Carbon ions/species

In many metal-u-organo complexes (represented by M—R where M can be a complex with other ligands) it seems probable that the first step in their decomposition is the dissociation of the M-carbon bond. This may dissociate homolytically or heterolytically, forming either a carbon radical or carbon ion species. In both cases, the carbon fragments would normally be very reactive and readily form stable products, for example by dimerization, or polymerization (see Figure 51). It is the formation of these more... 

Modifications of the basic process are undersoftening, spHt recarbonation, and spHt treatment. In undersoftening, the pH is raised to 8.5—8.7 to remove only calcium. No recarbonation is required. SpHt recarbonation involves the use of two units in series. In the first or primary unit, the required lime and soda ash are added and the water is allowed to settie and is recarbonated just to pH 10.3, which is the minimum pH at which the carbonic species are present principally as the carbonate ion. The primary effluent then enters the second or secondary unit, where it contacts recycled sludge from the secondary unit resulting in the precipitation of almost pure calcium carbonate. The effluent setties, is recarbonated to the pH of saturation, and is filtered. The advantages over conventional treatment ate reductions in lime, soda ash, and COg requirements very low alkalinities and reduced maintenance costs because of the stabiUty of the effluent. The main disadvantages are the necessity for very careful pH control and the requirement for twice the normal plant capacity. 

The initial step is the protonation of the aldehyde—e.g. formaldehyde—at the carbonyl oxygen. The hydroxycarbenium ion 6 is thus formed as reactive species, which reacts as electrophile with the carbon-carbon double bond of the olefinic substrate by formation of a carbenium ion species 7. A subsequent loss of a proton from 7 leads to formation of an allylic alcohol 4, while reaction with water, followed by loss of a proton, leads to formation of a 1,3-diol 3 " ... 

In an initial step the carbenium ion species 2 has to be generated, for example by protonation of an alcohol 1 at the hydroxyl oxygen under acidic conditions and subsequent loss of water. The carbenium ion 2 can further react in various ways to give a more stable product—e.g. by addition of a nucleophile, or by loss of a proton from an adjacent carbon center the latter pathway results in the formation of an alkene 3. 

In experiments where Mono Lake water was acidified to remove carbonate and bicarbonate ions and again adjusted to pH 10, more than 90 percent of the soluble plutonium moved to the sediment phase. When carbonate ion concentration was restored, the plutonium returned to solution—strong evidence of the importance of inorganic carbon to solubility in that system(13). Early studies with Lake Michigan water, which has low DOC, had also implicated bicarbonate and carbonate as stabilizing ligands for plutonium at pH 8(14). This latter research characterized the soluble species as mainly anionic in character. 

The complexation of Pu(IV) with carbonate ions is investigated by solubility measurements of 238Pu02 in neutral to alkaline solutions containing sodium carbonate and bicarbonate. The total concentration of carbonate ions and pH are varied at the constant ionic strength (I = 1.0), in which the initial pH values are adjusted by altering the ratio of carbonate to bicarbonate ions. The oxidation state of dissolved species in equilibrium solutions are determined by absorption spectrophotometry and differential pulse polarography. The most stable oxidation state of Pu in carbonate solutions is found to be Pu(IV), which is present as hydroxocarbonate or carbonate species. The formation constants of these complexes are calculated on the basis of solubility data which are determined to be a function of two variable parameters the carbonate concentration and pH. The hydrolysis reactions of Pu(IV) in the present experimental system assessed by using the literature data are taken into account for calculation of the carbonate complexation. 

Based on Equation 4, it is possible to evaluate the dissolved concentration of Pu as a function of pH, provided polymer and other complex species are not present. However, the polymerization of hydrolysed species enhances the solubility of Pu02 and hence the dissolved Pu concentration is expected to be greater than the quantity calculated by Equation 4. On the other hand, the presence of a strong complexing anion, e.g. carbonate ion, may... 

The Bronsted definition also includes the possibility that an ion is an acid (an option not allowed by the Arrhenius definition). For instance, a hydrogen carbonate ion, HC03, one of the species present in natural waters, can act as an acid and lose a proton, and the resulting carbonate ion is removed by precipitation if suitable cations are present (Fig. 10.2) ... 

Bushnell and co-workers [117] employed extensive molecular modelling to understand the nature of cis and trans isomerism in tetrahedral p-phenylene vinylene oligomers, and to aid the interpretation of time of flight mass spectrometry and ion mobility studies. Molecules such as T4R, shown in Figure 18, with four equivalent arms can be used to control the crystallinity in thin films. The authors reported the observation of a species in the mass spectrum resulting from the loss of an arm from the central carbon. This species will be referred to as P4R. 

The basic constituent of seashells is calcium carbonate, an insoluble compound formed from calcium ions secreted from the cells of the shellfish and carbonate ions present in seawater. But calcium carbonate is a white solid. The colors of seashells often arise from impurities and metabolic waste products captured in the solid shell as it is formed. Coloration is dictated by both diet and water habitat. For example, some cowries that live and feed on soft corals take on the hue of the coral species. Yellow and red colors often arise from carotenoid pigments such as //-carotene. Light refraction often generates the iridescent mother-of-pearl hues. 

In addition to soil solution, speciation of trace elements in water of the Nahr-Ibrahim river valley of Lebanon was studied with the AQUACHEM model. The results indicate that a high percentage of Pb and Zn is present as carbonate species, but in low percentages in free hydrated ion species. Cadmium exhibits as a high percentage of a free hydrated Cd2+. 

HCOj, and carbonate ions COj. The concentrations of these species are governed by equilibrium relationships (Broecker and Peng, 1982). 

Of particular concern are the impacts of seawater acidification on biocalcification and the burial rates of sedimentary carbon. Carbonate ion concentrations in the surface waters have already declined by 16%. Thus, it is not surprising that the abundance of tropical/subtropic planktonic foraminiferan species appears to have declined since the 1960s. This information was obtained by studying the rapidly accumulating sediments of the Santa Barbara Basins off the coast of California. 

HNO3 is a source of H which would reduce the amount of carbonate ion (the H reacts with the weak base, CO ). NH3 forms Ag(NH3) removing Ag from solution. Furthermore, according to Le ChateUer s Principle, when the concentration of a species is reduced, the reaction shifts in the direction necessary to reform that species. in this case, toward the right and toward ionization. 

The Pu +/Pu + couple for a series of Pu(IV)/(EDTA ) based complexes, where EDTA = ethylenediaminetetraacetate, has been studied as a function of pH and EDTA concentration [118]. The voltammetry was also studied with citrate and carbonate ions present in solution. At a relatively low pH of 2.3 and equimolar Pu +/EDTA concentrations a quasi-reversible one-electron reduction is observed for Pu(EDTA) at E /2 = 0.342 V versus SHE. The quasireversibility of this process remains as the pH is raised to 4.6. Additional voltammetry studies are discussed in the paper for the higher coordinate Pu + species, Pu(EDTA)-L (where L = EDTA, carbonate, citrato), all of which show irreversible electron-transfer behavior. 

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