Alkaline nitration

Sulphates, silicates, carbonates, colloids and certain organic compounds act as inhibitors if evenly distributed, and sodium silicate has been used as such in certain media. Nitrates tend to promote corrosion, especially in acid soil waters, due to cathodic de-polarisation and to the formation of soluble nitrates. Alkaline soils can cause serious corrosion with the formation of alkali plumbites which decompose to give (red) lead monoxide. Organic acids and carbon dioxide from rotting vegetable matter or manure also have a strong corrosive action. This is probably the explanation of phenol corrosion , which is not caused by phenol, but thought to be caused by decomposition of jute or hessian in applied protective layers. ... 

Powdered antimony reacts explosively when it is carefully mixed with alkaline nitrates alkaline antimonates are formed. The same happens with molten ammonium nitrate, which combusts violently when it is ground up with potassium permanganate (to be compared with arsenic on p.210). 

Alkaline earth (Calcium carbonate) Phosphorus of Homberg (Calcium chloride) Alkalme earth (Calcium carbonate) Salpetre of lime (Calcium nitrate) Alkaline earth (Calcium carb[Pg.144]

Acetone cyanohydrin nitrate Alkaline nitration N-Nitramines... 

Prepared by heating p-nitrochlorobenzene with concentrated aqueous ammonia in an autoclave at 170°C. It is also prepared by alkaline hydrolysis of p-nitroacetanilide or by nitrating and hydrolysing benzylideneaniline. 

For the most part it is true to say that the chemistry of the alkali and alkaline earth metal compounds is not that of the metal ion but rather that of the anion with which the ion is associated. Where appropriate, therefore, the chemistry of these compounds will be discussed in other sections, for example nitrates with Group V compounds, sulphates with Group VI compounds, and only a few compounds will be discussed here. 

With a nitrate in alkaline solution, ammonia is evolved quantitatively by Devarda s alloy (Al, 45% Cu, 50% and Zn, 5%). This reaction can be used to estimate nitrate in absence of ammonium ions (see below) ... 

In neutral solution, the indicator is potassium chromate(VI). In acid solution the CrOj" ion changes to CrjO (p. 378). and since silver dichromatefVI) is soluble, chromate(VI) is not a suitable indicator other methods can be used under these conditions. (In alkaline solution, silverfl) oxide precipitates, so silver(I) nitrate cannot be used under these conditions.)... 

Originally, general methods of separation were based on small differences in the solubilities of their salts, for examples the nitrates, and a laborious series of fractional crystallisations had to be carried out to obtain the pure salts. In a few cases, individual lanthanides could be separated because they yielded oxidation states other than three. Thus the commonest lanthanide, cerium, exhibits oxidation states of h-3 and -t-4 hence oxidation of a mixture of lanthanide salts in alkaline solution with chlorine yields the soluble chlorates(I) of all the -1-3 lanthanides (which are not oxidised) but gives a precipitate of cerium(IV) hydroxide, Ce(OH)4, since this is too weak a base to form a chlorate(I). In some cases also, preferential reduction to the metal by sodium amalgam could be used to separate out individual lanthanides. 

Note. Phenols (unless nitrated) do not liberate CO, from Na,CO, solution. (e) Weakly alkaline. Alkali salts of some weak acids, pyridine. 

Aromatic aldehydes react with the dimedone reagent (Section 111,70,2). All aromatic aldehydes (i) reduce ammoniacal silver nitrate solution and (ii) restore the colour of SchifiF s reagent many react with sodium bisulphite solution. They do not, in general, reduce Fehling s solution or Benedict s solution. Unlike aliphatic aldehydes, they usually undergo the Cannizzaro reaction (see Section IV,123) under the influence of sodium hydroxide solution. For full experimental details of the above tests, see under Ali-phalic Aldehydes, Section 111,70. They are easily oxidised by dilute alkaline permanganate solution at the ordinary temperature after removal of the manganese dioxide by sulphur dioxide or by sodium bisulphite, the acid can be obtained by acidification of the solution. 

Sulphur, as sulphide ion, is detected by precipitation as black lead sulphide with lead acetate solution and acetic acid or with sodium plumbite solution (an alkaLine solution of lead acetate). Halogens are detected as the characteristic silver halides by the addition of silver nitrate solution and dilute nitric acid the interfering influence of sulphide and cyanide ions in the latter tests are discussed under the individual elements. 

TrialkyIboranes (p. 9), which can be synthesized from olefins and diborane, undergo alkyl coupling on oxidation with alkaline silver nitrate via short-lived silver organyls. Two out of three alkyl substituents are coupled in this reaction. Terminal olefins may be coupled by this reaction sequence in 40 - 80% yield. With non-terminal olefins yields drop to 30 - 50% (H.C. Brown, 1972C, 1975). 

Acid—Base Chemistry. Acetic acid dissociates in water, pK = 4.76 at 25°C. It is a mild acid which can be used for analysis of bases too weak to detect in water (26). It readily neutralizes the ordinary hydroxides of the alkaU metals and the alkaline earths to form the corresponding acetates. When the cmde material pyroligneous acid is neutralized with limestone or magnesia the commercial acetate of lime or acetate of magnesia is obtained (7). Acetic acid accepts protons only from the strongest acids such as nitric acid and sulfuric acid. Other acids exhibit very powerful, superacid properties in acetic acid solutions and are thus useful catalysts for esterifications of olefins and alcohols (27). Nitrations conducted in acetic acid solvent are effected because of the formation of the nitronium ion, NO Hexamethylenetetramine [100-97-0] may be nitrated in acetic acid solvent to yield the explosive cycl o trim ethyl en etrin itram in e [121 -82-4] also known as cyclonit or RDX. 

Analytical Procedures. Standard methods for analysis of food-grade adipic acid are described ia the Food Chemicals Codex (see Refs, ia Table 8). Classical methods are used for assay (titration), trace metals (As, heavy metals as Pb), and total ash. Water is determined by Kad-Fisher titration of a methanol solution of the acid. Determination of color ia methanol solution (APHA, Hazen equivalent, max. 10), as well as iron and other metals, are also described elsewhere (175). Other analyses frequendy are required for resia-grade acid. For example, hydrolyzable nitrogen (NH, amides, nitriles, etc) is determined by distillation of ammonia from an alkaline solution. Reducible nitrogen (nitrates and nitroorganics) may then be determined by adding DeVarda s alloy and continuing the distillation. Hydrocarbon oil contaminants may be determined by ir analysis of halocarbon extracts of alkaline solutions of the acid. 

Potassium nitrate is being used increasingly on intensive crops such as tomatoes, potatoes, tobacco, leafy vegetables, citms, and peaches. The properties that make it particularly desirable for these crops are low salt index, nitrate nitrogen, favorable N K20 ratio, negligible CU content, and alkaline residual reaction in the soil. The low hygroscopicity of KNO (Table 9) leads to its use in direct appHcation and in mixtures. It is an excellent fertilizer but the high cost of production limits its use to specialty fertilizers. 

For many years fluorine has been deterrnined by the Willard-Winters method in which finely ground ore, after removal of organic matter, is distilled with 72% perchloric acid in glass apparatus. The distillate, a dilute solution of fluorosiUcic acid, is made alkaline to release fluoride ion, adjusted with monochloroacetic acid at pH 3.4, and titrated with thorium nitrate, using sodium a1i2arine sulfonate as indicator. 

Sahcylaldehyde is readily oxidized, however, to sahcyhc acid by reaction with solutions of potassium permanganate, or aqueous silver oxide suspension. 4-Hydroxybenzaldehyde can be oxidized to 4-hydroxybenzoic acid with aqueous silver nitrate (44). Organic peracids, in basic organic solvents, can also be used for these transformations into benzoic acids (45). Another type of oxidation is the reaction of sahcylaldehyde with alkaline potassium persulfate, which yields 2,5-dihydroxybenzaldehyde (46). 

The solution leaving the flotation cell, containing about 0.4 g/L iodine, is sent to a kerosene solvent extraction process to recover the dissolved product. After neutralization with soda ash to the initial incoming alkalinity, the solution is returned to the nitrate lixiviation process. The iodine-chaiged kerosene is contacted with an acidic concentrated iodide solution containing SO2, which reduces the iodine to iodide. 

Uranium ores are leached with dilute sulfuric acid or an alkaline carbonate [3812-32-6] solution. Hexavalent uranium forms anionic complexes, such as uranyl sulfate [56959-61-6], U02(S0 3, which are more selectively adsorbed by strong base anion exchangers than are other anions in the leach Hquors. Sulfate complexes are eluted with an acidified NaCl or ammonium nitrate [6484-52-2], NH NO, solution. Carbonate complexes are eluted with a neutral brine solution. Uranium is precipitated from the eluent and shipped to other locations for enrichment. Columnar recovery systems were popular in South Africa and Canada. Continuous resin-in-pulp (RIP) systems gained popularity in the United States since they eliminated a difficult and cosdy ore particle/leach hquor separation step. 

In general, the chemistry of inorganic lead compounds is similar to that of the alkaline-earth elements. Thus the carbonate, nitrate, and sulfate of lead are isomorphous with the corresponding compounds of calcium, barium, and strontium. In addition, many inorganic lead compounds possess two or more crystalline forms having different properties. For example, the oxides and the sulfide of bivalent lead are frequendy colored as a result of their state of crystallisation. Pure, tetragonal a-PbO is red pure, orthorhombic P PbO is yeUow and crystals of lead sulfide, PbS, have a black, metallic luster. 

This secondary reaction starts at about 180°C, but the mass must be heated to 350—400°C to bring the reaction to completion and produce a nitrate-free product. The off-gases are extremely corrosive and poisonous, and considerable attention and expense is required for equipment maintenance and caustic-wash absorption towers. Treatment of the alkaline wash Hquor for removal of mercury is required both for economic reasons and to comply with governmental regulations pertaining to mercury ia plant effluents. 

Uses. Nickel nitrate is an intermediate in the manufacture of nickel catalysts, especially those that are sensitive to sulfur and therefore preclude the use of the less expensive nickel sulfate. Nickel nitrate also is an intermediate in loading active mass in nickel—alkaline batteries of the sintered plate type (see Batteries, SECONDARY cells). Typically, hot nickel nitrate symp is impregnated in the porous sintered nickel positive plates. Subsequendy, the plates are soaked in potassium hydroxide solution, whereupon nickel hydroxide [12054-48-7] precipitates within the pores of the plate. 

When nickel hydroxide is oxidized at the nickel electrode in alkaline storage batteries the black trivalent gelatinous nickel hydroxide oxide [12026-04-9], Ni(0H)0, is formed. In nickel battery technology, nickel hydroxide oxide is known as the nickel active mass (see Batteries, secondary cells). Nickel hydroxide nitrate [56171-41-6], Ni(0H)N02, and nickel chloride hydroxide [25965-88-2], NiCl(OH), are frequently mentioned as intermediates for the production of nickel powder in aqueous solution. The binding energies for these compounds have been studied (55). 

Devarda s Method. Nitrogen in nitrates or nitric acid also may be deterrnined by the Kjeldahl method or by Devarda s method. The latter is both convenient and accurate when no organic nitrogen is present. The nitrate is reduced by Devarda s alloy to ammonia in an alkaline solution. The ammonia is distilled and titrated with standard acid. 

Chemical Properties and Reactivity. LLDPE is a saturated branched hydrocarbon. The most reactive parts of LLDPE molecules are the tertiary CH bonds in branches and the double bonds at chain ends. Although LLDPE is nonreactive with both inorganic and organic acids, it can form sulfo-compounds in concentrated solutions of H2SO4 (>70%) at elevated temperatures and can also be nitrated with concentrated HNO. LLDPE is also stable in alkaline and salt solutions. At room temperature, LLDPE resins are not soluble in any known solvent (except for those fractions with the highest branching contents) at temperatures above 80—100°C, however, the resins can be dissolved in various aromatic, aUphatic, and halogenated hydrocarbons such as xylenes, tetralin, decalin, and chlorobenzenes. 

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