silicate layer on each side. Many principles and techniques of surface chemistry were first found with clay minerals. Nevertheless, the clay minerals will not be considered in this article, except for some comparison and analogies with surface compounds. 

Clay minerals behave like Bronsted acids, donating protons, or as Lewis acids (Sect. 6.3), accepting electron pairs. Catalytic reactions on clay surfaces involve surface Bronsted and Lewis acidity and the hydrolysis of organic molecules, which is affected by the type of clay and the clay-saturating cation involved in the reaction. Dissociation of water molecules coordinated to surface, clay-bound cations contributes to the formation active protons, which is expressed as a Bronsted acidity. This process is affected by the clay hydration status, the polarizing power of the surface bond, and structural cations on mineral colloids (Mortland 1970, 1986). On the other hand, ions such as A1 and Fe, which are exposed at the edge of mineral clay coUoids, induce the formation of Lewis acidity (McBride 1994). 

Rearrangement reactions catalyzed by the clay surface were observed for par-athion (an organophosphate pesticide) when it was adsorbed on montmorillonite or kaolinite in the absence of a liquid phase. The rate of rearrangement reactions increased with the polarization of the hydration water of the exchangeable cation (Mingelgrin and Saltzman 1977). Table 14.1 summarizes a series of reactions catalyzed by clay surfaces, as reported in the literature. 

Table 14.1 Selected examples of reactions catalyzed by clay surfaces (Wolfe et al. 1990)...

Chaussidon J, Calvet R (1974) Catalytic reactions on clay surfaces. Third int congr of pesticides chemistry (lUPAC), Helsinki In Coulton E, Albaky NY, Konle E (eds) Environmental quaUty and safety, vol 3. Gerg Thiem. Stuttgart... 

Mingelgrin U, Saltzman S (1977) Surface reactions of parathion on clays. Qays Clay Miner 27 72-78... 

Because chlorite is an anion, sorption of chlorite ions onto suspend particles, sediment, or clay surfaces is expected to be limited under enviromnental conditions. Thus, chlorite ions may be mobile in soils and leach into groundwater. However, chlorite (ions or salts) will undergo oxidation-reduction reactions with components in soils, suspend particles, and sediments (e.g., Fe, Mn ions see Section 6.3.2.2). Thus, oxidation-reduction reactions may reduce the concentration of chlorite ions capable of leaching into groundwater. 

These examples illustrate that biomolecules may act as catalysts in soils to alter the structure of organic contaminants. The exact nature of the reaction may be modified by interaction of the biocatalyst with soil colloids. It is also possible that the catalytic reaction requires a specific mineral-biomolecule combination. Mortland (1984) demonstrated that py ridoxal-5 -phosphate (PLP) catalyzes glutamic acid deamination at 20 °C in the presence of copper-substituted smectite. The proposed pathway for deamination involved formation ofa Schiff base between PLP and glutamic acid, followed by complexation with Cu2+ on the clay surface. Substituted Cu2+ stabilized the Schiff base by chelation of the carboxylate, imine nitrogen, and the phenolic oxygen. In this case, catalysis required combination of the biomolecule with a specific metal-substituted clay. 

The rates of uptake of molybdenum, tellurium, and rubidium oxide vapors by substrates of calcium ferrite and a clay loam have been measured in air over a temperature range of 900° to 1500°C. and a partial pressure range of about 10r7 to 10 atm. The measured rates of uptake of molybdenum and tellurium oxide vapors by molten calcium ferrite and of rubidium oxide vapor by both molten clay loam and calcium ferrite were controlled by the rates of diffusion of the oxide vapors through the air. The measured rates of uptake of molybdenum and tellurium oxide vapors by molten clay loam were controlled by a combination of a slow surface reaction and slow diffusion of the condensate into the substrate. 

Test of Uptake Model Based on a Slow Surface Reaction Combined with Diffusion within the Particle. Since the simple diffusion model is inadequate to describe the uptake behavior of the molybdenum and tellurium oxide vapors by the clay loam particles, a more complex model is required, in which the effects of a slow surface reaction and of diffusion of the condensed vapor into the particle are combined. Consider the condensation of a vapor at the surface of a substrate (of any geometry) and the passage by diffusion of the condensed vapor through a thin surface layer into the body of the substrate. The change in concentration of solute per unit volume in the surface layer caused by vapor condensa-... 

Interpretation of the mechanisms of the hydrocarbon desorption reactions mentioned above was considered (31,291) with due regard for the possible role of clay dehydration. While this water evolution process is not regarded as a heterogeneous catalytic reaction, it is at least possible that water loss occurs at an interface (293) so that estimations of preexponential factors per unit area can be made. On this assumption, Arrhenius parameters (in the units used throughout the present review) were calculated from the available observations in the literature and it was found (Fig. 9, Table V, S) that compensation trends were present in the kinetic data for the dehydration reactions of illite (+) (294), kaolinite ( ) (293,295 298), montmorillonite (x) (294) and muscovite (O) (299). If these surface reactions are at least partially reversible,... 

From the discussion presented in the previous paragraphs, we identify the kinetic characteristics of the hydrocarbon evolution reactions (31,291,292) and the clay dehydration processes with the common mechanistic features reversibility and similar characteristic temperatures of onset of the water evolution step. The compensation effects observed for the two groups of related reactions (Table V, R and S) were not identical, however, since the species participating in the equilibria on the surfaces (believed to be represented by the kinetic characteristics described in Appendix I) are different. Undoubtedly, the interaction of hydroxyl groups to yield water was common to both types of reaction (surface desorption and lattice dehydration) and the properties and reactivities of these species probably determine the temperature at which significant surface activity and product evolution becomes apparent. This surface reaction is... 

Clayfen (1.13 g, 1.2 mmol of iron(III) nitrate) is thoroughly mixed with neat thioacetal lb (0.227 g, 1 mmol) in the solid state. The material is transferred in a test tube and placed in an alumina bath inside the microwave oven and irradiated (40 s). Upon completion of the reaction, monitored on TLC (hexane-EtOAc, 8 2, v/v), the product was extracted into ethylene chloride. The resulting solution is passed through a small bed of neutral alumina. Evaporation of the solvent delivers pure p-nitrobenzaldehyde 2b in 97% yield. In the case of cyclic thio acetals and ketals, the liberated dithiols bind to the clay surface rather tightly and a simple washing of the clayfen affords clean products. 

The adsorption of aluminum onto clay surfaces can be a significant factor in controlling aluminum mobility in the environment, and these adsorption reactions, measured in one study at pH 3.0-4.1, have been observed to be very rapid (Walker et al. 1988). However, clays may act either as a sink or a source for soluble aluminum depending on the degree of aluminum saturation on the clay surface (Walker et al. 1988). 

Clays, and especially swelling clays, are made from anisotropic microcrystals displaying large specific surface areas. However, because these microcrystals have a strong tendency to aggregate into tactoids, only a fraction of the surface area is available for surface reactions. 

Therefore, not only the nature of the surface active sites, as related to the structure, but their availability, as related to the particular texture are discussed as well. The relationship between these two aspects of clay surface reactivity is more heavily emphasized here than is the specific chemistry of reactions occurring on the surface of clays. 

Hydrated clay surfaces are acidic. When isomorphic substitution occurs in the tetrahedral layer, acid leaching or NH thermal decomposition may generate acidic surface OH. For clays whose negative charges are produced by isomorphic substitutions in the octahedral layer, mild dehydration removes the source of acidity, because of the reversibility of reaction (3). Deamination of the ammonium exchanged clay with octahedral substitution drives protons into the octahedral layer, as evidenced by the lowered temperature at structural dehydroxylation. 

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