Insoluble precipitates

Thus far we have examined titrimetric methods based on acid-base, complexation, and redox reactions. A reaction in which the analyte and titrant form an insoluble precipitate also can form the basis for a titration. We call this type of titration a precipitation titration. 

Niobic Acid. Niobic acid, Nb20 XH2O, includes all hydrated forms of niobium pentoxide, where the degree of hydration depends on the method of preparation, age, etc. It is a white insoluble precipitate formed by acid hydrolysis of niobates that are prepared by alkaH pyrosulfate, carbonate, or hydroxide fusion base hydrolysis of niobium fluoride solutions or aqueous hydrolysis of chlorides or bromides. When it is formed in the presence of tannin, a volurninous red complex forms. Freshly precipitated niobic acid usually is coUoidal and is peptized by water washing, thus it is difficult to free from traces of electrolyte. Its properties vary with age and reactivity is noticeably diminished on standing for even a few days. It is soluble in concentrated hydrochloric and sulfuric acids but is reprecipitated on dilution and boiling and can be complexed when it is freshly made with oxaHc or tartaric acid. It is soluble in hydrofluoric acid of any concentration. 

Sequestration forms the basis for detergent and water-treatment appHcations of polyphosphates. Sequestration of hardness ions by sodium tripolyphosphate used in detergent formulations prevents the precipitation of surfactants by the hardness ions. Sodium polyphosphate glass (SHMP) may be added to water system to prevent the formation of calcium or magnesium scales by reducing the activity of the hardness ions. However, if the ratio of cation to polyphosphate is too high at a given pH, insoluble precipitates such as may result instead of the soluble polyphosphate complexes. The... 

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). 

Tantalic Acid and Tantalates. Tantahc acid [75397-94-3] Ta20 is the name of the white insoluble precipitate formed by hydrolysis... 

Precipitating (cathodic) inhibitors are simply chemicals that form insoluble precipitates that can coat and protect the surface precipitated films are not as tenacious as passive films and take longer to repair after a system upset. 

Both iron and aluminum are particulady troublesome because of their abiUty to act as coagulants. Also, their soluble and insoluble hydroxide forms can each cause precipitation of some water treatment chemicals, such as orthophosphate. Airborne contaminants usually consist of clay and dirt particles but can include gases such as hydrogen sulfide, which forms insoluble precipitates with many metal ions. Process leaks introduce a variety of contaminants that accelerate deposition and corrosion. 

An aqueous dispersion of an unmodified starch containing amylose wiU gradually form an insoluble precipitate through association of linear segments. This process is called retrogradation or set-back. 

Precipitation involves the alteration of the ionic equilibrium to produce insoluble precipitates. To remove the sediment, chemical precipitation is allied with solids separation processes such as filtration. Undesirable metal ions and anions are commonly removed from waste streams by converting them to an insoluble form. The process is sometimes preceded by chemical reduction of the metal ions to a form that can be precipitated more easily. Chemical equilibrium can be affected by a variety of means to change the solubility of certain compounds. For e.xample, precipitation can be induced by alkaline agents, sulfides, sulfates, and carbonates. Precipitation with chemicals is a common waste stream treatment process and is effective and reliable. The treatment of sludges is covered next. 

Neuberg and Tiemann propose the following method, depending on the fact that most aldehydes form a compound with thiosemi-car-bazide. The oil containing aldehyde is heated in alcoholic solution on a water-bath, with thiosemi-carbazide. Various salts of the heavy metals will form insoluble precipitates with the thiosemi-carbazone formed, and such precipitate is dissolved in alcohol, and a current of hydrogen sulphide passed through until the metal is precipitated, leaving the thiosemi-carbazone dissolved in the alcohol. 

Calcium ions in seawater muds can be controlled and removed by forming insoluble precipitates accomplished by adding alkalis such as caustic soda, lime, or barium hydroxide. Soda ash or sodium bicarbonate is of no value in controlling the total hardness of sea water. 

Components in the invading water-based filtrate and in the formation waters may react to form insoluble precipitates which can block the pores and give rise to skin damage. The scale can be formed by interaction of calcium-based brines with carbon dioxide or sulfate ions in the formation water. Alternatively sulfate ions in the invading fluid may react with calcium or barium ions in the formation water. Analysis of the formation water can identify whether such a problem may arise. 

Generally, the most common cations in the soil solution are potassium, sodium, magnesium and calcium. Alkali soils are high in sodium and potassium, while calcareous soils contain predominantly magnesium and calcium. Salts of all four of these elements tend to accelerate metallic corrosion by the mechanisms mentioned. The alkaline earth elements, calcium and magnesium, however, tend to form insoluble oxides and carbonates in nonacid conditions. These insoluble precipitates may result in a protective layer on the metal surface and reduced corrosive activity. 

The optimal temperature range for the fluorination process was found to be about 230-290°C. The resulting cake was leached with water. The prepared solution was separated from the precipitate by regular filtration and the separated insoluble precipitate was identified as lithium fluoride, LiF. The solution contained up to 90 g/1 Ta205. Solution acidity was relatively low, with a typical pH = 3-4, and was suitable for the precipitation of potassium heptafluorotantalate, K2TaF7, tantalum hydroxide or further purification by liquid-liquid extraction after appropriate adjustment of the solution acidity [113]. 

The quantitative execution of chemical reactions is the basis of the traditional or classical methods of chemical analysis gravimetry, titrimetry and volumetry. In gravimetric analysis the substance being determined is converted into an insoluble precipitate which is collected and weighed, or in the special case of electrogravimetry electrolysis is carried out and the material deposited on one of the electrodes is weighed. 

Mercury-EDTA solution. Mix small equal volumes of 0.05M mercury(II) nitrate and 0.05 M EDTA neutralise the liberated acid by the addition of a few drops of 3M ammonia solution. (In acid solution an insoluble precipitate, probably HgH2Y, forms after a few days.) Dilute 10.0 mL of this solution to 100 mL with distilled water. The resulting ca 0.0025 M mercury-EDTA solution is used for most titrations. 

The steps involved in converting soluble hardness salts in the RW to insoluble precipitants that can be subsequently removed by filtration or clarification, are ... 

To a freshly prepared solution of 11.3 g. (0.10 mole) of hydrox-ylamine-O-sulfonic acid (Note 1) in 64 ml. of cold water there is added 24 ml. (24 g., 0.30 mole) of pyridine (Note 2). The mixture is heated at about 90° on a steam bath for 20 minutes. It is then cooled to room temperature with stirring, and 13.8 g. (0.10 mole) of potassium carbonate is added. The water and excess pyridine are removed from the mixture by heating it at 30-40° in a rotatory evaporator in conjunction with a water aspirator. The residue is treated with 120 ml. of ethanol, and the insoluble precipitate of potassium sulfate is removed by filtration. 

When the mixture was heated above 40° by the submitters, it became discolored and an insoluble precipitate was formed. 

Precipitation. The formation of insoluble precipitates which enable the phagocytes to eliminate soluble antigen firm the body. 

Granular bed filters are used in porcelain enameling wastewater treatment to remove residual solids from clarifier effluent (sedimentation effluent or flotation effluent). Filtration polishes the effluent and reduces suspended solids and insoluble precipitated metals to very low levels. Fine sand and coal are media commonly utilized in granular bed filtration. The filter is backwashed after becoming loaded with solids and the backwash is returned to the treatment plant influent for removal of solids in the clarification step.10-12... 

The total metal concentration in a solution can be easily determined using methods such as atomic absorption spectroscopy (AAS) however, the bioavailability of different metal species likely varies. In addition, much of the original concentration may have speciated into insoluble precipitates. Therefore, the concentration of some bioavailable species may be extremely low, perhaps even within or below the nanomolar range.99 Ion-selective electrodes are useful for measuring the bioavailable concentration of a metal because they measure only the free, ionic species, which is often most prevalent.102... 

Free, ionic species of metals are at their highest concentrations at lower pH, so metals tend to be more bioavailable under these conditions.121128 At acidic pH, more protons are available to saturate metal-binding sites.99 For example, metals are less likely to form insoluble precipitates with phosphates when the pH of the system is lowered because much of the phosphate has been protonated. Under basic conditions, metal ions can replace protons to form other species, such as hydroxo-metal complexes. Some of the hydroxo-metal complexes are soluble, such as those formed with cadmium, nickel, and zinc, whereas those formed with chromium and iron are insoluble. 

Treatment additives, chelating agents, and clay minerals can be added to a system to bind to metals and reduce metal mobility. Treatment additives, such as carbonates, phosphates, and hydroxides, form insoluble precipitates with metals, thus decreasing their bioavailability. Jonioh et al.141... 

CHRED Chemical reduction Chemical reduction converts metal and inorganic constituents in wastewater into insoluble precipitates that are later settled out of the wastewater, leaving a lower concentration of metals and inorganics in the wastewater... 

Precipitation usually occurs when the concentration of a compound in solution exceeds the equilibrium solubility, although slow reaction kinetics may result in supersaturated solutions. For organic wastes in the deep-well environment, precipitation is not generally a significant partitioning process in certain circumstances, however, it may need to be considered. For example, pentach-lorophenol precipitates out of solution when the solution has a pH of <5,35,36 and polychlorophenols form insoluble precipitates in water high in Mg2+ and Ca2+ ions.37 Also, organic anions react with such elements as Ca2+, Fe2+, and Al3+ to form slowly soluble to nearly insoluble compounds. 

Several agents are currently used for plugging high permeability strata. These include small fibers that are carried in the waterflood and deposited in the high permeability zgnes and chemical reactions forming insoluble precipitations. Some of the current methods available, for example polymers or foams, are subject to deterioration and are costly. This gives them limited application as they are not able to penetrate deep into the strata. 

Sonication of 0.05 M Hg2(N03)2 solution for 10,20 and 30 min and the simultaneous measurements of conductivity, temperature change and turbidity (Table 9.2) indicated a rise in the turbidity due to the formation of an insoluble precipitate. This could probably be due to the formation of Hg2(OH)2, as a consequence of hydrolysis, along with Hg free radical and Hg° particles which could be responsible for increase in the turbidity after sonication. The turbidity increased further with time. Mobility of NO3 ions was more or less restricted due to resonance in this ion, which helped, in the smooth and uniform distribution of charge density over NO3 ion surface. Hence the contribution of NOJ ion towards the electrical conductance was perhaps much too less than the conduction of cationic species with which it was associated in the molecular (compound) form. Since in case of Hg2(N03)2, Hg2(OH)2 species were being formed which also destroyed the cationic nature of Hg22+, therefore a decrease in the electrical conductance of solution could be predicted. The simultaneous passivity of its anionic part did not increase the conductivity due to rise in temperature as anticipated and could be seen through the Table 9.2. These observations could now be summarized in reaction steps as under ... 

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