Mercury ions cobalt complexes

Sulphuric acid is not recommended, because sulphate ions have a certain tendency to form complexes with iron(III) ions. Silver, copper, nickel, cobalt, titanium, uranium, molybdenum, mercury (>lgL-1), zinc, cadmium, and bismuth interfere. Mercury(I) and tin(II) salts, if present, should be converted into the mercury(II) and tin(IV) salts, otherwise the colour is destroyed. Phosphates, arsenates, fluorides, oxalates, and tartrates interfere, since they form fairly stable complexes with iron(III) ions the influence of phosphates and arsenates is reduced by the presence of a comparatively high concentration of acid. 

During oxidation of tin(II) ions by hydrogen peroxide, iodine, bromine, mercury(ir) and thallium(III) the induced reduction of cobalt(in) complexes cannot be observed. Therefore, it was concluded that these reactions proceed by 2-equivalent changes in the oxidation states of the reactants. 

Metal ion catalyzed substitutions for the halide (or methyl) ligands of cobalt(III) complexes are well documented (24, 25). Mercury(II) is particularly effective in catalyzing such simple hydrolytic substitutions on Co(III). However,... 

Chloropentaamminecobalt(III) chloride forms red-violet rhomb-shaped crystals which decompose on heating above 150° with the stepwise loss of ammonia. The solubility of the salt in water at 25° is 0.4 g./lOO ml. The compound readily aquates in hot water, forming the aquopentaammine chloride. Chloropentaamminecobalt(III) chloride reacts with hot aqueous ethylenediamine or dZ-propylenediamine to form tris (ethylenediamine) cobalt (III) chloride or the corresponding propylenediamine compound, with liberation of ammonia. Concentrated sulfuric acid at room temperature produces a complex hydrogen sulfate of the chloro-pentaamminecobalt(III) ion. Aqueous mercury(II) chloride forms a characteristic precipitate of a double salt, [Co(NH3)6Cl]Cl2-3HgCl2, suitable for microchemical identification. Complete physical and chemical data may be found in Gmelin s handbook. ... 

The concentration of (EDTA) ", and thus the ability to complex metal ions, will depend upon the pH. A decrease in pH results in an increase in the deprotonation of EDTA and hence an increase in the concentration of the ED I A ion. The effect of this is that only metal ions with a very high affinity for EDTA will be able to form stable complexes. The stability constants for the EDTA and [diethylenetriaminepentaacetic acid] - (DTPA ) complexes with some important metal ions that are of particular interest for chelation therapy are listed in Table 7.3. It is important to note that the stability of the EDTA and DTPA complexes with toxic metals, such as lead, mercury, cadmium, or plutonium are quite similar to those with essential metals such as zinc, cobalt or copper however, the Ca complex is many orders of magnitude lower. This has important implications for chelation therapy. First, the mobilization and excretion of zinc and other essential metals are likely to be increased, along with that of the toxic metal during EDTA treatment and secondly, the chelation of the ionic calcium in the blood, that can cause tetany and even death, can be avoided by administering the chelator as the calcium salt. 

Hydrolysis of complexes of the type MFe is catalysed not only by acid but also by a series of metal ions. Kinetic data have been obtained for catalysis of hydrolysis of PFe, AsFg", AsFgCOH)- and also of BF4-, by beryllium(ii), aluminium(iii), zirconium(iv), and thorium(rv). Again this may be seen as an extension of studies on cation catalysis of hydrolysis of transition-metal complexes, e.g. the numerous studies of mercury(ii)-catalysed aquations of cobalt(iii)-ammine-halide complexes, or the recent study of metal ion catalysis of chloro(ethylenediaminetriacetato)-cobaltate(m). ... 

Adsorption by carbon, which is one of the oldest adsorption methods used, has been reviewed and evaluated for the preconcentration of trace metals (794). Many authors have discussed the preparation of activated charcoal and carbon from a wide variety of usually local sources. The applications to water treatment are far too numerous to mention other than a few. Jo (795) carbonized a resin and a gum and hydrated the residue above 600 C to produce an adsorbant selective for cadmium(II). Kuzin et al, 196) used deashed active carbon and oxidized carbon for the quantitative sorption of copper, lead, zinc, and nickel from nearly neutral solutions containing 1-2 M alkali-metal halide. Pearson and Siviour (797) converted the metal-ion species to amine complexes before adsorbing these onto carbonaceous materials such as brown charcoal char or cellulose. Mercury vapor can be removed from a solution by reduction followed by passage of a nitrogen stream and adsorption by activated charcoal (798). Activated carbon, which had been oxidized with nitric acid, has been used to extract several metals including divalent nickel, cadmium, cobalt, zinc, manganese, and mercury from fresh water, brine, and seawater (799, 200). 

Kinetic studies of the transfer of co-ordinated carbanions from cobalt(in) to mercury(n) are reported for two families of model vitamin 613 compounds. Previous studies in this area have indicated a single-step mechanism, with occasional complications such as the complexing of the benzimidazole of cobalamins by the mercury(n) ion, and the protonation of cobaloximes. In the recent study with complexes of the type /ra s-[RCo(L)OH2] [L = (12) L = salen = (13)],... 

The mechanism of 1 1 complex formation between palladium(II) and catechol and 4-methylcatechol has been studied in acidic media, and the rate of 1 1 (and 1 2) complex formation between silver(II) and several diols is an order of magnitude higher in basic solution than in acidic. The kinetics of formation and dissociation of the complex between cop-per(II) and cryptand (2,2,1) in aqueous DMSO have been measured and the dissociation rate constant, in particular, found to be strongly dependent upon water concentration. The kinetics of the formation of the zinc(II) and mercury(II) complexes of 2-methyl-2-(2-pyridyl)thiazolidine have been measured, as they have for the metal exchange reaction between Cu " and the nitrilotriacetate complexes of cobalt(II) and lead(II). Two pathways are observed for ligand transfer between Ni(II), Cu(II), Zn(II), Cd(II), Pb(II) and Hg(II) and their dithiocarbamate complexes in DMSO the first involves dissociation of the ligand from the complex followed by substitution at the metal ion, while the second involves direct electrophilic attack by the metal ion on the dithiocarbamate complex. As expected, the relative importance of the pathways depends on the stability of the complex and the lability and electrophilic character of the metal ion. 

Rate constants have been determined for mercury(II)-catalyzed aquation of the hexachlororhenate(IV) anion in a range of binary aqueous solvent mixtures. With the aid of ancillary information on Gibbs free energies of transfer for the reactant ions from water into the solvent mixtures it proved possible to analyze the observed reactivity trends into initial state and transition state components. The results are discussed below, in conjunction with a parallel study of mer-cury(II) catalysis of aquation of chloro-cobalt(III) complexes. 

Metal Ion Catalysis.—Mercury(u). The most commonly encountered catalyst for aquation of cobalt(m) complexes is mercury(n). In aquation of a series of complexes c y-[Co(en)2LCl] +, where L = an alkylpyridine, the mechanism proposed is a rapidly established pre-equilibrium... 

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