Structure,insertion electrochemistry,and magnetic properties of a new type of substitutional solid solutions of copper,nickel, and iron hexacyanoferrates/hexacyanocobaltates

Substitutional solid solutions of metal hexacyanometalates in which low-spin iron(III) and cobalt(III) ions populate the carbon-coordinated sites were synthesized and studied by powder diffraction including Rietveld refinement, cyclic voltammetry of immobilized microparticles, diffuse reflection vis-spectrometry, and magnetization techniques. The continuous solid solution series of potassium copper(II), potassium nickel(II), and iron(III) [(hexacyanoferrate(III))(1-x)(hexacyanocobaltate(III))(x)] show that the substitution of low-spin iron(III) by cobalt(III) in the hexacyanometalate units more strongly affects the formal potentials of the nitrogen-coordinated copper(II) and high-spin iron(III) ions than those of the remaining low-spin iron(III) ions. In the case of copper(II) and iron(III) [(hexacyanoferrate(III))(1-x)(hexacyanocobaltate(III))(x)] the peak currents decrease much more than can be explained by stoichiometry, indicating that the charge propagation is slowed by the substitution of low-spin iron(III) by cobalt(III). The Rietveld refinement of all compounds confirmed the structure initially proposed by Keggin for Prussian blue and contradicts the structure described later by Ludi. The dependencies of lattice parameters on composition exhibit in all series of solid solutions studied similar, although small, deviations from ideality, which correlate with the electrochemical behavior. Finally, a series of solid solutions of the composition KNi(0.5)(II)Cu(0.5)(II)[Fe(III)(CN)(6)](1-x)[Co(III)(CN)(6)](x), where both the nitrogen- and carbon-coordinated metal ions are mixed populated and were synthesized and characterized. These are the first examples of solid solutions of metal hexacyanometalates with four different metal ions, where both the nitrogen- and the carbon-coordinated sites possess a mixed population.     

Deep Purification of Aqueous Solutions To Remove Iron(III) with Carbonate-Containing Industrial Waste

The possibility of using a carbonate-containing industrial waste in purification of aqueous solutions to remove iron(III) ions to below the maximum permissible concentration was analyzed. The sorbent capacities were calculated for iron(III) solutions with various initial concentrations. The influence exerted by the time, temperature, anionic composition of iron(III) salt solutions, and other factors on sorption was assessed.     

Intradiffusion and viscosity measurements in acidified iron(III) chloride solutions at 25°C

Intradiffusion of species in acidified (using eithe hydrochloric or perchloric acid) iron(III) chloride solutions has been studied using labeled iron(III), chloride and water. Comparison with data for iron(III) perchlorate has enabled the influence of complexed species upon the diffusion to be ascertained. The chloro-iron species formed have larger diffusion coefficients than the free iron(III) ion as would be expected from their lower net charge. Simple diffusion models have been employed to enable estimates of the diffusion of the complexed species and of the free chloride diffusion coefficients to be obtained. These are discussed in relation to literature data for similar systems. In addition esitmates of the effective hydration of the iron(III) species in solutions have been obtained from the diffusion data. These are discussed in relation to two other trivalent metal salt systems, chromium chloride and lanthanum chloride; the overall hydration of the three cations is virtually identical.     

Study of the mechanism of the electrochemical reduction of hydrolysed iron(III) species,in connection with their colloidal properties

The voltammetric properties of hydrolysed iron(III) solutions are studied. A characteristic polarographic wave related to a polymeric compound, whose molecular weight is about 5000–10000, is observed in these solutions. A quantitative interpretation of this wave is proposed. Its usefulness for the control of hydrolysis of iron(III) solution, and for the control of the coagulation process of silicates with iron(III) solutions, with regards to chemical water treatment is discussed.     

Sorption of iron(III) in ionic and colloidal states on iron(III) oxide deposited on a silica gel sufrace

The sorption of iron(III) in ionic and colloidal states on iron(III) oxide deposited on a silica gel surface has been studied as a function of pH of aqueous solution by batch equilibrations. The behaviour of Fe³⁺ and colloidal Fe(III) on the sorbent column has also been investigated. Conditions for sorption of iron from aqueous solutions are given. The colloidal iron(III) can be quantitatively separated from Fe³⁺ on the sorbent column under given experimental conditions.     

Chemical sensors based on metal-electrolyte-insulator-semiconductor structures for determining carbon dioxide in air

Separation of iron(III) and palladium(III) in recovery from binary hydrochloric solutions with liquid membranes containing diphenylthiocarbamide in 1,2-dichloroethane was studied under galvanostatic electrodialysis conditions. The effect of the current density, process duration, and compositions of the receiving solution and liquid membrane on the iron(III) recovery rate was examined.     

Electrodialytic recovery of iron(III) with liquid membranes based on diphenylthiocarbamide in the presence of palladium(II)

Separation of iron(III) and palladium(III) in recovery from binary hydrochloric solutions with liquid membranes containing diphenylthiocarbamide in 1,2-dichloroethane was studied under galvanostatic electrodialysis conditions. The effect of the current density, process duration, and compositions of the receiving solution and liquid membrane on the iron(III) recovery rate was examined.     

Spectrophotometric titration of bismuth with EDTA

A new spectrophotometnc method for the estimation of bismuth with EDTA, using iron-salicylate complex as the indicator, has been developed. The determinations were carried out by measuring the absorbance at 520 mmu. of solutions containing bismuth, iron(III), salicylic acid and various quantities of EDTA, at pH 0.5. It has been shown from the stability constants of the complexes present that before the end-point iron(III) will not react appreciably with the Bi-EDTA complex. The interference from iron(III) in the estimation of bismuth, which is a serious drawback in many other methods, is eliminated in the present method, as iron(III) acts as the indicator.     

Niobium(III) as an analytical reagent. : Part I. The titrimetric determination of iron,copper, thallium,molybdenum, uranium and vanadium

Niobium(III) solutions can be used in direct titrations of copper(II), iron(III), thallium(III), moIybdenum(VI), vanadium(V) and uranium(VI) in milligram amounts. Phenosafranine is generally satisfactory as the indicator, but potentiometric end-points can also be used. Copper and iron can be determined successively when a mixed indicator containing phenosafranine and méthylene blue is used. Thallium(I) and thallium (III) can be determined in mixtures. The niobium (III) solutions are stable for several days under a carbon dioxide atmosphere.     

Electrochemical and spectral studies on the reductive nitrosylation of water-soluble iron porphyrin

The reaction of iron(III) (meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (Fe(III)TMPyP) with nitric oxide (NO) was studied by electronic absorption spectroscopy, ESR, and electrochemical and spectroelectrochemical techniques in aqueous solutions with pH from 2.2 to 12.0. Fe(III)TMPyP has been found to undergo a reductive nitrosylation in all pHs, and the product of nitric oxide binding to the porphyrin has been determined as iron(II) porphyrin nitrosyl complex ([Fe(II)(NO)TMPyP]). The rate of the reductive nitrosylation exhibits a tendency to get faster with increase in pH. An intermediate species was observed around neutral pH by spectroelectrochemical technique and was proposed to be the iron(II) nitrosyl complex of the mu-oxo dimeric form of FeTMPyP, which is known to be a predominant in neutral solutions.     

Kinetics of Fe(III) → Fe(0) Reduction on Aluminum in Aqueous Solutions

The reduction of iron(III) ions by dispersed aluminum in chloride-containing aqueous solutions and the influence exerted by the initial iron(III) ion concentration and the degree of aluminum dispersion on the kinetics of the process were studied.     

Studies on extraction of iron(III) and cobalt(II) chlorides by quaternary ammonium halides

Summary The extraction of iron(III) and cobalt(II) from hydrochloric acid solutions by Hyamine 1622, a quaternary ammonium halide, in dichloroethane is described. The effect of acidity, salting-out agent, metal and extradant concentrations and temperature, has been investigated. The extraction mechanism is discussed in the light of results obtained. Separation of iron(III) and cobalt(II) is also outlined.     

Extraction studies on iron

The extraction of Fe(III) and Fe(II) from various aqueous acidic solutions, with nitrobenzene, Amberlite LA-2, TBP and HDEHP is described. Conditions are given for the separation of Fe(III) from Fe(II). The extraction and separation of Fe(III) and Fe(II) is most adequate from HCl solutions, using the four solvents. The extraction of iron halides from H₂SO₄ solutions has been studied. The effect of water-miscible alcohols on the distribution of Fe(III) and Fe(II) was also studied. Extraction equilibria and mechanisms were proposed on the basis of the obtained results.     

Selective extraction of iron(III) from aqueous nitrate solution in the presence of cobalt(II), copper(II) and nickel(II) ions using bis(delta2-2-imidazolinyl)-5,5'-dioxime.

The feasibility of using bis(delta2-2-imidazolinyl)-5,5'-dioxime (H2L) for the selective extraction of iron(III) from aqueous solutions was investigated by employing an solvent-extraction technique. The extraction of iron(III) from an aqueous nitrate solution in the presence of metal ions, such as cobalt(II), copper(II) and nickel(II), was carried out using H2L in binary and multicomponent mixtures. Iron(III) extraction has been studied as a function of the pH, equilibrium time and extractant concentration. From the extracted complex species in the organic phase, iron(III) was stripped with 2 M HNO3, and later determined using atomic-absorption spectrometry. The extraction was found to significantly depend on the aqueous solution pH. The extraction of iron(III) with H2L increases with the pH value, reaching a maximum in the zone of pH 2.0, remaining constant between 2 and 3.5 and subsequently decreasing. The quantitative extraction of iron(III) with 5 x 10(-30 M H2L in toluene is observed at pH 2.0. H2L was found to react with iron(III) to form ligand complex having a composition of 1:2 (Fe:H2L).     

Vacuum balance and related studies of green and red rusts

Green and red rusts are formed when iron is partially or completely oxidised. Analogues of the rusts may be precipitated from iron(II) and iron (III) salt solutions treated with alkali under reducing or oxidising conditions. Variations in surface area and porosity have been investigated by gravimetric nitrogen gas sorption, using vacuum microbalance techniques.Freshly-precipitated red rusts, hydrous iron (III) oxide, have surface areas of about 200–400 m²g^?1. When they are added to iron (II) hydroxide suspensions kept at pH 7, the green Fe (II)-Fe (III) rusts formed have lower surface areas of about 40–100 m²g^?1, depending on the initial iron(II) sulphate concentrations.     

Chelating ion-exchangers containing n-substituted hydroxylamine functional groups: Part V. Iron,copper, and uranium separations on Duolite CS-346 resin

The separation of iron(III), copper(II) and uranyl(II) ions from a series of salt solutions by chelating ion exchange on Duolite CS-346 resin by pH control is described. Recoveries of these ions from cobalt and nickel salt solutions were quantitative. Iron may also be separated from copper by selective sorption with pH control, and uranium from iron and copper by selective desorption with sodium carbonate solution as eluent.     

Intradiffusion coefficients for iron and water and shear viscosities in aqueous iron(II) perchlorate solutions at 25°C

Intradiffusion coefficients of iron(II) and water were determined in acidified solutions of iron(II) perchlorate for an iron concentration range of 0 to 2.5 mol-dm^–3 at 25°C. In addition ancillary shear viscosity and density data were measured for each solution. Results were compared with existing diffusion data for iron(III) perchlorate solutions and highlighted the differences in the solvent dynamics around the two metal ions. By use of a simple model the effective hydration of the iron(II) ion was estimated to be 12, comparable to that of other divalent, uncomplexed metal cations; the same model indicates an effective hydration of 19 for iron(III).     

Small-angle maxima and cation-cation distances. Differences between iron nitrate and perchlorate solutions

X-ray diffraction data of aqueous solutions of iron(III) nitrate show a small-angle peak at an s value of about 0.5–0.9 A^?1. A constant relationship between peak position and concentration leads to reject the hypothesis of a quasi-lattice structure for the solutions investigated. On the contrary, no peak is present in the same s range of diffraction data of iron (III) perchlorate solutions.     

A rapid titrimetric determination of iron in copper concentrates and copper-bearing leach solutions

A titrimetric method for the determination of iron(III) in the presence of copper is presented. This method involves the reduction of iron(III) with titanous sulphate followed by titration with dichromate. It has been successfully used for the determination of iron in both leach solutions and copper concentrates with a relative error of 1%.     

Determination of gallium in an iron-aluminium matrix by solvent extraction and flame emission spectroscopy

Solvent extraction of gallium(III) into methyl isobutyl ketone from hydrochloric acid solutions containing titanium (III) sulphate provides a rapid method for separation of gallium from an iron/aluminium matrix and may be employed to eliminate the interference of these elements in the flame emission spectrometric determination of gallium.