Ferric precipitates

The above reaction represents, in a simplified way, the origin of acid mine drainage. Streambeds in areas of acid drainage characteristically become coated with an orange layer of ferric precipitate. We can write a reaction representing the overall process by swapping ferric hydroxide in place of the ferrous ion ... 

It is useful to compare the capacity for each metal to be sorbed (the amount of each that could sorb if it occupied every surface site) with the metal concentrations in solution. To calculate the capacities, we take into account the amount of ferric precipitate formed in the calculation (0.89 mmol), the number of moles of strongly and weakly binding surface sites per mole of precipitate (0.005 and 0.2, respectively, according to the surface complexation model), and the site types that accept each metal [As(OH)4 and ASO4 sorb on weak sites only, whereas Pb++, Cu++, and Zn++ sorb on both strong and weak]. 

Next we explore using the 5 Fe value of the ferric oxide/oxyhydroxide precipitate as a proxy for 5pe(ni)aq, which allows Equation (21) to be used to calculate the Ape(ni)-Fe(n) fractionation from the measured 5 Fe values for the ferric precipitate and Fe(II)aq. This approach is valid when the molar proportion of Fe(III)3q is very small. However, if there is a significant Fe isotope fractionation between Fe(III)3q and ferric hydroxide precipitate, this must be taken into account. As discussed in the previous chapter (Chapter 10A Beard and Johnson 2004), at low... 

Figure 16. Conceptual model for biological redox cycling in a hot spring environment. Influx of external aqueous Fe(II) [Aeap-Ext] may reflect hydrothermal fluids or other sources of Fe(II),q. Oxidation of Fe(II),qis envisioned to occur by Fe(II)-oxidizing phototrophs in anaerobic conditions, but could also occur through interaction of Fe(II), with an oxygen-rich atmosphere. Oxidation of Fe(II) produces a flux of ferric oxide/hydroxide precipitates [Aeanjppt] that settle to the lower, anaerobic sections of the pool. These ferric precipitates are in turn partially reduced by DIR bacteria, returning a flux of Fe(II), to the pool [Aem-Bio] ...

Rose, S. Elliott, W.C. (2000) The effects of pH regulation upon the release of sulfate from ferric precipitates formed in acid mine drainage. Appl. Geochem. 15 27-34 Rosier, H.J. (1983) Lehrbuch der Mineralogie. Verlag fiir Grundstoffindustrie, Leipzig,... 

The empirical rate law in Eq. 23 holds only for the initial rates. Tamura et al. (1976) observed an autocatalytic effect of the ferric precipitates produced in the reaction. Sung and Morgan (1980) identified y-FeOOH as the primary oxidation product at neutral pH and confirmed its autocatalytic effect. Adsorbed Fe(II) seems to compete in an additional parallel reaction with the dissolved ferrous species. Fast surface reaction rates resulted from a fit of the kinetic data. Examples of these constants are included in Fig. la for comparison. They represent only estimates of an order of magnitude because Tamura et al. (1976) did not determine the surface concentration of Fe(II). However, Figure 2 shows qualitatively that the ferrous ion is adsorbed specifically to mineral surfaces. 

A typical example is that of ferric precipitation in white wines (Section 4.6.2). Aeration of wine leads to the oxidation of ferrous iron to ferric iron. Relatively insoluble ferric phosphate is formed. The molecules agglomerate, forming colloidal... 

Anhydrous cupric sulphate is white but forms a blue hydrate and a blue aqueous solution. The solution turns yellow when treated with concentrated hydrochloric acid, dark blue with ammonia, and gives a white precipitate and brown solution when treated with potassium iodide. A yellow-brown aqueous solution of ferric chloride becomes paler on acidification with sulphuric or nitric... 

Dissolve a small portion of the sodium derivative in a few mi. of water in a test-tube, and add one drop of ferric chloride solution. A deep red coloration is produced, but rapidly disappears as the iron is precipitated as ferric hydroxide. The sodium (derivative (A) of the nitromethane wh dissolved in water undergoes partial hydrolysis,... 

Add about 0 2 g. of ferrous sulphate crystals to the first portion of the filtrate contained in a boiling-tube. An immediate dark greenish-grey precipitate of ferrous hydroxide should occur if the mixture remains clear, add a few ml. of sodium hydroxide solution. Now boil the mixture gently for a few minutes to ensure formation of the ferrocyanide, cool under the tap, add one drop of ferric chloride solution, and then acidify... 

Ferric chloride solution sometimes contains a large excess of HCl which would interfere with the following reactions. If it is very markedly acidic add dil. NaOH solution, drop by drop, to the ferric chloride solution until a small but permanent precipitate of ferric hydroxide is obtained. Filter this off through a small fluted filter paper, and use the clear filtrate. The latter is still not quite neutral owing to hydrolysis, but this feeble acidity does not interfere with the tests given below. 

Colorations or coloured precipitates are frequently given by the reaction of ferric chloride solution with.(i) solutions of neutral salts of acids, (ii) phenols and many of their derivatives, (iii) a few amines. If a free acid is under investigation it must first be neutralised as follows Place about 01 g. of the acid in a boiling-tube and add a slight excess of ammonia solution, i,e., until the solution is just alkaline to litmus-paper. Add a piece of unglazed porcelain and boil until the odour of ammonia is completely removed, and then cool. To the solution so obtained add a few drops of the "neutralised ferric chloride solution. Perform this test with the following acids and note the result ... 

Dissolve 2 3 drops of o toluidine in a few drops of dil. HCl and add 2 3 drops of ferric chloride solution a green coloration is produced and is slowly replaced by a bluish-green or blue precipitate. 

Unless all the excess of ammonia has been driven off in the preparation of the neutral salt, the result obtained on adding ferric chloride will be misleading owing to the precipitation of ferric hydroxide. If this is suspected, the tests should be repeated using an aqueous solution of the pure sodium salts of these acids for comparison. 

The neutral salts of many acids treated with ferric chloride give colorations or precipitates. 

Ferric chloride reaction. For the success of this reaction it is important that the solution should be neutral. Excess of acid usually inhibits the production of colour or precipitate, and excess of alkali gives a reddish-brown precipitate of ferric hydroxide. A neutral solution may be made as follows ... 

Succinate, benzoate, phthalate and cinnamate give buff or brownish coloured precipitates of the basic ferric salts in the cold. Add dil. H2SO4. The basic ferric succinate dissolves giving a clear solution the other basic ferric salts also dissolve, but simultaneously a white precipitate of the free acid is also formed. 

Dissolve 100 g. of iron alum (ferric ammonium sulphate) in 300 ml. of water at 65°, Pour the solution, with stirring, into a solution of 25 g. of hydroquinone in 100 ml, of water contained in a 600 ml. beaker. The quinhydrone is precipitated in fine needles. Cool the mixture in ice, filter with suction, and wash three or four times with cold water. Dry in the air between filter paper. The yield of quinhydrone, m.p, 172°, is 15 g. It contains a trace of iron, but this has no influence upon the e.m.f, of the quinhydrone electrode provided that the washing of the crude material has been thorough. The quinhydrone should be stored in a tightly-Btoppered bottle. 

Prepare the neutral ferric chloride solution (i.e., free from hydrochloric acid) by adding dilute sodium hydroxide solution dropwise to the bench reagent until a slight precipitate of ferric hydroxide is formed. Filter off the precipitate and use the clear filtrate for the test. 

In the removal of contaminating ions such as (PO or Fe " a precipitate such as Ca2(P0 2 Fe(OH)2, after oxidizing ferrous ion to ferric, is formed and the soHd is removed. The addition of surfactants is usually not essential (nor desirable) since most waters contain natural surfactants that would render the soflds sufficiently hydrophobic for flotation to occur. Such surfactants derive from the degradation of organic matter, and humic substances abundantly available in nature (30). 

Thus, at a concentration of 0.95 g Na2S /100 g solution, the solubihty of mercuric sulfide has increased to 2100 ppm. It is customary to use no greater than a 20% excess of the alkah sulfide. Because the particle size of the precipitated mercuric sulfide is so small, it is helpful to add a ferric compound such as ferric chloride or ferric sulfate to effect flocculation. Sometimes other flocculating agents (qv) may also be added, eg, starch or gum arabic. 

Hydrogenis prevented from forming a passivating layer on the surface by an oxidant additive which also oxidizes ferrous iron to ferric iron. Ferric phosphate then precipitates as sludge away from the metal surface. Depending on bath parameters, tertiary iron phosphate may also deposit and ferrous iron can be incorporated into the crystal lattice. When other metals are included in the bath, these are also incorporated at distinct levels to generate species that can be written as Zn2Me(P0 2> where Me can represent Ni, Mn, Ca, Mg, or Fe. 

Metals and Metallic Ions. Under appropriate conditions, ozone oxidizes most metals with the exception of gold and the platinum group. When oxidized by ozone, heavy metal ions, such as Fe and Mn , result in the precipitation of insoluble hydroxides or oxides upon hydrolysis (48—50). Excess ozone oxidizes ferric hydroxide in alkaline media to ferrate, and Mn02 to MnO. ... 

In the double-neutralization process, Na2SiFg is precipitated and removed by filtration at a pH of 3—4 (9). Upon raising the pH to 7—9, insoluble phosphates of Fe, Al, Ca, and Mg form and separate. Iron can be precipitated as hydrous ferric oxide, reducing the phosphate loss at the second filter cake. Both the fluorosihcate and metal phosphate filter residues tend to be voluminous cakes that shrink when dewatered recovery of soluble phosphates trapped within the cakes is difficult. 

In the direct precipitation process, the seeds of iron(III) oxide are added to an iron salt solution, most often iron(II) sulfate, which is subsequendy oxidized by air. The released sulfuric acid is removed by the addition of metallic iron with which it reacts to iron(II) sulfate. The overall reaction shows that ferrous sulfate is not consumed during the process. It only helps to oxidize metallic iron to ferric oxide ... 

The Penniman-Zoph process involves the preparation of seeds or nucleating particles by the alkaU precipitation of ferrous sulfate. The reaction is carried out at alow temperature using an excess of ferrous ions. The hydroxide is then oxidized to the seeds of hydrated ferric oxide ... 

Iron oxide yellows can also be produced by the direct hydrolysis of various ferric solutions with alkahes such as NaOH, Ca(OH)2, and NH. To make this process economical, ferric solutions are prepared by the oxidation of ferrous salts, eg, ferrous chloride and sulfate, that are available as waste from metallurgical operations. The produced precipitate is washed, separated by sedimentation, and dried at about 120°C. Pigments prepared by this method have lower coverage, and because of their high surface area have a high oil absorption. 

Iron Browns. Iron browns are often prepared by blending red, yellow, and black synthetic iron oxides to the desired shade. The most effective mixing can be achieved by blending iron oxide pastes, rather than dry powders. After mixing, the paste has to be dried at temperatures around 100°C, as higher temperatures might result in the decomposition of the temperature-sensitive iron yellows and blacks. Iron browns can also be prepared directiy by heating hydrated ferric oxides in the presence of phosphoric acid, or alkaU phosphates, under atmospheric or increased pressure. The products of precipitation processes, ie, the yellows, blacks, and browns, can also be calcined to reds and browns. 

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