Metal organic complexation

The Debye temperature is usually high for metallic systems and low for metal-organic complexes. For metals with simple cubic lattices, for which the model was developed, is found in the range from 300 K to well above 10 K. The other extreme may be found for iron in proteins, which may yield d as low as 100-200 K. Figure 2.5a demonstrates how sharply/(T) drops with temperature for such systems. Since the intensity of a Mossbauer spectrum is proportional to the... 

Armannsson [659] has described a procedure involving dithizone extraction and flame atomic absorption spectrometry for the determination of cadmium, zinc, lead, copper, nickel, cobalt, and silver in seawater. In this procedure 500 ml of seawater taken in a plastic container is exposed to a 1000 W mercury arc lamp for 5-15 h to break down metal organic complexes. The solution is adjusted to pH 8, and 10 ml of 0.2% dithizone in chloroform added. The 10 ml of chloroform is run off and after adjustment to pH 9.5 the aqueous phase is extracted with a further 10 ml of dithizone. The combined extracts are washed with 50 ml of dilute ammonia. To the organic phases is added 50 ml of 0.2 M-hydrochloric acid. The phases are separated and the aqueous portion washed with 5 ml of chloroform. The aqueous portion is evaporated to dryness and the residue dissolved in 5 ml of 2 M hydrochloric acid (solution A). Perchloric acid (3 ml) is added to the organic portion, evaporated to dryness, and a further 2 ml of 60% perchloric acid added to ensure that all organic matter has been... 

System 7, 9, 10. roots-rizosphere (VII) plants (VIII) their biological reactions— metabolism (VIII) soil-soil solution, air (IV) aerosols—atmospheric air (26, 28). In this system, the influence of metal-organic complexes on the plant development and their metabolism is considered. Under deficient or excessive contents of some chemical species, the metabolism may be destroyed (see Figure 2). 

Box 5. The role of metal-organic complexes in biogeochemical migration of trace elements (after Newman and McIntosh, 1991)... 

For understanding these tendencies, we will consider the values of the biogeo-chemical coefficient of aqueous migration. This coefficient Cw is the ratio between the content of an element in the sum of water-soluble salts and in geological rocks. The values of Cw for certain chemical species are smaller in Arid ecosystems than those in Forest ecosystems. We can suggest two explanations. First, soils of Forest ecosystems are enriched in water-soluble metal-organic complexes (see Chapter 7). Second, most chemical species are trapped in the transpiration barrier of upper soil layers of Arid ecosystems. 

As a result of microbial formation of metal-organic complexes with fulvic acids in soils of Tropical Rain Forest ecosystems, the surface and sub-surface runoff waters are enriched in some heavy metals like manganese and copper. A similar tendency has been shown for boron, strontium and fluorine. 

The sixth class of green emitters is metal organic complexes. Alq3 was the first green emitter. Alq3 emission exhibits relatively saturated green color (CIE 1931 coordinates (0.32,0.55)) and so far, it is still one of the best green emitters available. 

In addition to stabilizing organic products by reaction with metal-exchanged clays, as indicated above, aluminosilicate minerals may enable the preparation of metal organic complexes that cannot be formed in solution. Thus a complex of Cu(II) with rubeanic acid (dithiooxamide) could be prepared by soaking Cu montmorillonite in an acetone solution of rubeanic acid (93). The intercalated complex was monomeric, aligned with Its molecular plane parallel to the interlamellar surfaces, and had a metal ligand ratio of 1 2 despite the tetradentate nature of the rubeanic acid. 

The hybridizing component can also be formed directly on the surface of a pristine or modified nanocarbon using molecular precursors, such as organic monomers, metal salts or metal organic complexes. Depending on the desired compound, in situ deposition can be carried out either in solution, such as via direct network formation via in situ polymerization, chemical reduction, electro- or electroless deposition, and sol-gel processes, or from the gas phase using chemical deposition (i.e. CVD or ALD) or physical deposition (i.e. laser ablation, electron beam deposition, thermal evaporation, or sputtering). 

This example illustrates a case of considerable analytical importance, especially for the determination of complex formation constants for hydrophilic complexes, as discussed in section 4.12, when the equilibrium constants for the stepwise metal-organic complexes are of secondary interest. values are tabulated in several reference works. is a conditional constant and only valid provided no other species are formed besides the extracted one. 

Metal-Organic Complexes with Organic Adduct Formers, Type MA B ... 

Solvent extraction has become a common technique for the determination of formation constants, P , of aqneons hydrophilic metal complexes of type MX , particularly in the case when the metal is only available in trace concentrations, as the distribntion can easily be measnred with radioactive techniques (see also section 4.15). The method reqnires the formation of an extractable complex of the metal ion, which, in the simplest and most commonly used case, is an nn-charged lipophilic complex of type MA. The metal-organic complex MA serves as a probe for the concentration of metal ions in the aqueous phase through its equilibrium with the free section 4.8.2. This same principle is used in the design of metal selective electrodes (see Chapter 15). Extractants typically used for this purpose are P-diketones like acetylacetone (HAA) or thenoyltrifluoroacteone (TTA), and weak large organic acids like dinonyl naph-talene sulphonic acid (DNNA). 

Few solubility parameters are available for the metal-organic complexes discussed in this chapter. Another approach is then necessary. The distribution constant for the reagent (extractant), R, can be expressed as ... 

In Chapters 2 and 3 several physicochemical factors of importance to solvent extraction have been described, and many of their effects have been illustrated in this chapter. Here, we summarize some observed regularities. The effect of various stractures on the bond strengths in metal organic complexes has been extensively treated in other publications [47-49]. 

The extractabilities of metal-organic complexes depend on whether inner or outer sphere complexes are formed. Case 1, section 4.2.1, the extraction of ura-nyl nitrate by TBP, is a good example. The free uranyl ion is surrounded by water of hydration, forming U02(H20)f, which from nitric acid solutions can be crystallized out as the salt U02(H20)6 (N03), though it commonly is written U02(N03)2(H20)6. Thus, in solution as well as in the solid salt, the UOf is surrounded by 6 HjO in an inner coordination sphere. In the solid nitrate salt, the distance du.o(nitrate) between the closest oxygen atoms of the nitrate anions, (0)2N0, and the U-atom is longer than the corresponding distance, du-o(water), to the water molecules, OH2, i.e., du.o(nitrate) > 4u.o(water) thus the nitrate anions are in an outer coordination sphere. 

Table 8.20 Metal-organic complexing (log j3°) for some trace elements in aqueous solution at pH = 8.2, T = 25 °C. I ionic strength of solution. References (1) Turner et al. (1981) (2) Mantoura et al. (1978) (3) Stevenson (1976).

Impressive improvements in our knowledge of thermodynamic properties of the various organic hgands and of our capability of calculating metal-organic complexation constants at the various P and T conditions of interest come from the systematizations of Shock and Helgeson (1990) and Shock and Koretsky (1995), which evaluated equation of state parameters to be used in the revised... 

Shock E. L. and Koretsky C. M. (1995). Metal-organic complexes in geochemical processes Estimation of standard partial molal thermodynamic properties of aqueous complexes between metal cations and monovalent organic acid ligands at high pressures and temperatures. Geochim. Cosmochim. Acta, 59 1497-1532. 

The modern investigations of trace elements in coals were pioneered by Goldschmidt, who developed the technique of quantitative chemical analysis by optical emission spectroscopy and applied it to coal ash. In these earliest works, Goldschmidt (31) was concerned with the chemical combinations of the trace elements in coals. In addition to identifying trace elements in inorganic combinations with the minerals in coal, he postulated the presence of metal organic complexes and attributed the observed concentrations of vanadium, molybdenum, and nickel to the presence of such complexes in coal. 

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