Cation exchangeable

Extensive intercalation of polar molecules takes place in this substance in an irreversible manner, and marked hysteresis results (Fig. 4.28). The driving force is thought to be the interaction between the polar molecules and the exchange cations present in the montmorillonitic sheets, since non-polar molecules give rise to a simple Type B hysteresis loop with no low-pressure hysteresis. 

A significant advantage of adsorbents over other separative agents Hes in the fact that favorable equiHbrium-phase relations can be developed for particular separations adsorbents can be produced that are much more selective in their affinity for various substances than are any known solvents. This selectivity is particularly tme of the synthetic crystalline zeoHtes containing exchangeable cations. These zeoHtes became available in the early 1960s under the name of molecular sieves (qv) (9). 

Zeolites are named to represent the exchangeable cations in them for example, NaY is zeohte Y with sodium ions in the cation exchange positions. 

Cation exchange capacity The ability of a soil or other solid to exchange cations (positive ions such as calcium) with a liquid. 

V. Laperche, J. F. Lambert, R. Prost, R., and J. J. Fripiat, High-resolution solid-state NMR of exchangeable cations in the interlayer surface of a swelling mica %a. 

Under the mineralogical name zeolite such sieves occur naturally. For technical purposes due to their higher uniformity only synthetic zeolites are used [10], In the empirical formula Me is an exchangeable cation of the valence n (zeolites are cation exchangers). Molecular sieves have a very regular and orderly crystal structure, which is characterized by a three-dimensional system of cavities with a diameter of 11 A. These cavities are interconnected by pores with a constant diameter. The value of this diameter depends on the type of the exchangeable cation Me. It is 5 A, if in the above formula Me stands for 75% Na+ and 25% Ca2+. 

Due to the relatively weak forces between the layers of MMT, water and other polar molecules can enter between the unit layers, causing the lattice to expand in the thickness direction. The charge deficiency on the sheet surface is typically balanced by exchangeable cations adsorbed between the unit layers and around their edges because of the substitution of ions of different valence. 

Bronsted acidity is the principal source of activity with the relative concentration of protonated and non-protonated reactants being dependent upon the nature of the exchangeable cation. Using FeCls - graphite intercalates - formed using a photochemical procedure and subsequently reduced using K/naphthalide - an efficient catalyst for the production of acetylene from syngas has been produced. 

Thin self-supporting clay films (appropriate for IR measurement) readily take up organic amines such as cyclohexylamine with displacement of the major fraction of the intercalated water. For the Ua -exchanged sample the majority of the amine is present in the unprotonated form - there being insufficient Bronsted acidity generated by the interlayer cation. When Al + is the exchangeable cation, however, a major fraction of the intercalated amine becomes protonated (see Figure 2). 

In clay mineral crystals, atoms having different valences commonly will be positioned within the sheets of the structure to create a negative potential at the crystal surface. In that case, a cation is adsorbed on the surface. These adsorbed cations are called exchangeable cations because they may chemically trade places with other cations when the clay crystal is suspended in water. In addition, ions may also be adsorbed on the clay crystal edges and exchange with other ions in the water. 

The important feature is the formation of a coordinatively unsaturated site (cus), permitting the reaction to occur in the coordinative sphere of the metal cation. The cus is a metal cationic site that is able to present at least three vacancies permitting, in the DeNOx process, to insert ligands such as NO, CO, H20, and any olefin or CxHyOz species that is able to behave like ligands in its coordinative environment. A cus can be located on kinks, ledges or corners of crystals [16] in such a location, they are unsaturated. This situation is quite comparable to an exchanged cation in a zeolite, as studied by Iizuka and Lundsford [17] or to a transition metal complex in solution, as studied by Hendriksen et al. [18] for NO reduction in the presence of CO. 

In this scheme, a counter ion Y", attached to the R+ group on the resin, is exchanged for another anion X" from solution. To exchange cations, we need a structure with exchange sites that are negatively charged, and associated positive counter ions ... 

For cationic zeolites Richardson (79) has demonstrated that the radical concentration is a function of the electron affinity of the exchangeable cation and the ionization potential of the hydrocarbon, provided the size of the molecule does not prevent entrance into the zeolite. In a study made on mixed cationic zeolites, such as MgCuY, Richardson used the ability of zeolites to form radicals as a measure of the polarizing effect of one metal cation upon another. He subsequently developed a theory for the catalytic activity of these materials based upon this polarizing ability of various cations. It should be pointed out that infrared and ESR evidence indicate that this same polarizing ability is effective in hydrolyzing water to form acidic sites in cationic zeolites (80, 81). 

The clay used is a montmorillonite referenced KC2 provided from CECA (France). Its general formula is (Si8 O2o AI4.X Mx)(OH)24 CEy. n H20, where CE are exchangeable cations. 

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