Acid variation with metal ions

Examples of acid modified polyolefins are the copolymers of ethylene with acrylic acid or methacrylic acid. Variations include the partially neutralised acid copolymers with metal ions (ionomers) or terpolymers of ethylene, an acid and an acrylate such as methyl acrylate or isobutyl acrylate. Acid-containing extrudable adhesives are widely used to bond to aluminium foil. Examples of anhydride-modified polyolefins include terpolymers of ethylene, maleic anhydride and acrylates such as ethyl acrylate or butyl acrylate and the anhydride-grafted polyolefins. Some typical applications and stmctures of a variety of multilayer materials with extruded polymer tie-layer adhesives, as described in Du-Pont trade literature, are detailed in Table 16.2. 

Although certain families of metal-ion complexes exhibit similar kinetic behavior, and the same mechanism may operate, there are still obvious and distinct differences from one metal ion to another. The variation with metal ion may be obvious merely from inspection of reaction products. For example, the series of compounds [M(NH3)5X]" [X = HCOO , 0CH-N(CH3)2, or F ] show in acid formation of only M(NH3)5(0H2), where M = Co(III) (90), yet exhibit a variety of be-... 

The formation of a coordinate bond is the result of the donation and acceptance of a pair of electrons. This in itself suggests that if a specific electron donor interacts with a series of metal ions (electron acceptors) there will be some variation in the stability of the coordinate bonds depending on the acidity of the metal ion. Conversely, if a specific metal ion is considered, there will be a difference in stability of the complexes formed with a series of electron pair donors (ligands). In fact, there are several factors that affect the stability of complexes formed between metal ions and ligands, and some of them will now be described. 

Example 14.3. The Belousov-Zhabotinsky reaction [22,27-29], The reaction is an oxidation of malonic acid by bromate ion in sulfuric acid, catalyzed by a Ce(III)/Ce(IV) redox couple. Many variations with other organic acids and transition-metal ions are possible [22] (Belousov used citric acid, and manganese, ruthenium, or iron can replace cerium). The color of the solution alternates between clear [Ce(III)] and pale yellow [Ce(IV)], and more dramatically between red and blue if ferroin is added as indicator. 

A variation of this method is the impregnation of layers with metal ions that act as central atoms. For example, thin-layer plates impregnated with cadmium, zinc, or manganese salts, have been used to separate alkaloids (201,202), amino acids (203), and sulfonamides (204). Impregnation with silver nitrate is especially important in this connection. The Ag ions are able to form complexes with n systems. In this way, selectivity is achieved with respect to the number, position, and geometry of double bonds. This property is used to separate chinones (205), fatty acid derivatives (206,207), lipids (208,210), and sterols (211,212). 

Surfactant effects on adsorption of herbicides on to soil have been investigated and suggested to be a factor to be considered in the overall effect of surfactant on toxicity towards the plant. The degradation, mobility and uptake of one such compound, picloram [4-amino-3,5,6-trichloropicolinic acid] (pK = 3.4) is affected by adsorption-desorption processes in solids. Picloram adsorption on to soils at pH 5 was reduced by 1 % anionic surfactant [284]. The mechanism involved in picloram adsorption included protonation of the molecule, metal-ion bridging and interaction with metal ions. Picloram adsorption was enhanced by cationic surfactants, suggesting that hydrophobic adsorption of the cationic monomers on to the soil provides a cationic surface for interaction of the anionic picloram. Different soils with different pH values resulted in some variations in these effects which are presented in Table 10.29. 

Fig. 6.11. Variation of metal ion retention time as a function of the mobile phase concentration of (A) tartaric acid, and (B) citric acid. Column 5-/im Asahipak GS-310H poly(vinyl alcohol) gel-type size exclusion, 250 mm x 7.6-mm i.d.. Mobile phases (A) tartaric acid + 0.05 M SDS, pH 4.4 (B) citric acid -h 0.05 M SDS, pH 4.3. Detection post-column reaction with PAR, photometric detection at 540 nm. (Reprinted with permission from ref [26], copyright 1988 American Chemical Society.)...

Because they are weak acids or bases, the iadicators may affect the pH of the sample, especially ia the case of a poorly buffered solution. Variations in the ionic strength or solvent composition, or both, also can produce large uncertainties in pH measurements, presumably caused by changes in the equihbria of the indicator species. Specific chemical reactions also may occur between solutes in the sample and the indicator species to produce appreciable pH errors. Examples of such interferences include binding of the indicator forms by proteins and colloidal substances and direct reaction with sample components, eg, oxidising agents and heavy-metal ions. 

The reaction was first tested with these substances as ligands but the organic molecule, in the absence of any added metal ion, proved to be the most enantioselective catalyst (library 1 19% ee vs. less than 13% ee for the best metal catalyst). The effects of selective variations of the amino acid nature and of the salicylidene moiety on the diamine structure were investigated for urea and thiourea derivatives via HTS (library 2 48 urea compounds and... 

The presence of residual unbound transition-metal ions on a dyed substrate is a potential health hazard. Various eco standards quote maximum permissible residual metal levels. These values are a measure of the amount of free metal ions extracted by a perspiration solution [53]. Histidine (5.67) is an essential amino acid that is naturally present as a component of perspiration. It is recognised to play a part in the desorption of metal-complex dyes in perspiration fastness problems and in the fading of such chromogens by the combined effects of perspiration and sunlight. The absorption of histidine by cellophane film from aqueous solution was measured as a function of time of immersion at various pH values. On addition of histidine to an aqueous solution of a copper-complex azo reactive dye, copper-histidine coordination bonds were formed and the stability constants of the species present were determined [54]. Variations of absorption spectra with pH that accompanied coordination of histidine with copper-complex azo dyes in solution were attributable to replacement of the dihydroxyazo dye molecule by the histidine ligand [55]. 

In order to quantify the transition metal ion concentration, Jones et al. [107] developed a highly sensitive fluorescent chemosensor in the form of dialkoxy-phenyleneethynylene-thiophene copolymers 68/69. The PAEs were functionalized on the thiophene unit with terpyridine (68), and included 2,2 -bipyridine (69) as a Lewis acid receptor. The terpyridine polymers [108] were found to respond quantitatively to transition metal ions at concentrations as low as 4x10 M (NP, Hg, Cr ", and Co " ). The additionally used bpy-PAE demonstrates that variation in the chelation at the receptor site is an important variable in tuning selectivity. The observed dynamic quenching mechanism, combined with the solubility of this material, provides the opportunity to extend these initial investigations to thin solid films for use in real-time monitoring applications. 

Owing to the large variety of surfactants, metal ions, and complex metal ions that have been incorporated into LB films, variations of the stoichiometry given in Eq. (2) are plentiful. Some of these are outlined in the following section. With fatty acid films, metal ions and complex metal ions containing something other than a divalent charge include Ag+, Fe3+, Ti(IV) from the transition metal series, U(III) from the actinide series, and M3+ from the lanthanide series (7). 

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