Readily exchangeable ions

In a more restrictive sense, the term "ion exchange" is used to characterize the replacement of one adsorbed, readily exchangeable ion by another. This circumscription, used in soil science (Sposito, 1989), implies a surface phenomenon involving charged species in outer-sphere complexes or in the diffuse ion swarm. It is not possible to adhere rigorously to this conceptualization because the distinction between inner-sphere and outer-sphere complexation is characterized by a continuous transition, (e.g., H+ binding to humus). 

A further difficulty is the distinction between a concept and an operation, for example in the definition of ion exchange capacity. Operationally, "the ion exchange capacity of a soil (or of soil-minerals in waters or sediments) is the number of moles of adsorbed ion charge that can be desorbed from unit mass of soil, under given conditions of temperature, pressure, soil solution composition, and soil-solution mass ratio" (Sposito, 1989). The measurement of an ion exchange capacity usually involves the replacement of (native) readily exchangeable ions by a "standard" cation or anion. 

Helfferich, F., Ion Exchange, McGraw-Hill, New York, 1962. For soil chemists, still the most readable experimentalist-oriented introduction to the pure chemistry of readily exchangeable ions. 

Ion exchange consists of the replacement of one adsorbed, readily exchangeable ion by another. The involvement of oxygen surfiice groups in the sorption mechanism by ion exchange was confirmed hy an improvement in adsorption onto oxidized adsorbents [10]. Carboxylic surface groups have been shown to be especially involved in the adsorption process [8], but this phenomenon may also occur with other ions such as [11] Ca, K, and Na " ". 

Metabolic Functions. Bones act as a reservoir of certain ions, in particular Ca " and which readily exchange between bones and blood. 

Physical Chemical Characterization. Thiamine, its derivatives, and its degradation products have been fully characterized by spectroscopic methods (9,10). The ultraviolet spectmm of thiamine shows pH-dependent maxima (11). H, and nuclear magnetic resonance spectra show protonation occurs at the 1-nitrogen, and not the 4-amino position (12—14). The H spectmm in D2O shows no resonance for the thiazole 2-hydrogen, as this is acidic and readily exchanged via formation of the thiazole yUd (13) an important intermediate in the biochemical functions of thiamine. Recent work has revised the piC values for the two ionization reactions to 4.8 and 18 respectively (9,10,15). The mass spectmm of thiamine hydrochloride shows no molecular ion under standard electron impact ionization conditions, but fast atom bombardment and chemical ionization allow observation of both an intense peak for the patent cation and its major fragmentation ion, the pyrimidinylmethyl cation (16). 

Substituted tetrazoles readily exchange the 5-hydrogen for deuterium in aqueous solution. A major rate-enhancing effect is observed with copper(II) or zinc ions due to complexation with the heterocycle. The rate of base-induced proton-deuterium exchange of 1-methyltetrazole is 10 times faster than 2-methyltetrazole (77AHC(2l)323). 

Due to the relatively high acidities of their hydroxy groups, hydroxyazoles readily exchange their protons with metal ions, which leads to stabilization of metal derivatives of the hydroxy tautomeric forms in metal coordination compounds of 2(5)-oxoazoles [97UK434 98AHC(72)1]. A typical example is the mercury complex 361 [93JCS(D)1003]. 

The most significant class of inorganic supports, which is used for the direct ion exchange of positively charged transition-metal complexes, are smectite clays. Pin-navaia has introduced the use of these swelling, layered silicate clays for catalysis. Other clays include montmorillonite, bentonite, and laponite. As shown by Pinna-vaia, cationic transition-metal complexes can be readily exchanged (intercalated) into the solvated interlayers of these silicates (Eq. (1)) [117] ... 

On the basis of the preceding discussion, it should be obvious that ultratrace elemental analysis can be performed without any major problems by atomic spectroscopy. A major disadvantage with elemental analysis is that it does not provide information on element speciation. Speciation has major significance since it can define whether the element can become bioavailable. For example, complexed iron will be metabolized more readily than unbound iron and the measure of total iron in the sample will not discriminate between the available and nonavailable forms. There are many other similar examples and analytical procedures that must be developed which will enable elemental speciation to be performed. Liquid chromatographic procedures (either ion-exchange, ion-pair, liquid-solid, or liquid-liquid chromatography) are the best methods to speciate samples since they can separate solutes on the basis of a number of parameters. Chromatographic separation can be used as part of the sample preparation step and the column effluent can be monitored with atomic spectroscopy. This mode of operation combines the excellent separation characteristics with the element selectivity of atomic spectroscopy. AAS with a flame as the atom reservoir or AES with an inductively coupled plasma have been used successfully to speciate various ultratrace elements. 

There are a number of more loosely defined terms for different types of adsorption that are related to the form of surface complexation. Specifically adsorbed ions are held in inner-sphere complexes whereas non-specifically adsorbed ions are in outer-sphere complexes or the diffuse-ion swarm. Readily exchangeable... 

An ion pair in which the constituent ions are separated by one or more solvent (or other neutral) molecules. If and Y represent the constituent ions, a loose ion pair is usually symbohzed by X+ Y. The constituent ions of a loose ion pair can readily exchange with other ions in solution this provides an experimental means for distinguishing loose ion pairs from tight ion pairs. In addition, there are at least two types of loose ion pairs solvent-shared and solvent-separated. See Ion Pair Tight Ion Pair Solvent-Shared Ion Pair Solvent-Separated Ion Pair... 

Information published during thepast few years about the faujasite class of zeolites indicated that they present a possibly unique system in which the necessary conditions might be met. Sherry (4, 5) reported that rare earths, as compared with alkali or alkaline earth metals, are readily exchanged into Linde X from dilute aqueous solutions, and that they strongly favor the zeolite phase. When such an exchanged zeolite is dehydrated by heating to 350-700° C, the lanthanide ions move into the small pore system (6>, 7) after which they are not readily exchanged back out of the crystal. Smith (8) has reviewed the structure of lanthanide X and Y zeolites. 

Bones act as a reservoir of certain ions, in particular Ca and PO/1". which readily exchange between bones and blood. Bone structure comprises a strong organic matrix combined with an inorganic phase which is principally hydroxyapatite, 3 CadPO/l- CaiOHH. Bones contain two forms of hydroxyapatite. The less soluble crystalline form contributes to the rigidity of the structure. The crystals are quite stable, hut because of the small size present a very large surface area available lor rapid... 

Injection of calcium disodium EDTA does not affect blood calcium levels but heavy metal ions in the body have a higher affinity for EDTA than does calcium, and hence these metals readily exchange in vivo to form soluble EDT A-heavy-metal complexes that are excreted in the urine. Because of its poor absorption from the alimentary tract, calcium disodium EDTA is usually injected intramuscularly or intravenously. These considerations led to its being used, initially in 195270), to treat lead encephalopathy. 

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