Complexation silver ions

Olefin Complexes. Silver ion forms complexes with olefins and many aromatic compounds. As a general rule, the stabihty of olefin complexes decreases as alkyl groups are substituted for the hydrogen bonded to the ethylene carbon atoms (19). 

The impact that a silver compound has in water is a function of the free or weaMy complexed silver ion concentration generated by that compound, not the total silver concentration (3—5,27,40—42). In a standardized, acute aquatic bioassay, fathead minnows were exposed to various concentrations of silver compounds for a 96-h period and the concentration of total silver lethal to half of the exposed population (96-h LC q) deterrnined. For silver nitrate, the value obtained was 16 )-lg/L. For silver sulfide and silver thiosulfate complexes, the values were >240 and >280 mg/L, respectively, the highest concentrations tested (27). 

Physical development is another type of development, in which soluble and usually complexed silver ion is reduced from solution onto nuclei, which can be latent image nuclei, other suitable nuclei, or silver produced by chemical development. Chemical development and physical development are traditional terms derived... 

The latent image catalyzes the reduction of silver ion either from the solid silver halide phase, as in chemical development, or from a soluble source of silver ion, as in physical development (Figure 21). One view of chemical development is that interstitial silver ions move through the silver halide crystal and are reduced on the underside of the latent image speck. In purely physical development complexed silver ion moves through the solution and is reduced on the nucleus. In this sense physical development and the early stages of chemical development are similar. 

The immobilisation of antibacterial coatings onto conductive materials such as stainless steel or carbon fibre used in orthopaedic implants was investigated by two methods. The formation of thin films by electrodeposition of polypyrrole doped with polyanions able to complex silver ions, and their characterisation by SEM, FTIR and microbiological testing is described. The alternative method, involving chemical grafting of a thin film of a quatemaiy ammonium polymer using a surface initiator, is also discussed. 2 refs. 

The transient product of the reduction of complexed silver ions is not the isolated atom but a complexed silver atom, Ag (CN)2 -, ... 

H NMR spectra (DMSO-dg) of the Ag" complexes of ruthenocenophanes (81) and (82) suggest no interaction between the ruthenium and the complexed silver ion. In this case, the methylene protons attached to sulfur atoms were shifted more than the protons of the ruthenocene nucleus. H NMR spectra of the mercury(II) complexes of (80)-(82) suggest that there is signihcant interaction between ruthenium and the mercury(II). The P protons of the Cp rings were shifted further downfield than the a protons, and the ethylene protons exhibited very little downfield shift <85BCJ3540>. 

The band maxima of metal species are different in the gaseous and condensed phases. The optical absorption bands of Ag° and Ag2 are highly dependent on the environment [45]. As shown in Table 1 and Fig. 2, the influence of the interaction of ligands CN, NH3, or EDTA with the atom or the dimer is important [46]. The transient product of the reduction in water of complexed silver ions is not the isolated atom but a complexed silver atom, Ag°(CN)2 [37], Ag°(NH3)2 [47], or Ag (EDTA) [37,48], respectively (Fig. 2), as well... 

Vielstich, W. and Gerischer, H. (1955) Electrolysis at constant potential. II. Kinetics of the deposition of simple zinc and complex silver ions. Z. Phys. Chem., 4, 10-23. 

As well as the cr-complexes discussed above, aromatic molecules combine with such compounds as quinones, polynitro-aromatics and tetra-cyanoethylene to give more loosely bound structures called charge-transfer complexes. Closely related to these, but usually known as Tt-complexes, are the associations formed by aromatic compounds and halogens, hydrogen halides, silver ions and other electrophiles. 

In TT-complexes formed from aromatic compounds and halogens, the halogen is not bound to any single carbon atom but to the 7r-electron structure of the aromatic, though the precise geometry of the complexes is uncertain. The complexes with silver ions also do not have the silver associated with a particular carbon atom of the aromatic ring, as is shown by the structure of the complex from benzene and silver perchlorate. ... 

The use of silver fluoroborate as a catalyst or reagent often depends on the precipitation of a silver haUde. Thus the silver ion abstracts a CU from a rhodium chloride complex, ((CgH )2As)2(CO)RhCl, yielding the cationic rhodium fluoroborate [30935-54-7] hydrogenation catalyst (99). The complexing tendency of olefins for AgBF has led to the development of chemisorption methods for ethylene separation (100,101). Copper(I) fluoroborate [14708-11-3] also forms complexes with olefins hydrocarbon separations are effected by similar means (102). 

An acidimetric quantitative determination is based on treatment of the hydantoia with silver nitrate and pyridine ia aqueous solution. Complexation of the silver ion at N-3 Hberates a proton, and the pyridinium ions thus formed are titrated usiag phenolphthaleia as an iadicator. In a different approach, the acidity of N-3—H is direcdy determined by neutralization with tetrabutylammonium hydroxide or sodium methoxide ia dimethylformarnide. 

Silver Chloride. Silver chloride, AgCl, is a white precipitate that forms when chloride ion is added to a silver nitrate solution. The order of solubility of the three silver halides is Cl" > Br" > I. Because of the formation of complexes, silver chloride is soluble in solutions containing excess chloride and in solutions of cyanide, thiosulfate, and ammonia. Silver chloride is insoluble in nitric and dilute sulfuric acid. Treatment with concentrated sulfuric acid gives silver sulfate. 

Silver Thiosulfate. Silver thiosulfate [23149-52-2], Ag 2 y is an insoluble precipitate formed when a soluble thiosulfate reacts with an excess of silver nitrate. In order to minimize the formation of silver sulfide, the silver ion can be complexed by haUdes before the addition of the thiosulfate solution. In the presence of excess thiosulfate, the very soluble Ag2(S203) 3 and Ag2(S203) 3 complexes form. These soluble thiosulfate complexes, which are very stable, are the basis of photographic fixers. Silver thiosulfate complexes are oxidized to form silver sulfide, sulfate, and elemental sulfur (see Thiosulfates). 

Silver ions form a number of complexes with both TT-bonding and non-TT-bonding ligands. Linear polynuclear complexes are known. The usual species are AgL and AgL2, but silver complexes up to AgL have been identified. Many of these complexes have commercial appHcation. 

Ammonia and Amine Complexes. In the presence of excess ammonia (qv), silver ion forms the complex ions Ag(NH3) 2 7 -g(NH3) 3. 

Halide Complexes. Silver hahdes form soluble complex ions, AgX and AgX , with excess chloride, bromide, and iodide. The relative stabihty of these complexes is 1 > Br > Cl. Complex formation affects solubihty greatiy. The solubihty of silver chloride in 1 A/ HCl is 100 times greater than in pure water. 

Sulfur Complexes. Silver compounds other than sulfide dissolve in excess thiosulfate. Stable silver complexes are also formed with thiourea. Except for the cyanide complexes, these sulfur complexes of silver are the most stable. In photography, solutions of sodium or ammonium thiosulfate fixers are used to solubilize silver hahdes present in processed photographic emulsions. When insoluble silver thiosulfate is dissolved in excess thiosulfate, various silver complexes form. At low thiosulfate concentrations, the principal silver species is Ag2(S203) 2j high thiosulfate concentrations, species such as Ag2(S203) 3 are present. Silver sulfide dissolves in alkaline sulfide solutions to form complex ions such as Ag(S 2 Ag(HS) 4. These ions are... 

Silver compounds having anions that are inherently toxic, eg, silver arsenate and silver cyanide, can cause adverse health effects. The reported rat oral LD values for silver nitrate, silver arsenate [13510-44-6] and silver cyanide are 500—800 (29), 200—400 (29), and 123 mg/kg (30), respectively. Silver compounds or complexes ia which the silver ion is not biologically available, eg, silver sulfide and silver thiosulfate complexes, are considered to be without adverse health effects and essentially nontoxic. 

Free ionic silver readily forms soluble complexes or insoluble materials with dissolved and suspended material present in natural waters, such as sediments and sulfide ions (44). The hardness of water is sometimes used as an indicator of its complex-forming capacity. Because of the direct relationship between the availabiUty of free silver ions and adverse environmental effects, the 1980 ambient freshwater criterion for the protection of aquatic life is expressed as a function of the hardness of the water in question. The maximum recommended concentration of total recoverable silver, in fresh water is thus given by the following expression (45) in Fg/L. 

In secondary wastewater treatment plants receiving silver thiosulfate complexes, microorganisms convert this complex predominately to silver sulfide and some metallic silver (see Wastes, INDUSTRIAL). These silver species are substantially removed from the treatment plant effluent at the settling step (47,48). Any silver entering municipal secondary treatment plants tends to bind quickly to sulfide ions present in the system and precipitate into the treatment plant sludge (49). Thus, silver discharged to secondary wastewater treatment plants or into natural waters is not present as the free silver ion but rather as a complexed or insoluble species. 

Electroplating. Most silver-plating baths employ alkaline solutions of silver cyanide. The silver cyanide complexes that are obtained in a very low concentration of free silver ion in solution produce a much firmer deposit of silver during electroplating than solutions that contain higher concentrations. An excess of cyanide beyond that needed to form the Ag(CN)2 complex is employed to control the concentration. The silver is added to the solution either directly as silver cyanide or by oxidation of a silver-rod electrode. Plating baths frequently contain 40—140 g/L of silver cyanide... 

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