Ammonium chloride, formation

In the following, we will consider the example of ammonium chloride formation in air. More exactly, reaction (4.237) most split into gaseous (monomolecular) and particulate (multimolecular) ammonium chloride ... 

Another method of preparation involving methyl formate has been reported whereia the formate reacts with ammonia and methanol ia the presence of ammonium chloride at 255°C and 2.9 MPa (28.6 atm) (15). In this case, monomethylformamide is present ia considerable quantities as a by-product. 

Ammonium chloride [12125-02-9], ammonium sulfate [7783-20-2], and diammonium phosphate [7708-28-0] have also been used for shale stabilization (102,103). Ammonium ions have essentially the same effect on shales as potassium ions but use of ammonium salts is often objectionable because of the alkaline nature of the mud. In the North Sea and northern Europe, where magnesium-bearing salt formations ate encountered, magnesium chloride [7786-30-3] is used, but in the United States it is used only on a small scale. 

The heat of formation of ammonium chloride from the elements is 317 kJ /mol (75.8 kcal/mol) it is 175 kJ /mol (41.9 kcal/mol) from gaseous ammonia and gaseous hydrogen chloride. The heat of formation of ammonium bromide from the elements, bromine in the Hquid form, is 273 kJ /mol (65.3 kcal/mol) for ammonium iodide, the corresponding heat of formation is 206 kJ /mol (49.3 kcal/mol). Iodine is in the soHd state. 

The ammonium sulfate and sodium chloride are simultaneously dissolved, preferably ia a heel of ammonium chloride solution. The sodium chloride is typically ia excess of about 5%. The pasty mixture is kept hot and agitated vigorously. When the mixture is separated by vacuum filtration, the filter and all connections are heated to avoid cmst formation. The crystalline sodium sulfate is washed to remove essentially all of the ammonium chloride and the washings recycled to the process. The ammonium chloride filtrate is transferred to acid resistant crystallising pans, concentrated, and cooled to effect crystallisation. The crystalline NH Cl is washed with water to remove sulfate and dried to yield a product of high purity. No attempt is made to recover ammonium chloride remaining ia solution. The mother Hquor remaining after crystallisation is reused as a heel. 

Nutrients are usuaUy added at concentrations ranging from 0.005 to 0.02% by weight (16). In a field appHcation using hydrogen peroxide, nutrients were added to the injected water at the foUowing concentrations 380 mg/L ammonium chloride 190 mg/L disodium phosphate, and 190 mg/L potassium phosphate, the latter used primarily to complex with iron in the formation to prevent decomposition of hydrogen peroxide (24). 

Ammonium chloride is used as a flux ia the melting furnace because the large surface of the cathodes favors the formation of dross, ie, oxide-coated globules of ziac. The dross is separated by Hquation or air-swept milling iato metal and oxide fractions. In the latter, the oxide fraction is swept out of the mill and can be returned to roasting for the elimination of chloride. Metallic ziac is recycled. Overall melting efficiency is 96—98%. 

In Leclanchn cells, the high concentration of ammonium chloride leads to the formation of insoluble diammine 2inc chloride through the reaction in the electrolyte. 

CeOCl. The anhydrous cerous chloride [7790-86-5] can be made from the hydrated salt by suppressing oxyhahde formation during thermal dehydration by the presence of hydrogen chloride or ammonium chloride. The anhydrous salt is soluble in a variety of organic solvents, eg, alcohols and ethers, has mp 817°C, and can be volatilized at high temperatures in vacuum. 

Liquid-phase chlorination of butadiene in hydroxyhc or other polar solvents can be quite compHcated in kinetics and lead to extensive formation of by-products that involve the solvent. In nonpolar solvents the reaction can be either free radical or polar in nature (20). The free-radical process results in excessive losses to tetrachlorobutanes if near-stoichiometric ratios of reactants ate used or polymer if excess of butadiene is used. The "ionic" reaction, if a small amount of air is used to inhibit free radicals, can be quite slow in a highly purified system but is accelerated by small traces of practically any polar impurity. Pyridine, dipolar aptotic solvents, and oil-soluble ammonium chlorides have been used to improve the reaction (21). As a commercial process, the use of a solvent requites that the products must be separated from solvent as well as from each other and the excess butadiene which is used, but high yields of the desired products can be obtained without formation of polymer at higher butadiene to chlorine ratio. 

Reactions of the Side Chain. Benzyl chloride is hydrolyzed slowly by boiling water and more rapidly at elevated temperature and pressure in the presence of alkaHes (11). Reaction with aqueous sodium cyanide, preferably in the presence of a quaternary ammonium chloride, produces phenylacetonitrile [140-29-4] in high yield (12). The presence of a lower molecular-weight alcohol gives faster rates and higher yields. In the presence of suitable catalysts benzyl chloride reacts with carbon monoxide to produce phenylacetic acid [103-82-2] (13—15). With different catalyst systems in the presence of calcium hydroxide, double carbonylation to phenylpymvic acid [156-06-9] occurs (16). Benzyl esters are formed by heating benzyl chloride with the sodium salts of acids benzyl ethers by reaction with sodium alkoxides. The ease of ether formation is improved by the use of phase-transfer catalysts (17) (see Catalysis, phase-thansfer). 

The formation of ammonium bisulfate is strongly temperature dependent. Formation is favored at the lower temperatures. The temperature at which ammonium bisulfate is not formed depends strongly on the SO concentration in the exhaust gas. The temperature needed to minimize bisulfate formation has been reported to increase by about I5°C (around about 350°C) when the SO concentration increases from 5 to 15 ppm (23). The formation of the bisulfate is reversible, ie, if the temperature is raised to 20°C above the minimum temperature, the reaction is shifted to result in the decomposition of the bisulfate formed. When chlorides are present, ammonium chlorides can be formed ... 

Ketonic carbonyl groups are commonly encountered in steroids and their reduction is facile, even in the absence of an alcohol. The lithium-ammonia reduction of androsta-l,4-diene-3,17-dione affords androst-4-ene-3,17-dione in 20% yield but concurrent reduction of the C-17 ketone results in formation of testosterone in 40% yield, even though the reduction is performed rapidly at —40 to —60° and excess lithium is destroyed with solid ammonium chloride. Similar reduction of the C-17 carbonyl group has been observed in other compounds. In the presence of an alcohol, a ketone is complete-... 

Methylsulfinyl carbanion (dimsyl ion) is prepared from 0.10 mole of sodium hydride in 50 ml of dimethyl sulfoxide under a nitrogen atmosphere as described in Chapter 10, Section III. The solution is diluted by the addition of 50 ml of dry THF and a small amount (1-10 mg) of triphenylmethane is added to act as an indicator. (The red color produced by triphenylmethyl carbanion is discharged when the dimsylsodium is consumed.) Acetylene (purified as described in Chapter 14, Section I) is introduced into the system with stirring through a gas inlet tube until the formation of sodium acetylide is complete, as indicated by disappearance of the red color. The gas inlet tube is replaced by a dropping funnel and a solution of 0.10 mole of the substrate in 20 ml of dry THF is added with stirring at room temperature over a period of about 1 hour. In the case of ethynylation of carbonyl compounds (given below), the solution is then cautiously treated with 6 g (0.11 mole) of ammonium chloride. The reaction mixture is then diluted with 500 ml of water, and the aqueous solution is extracted three times with 150-ml portions of ether. The ether solution is dried (sodium sulfate), the ether is removed (rotary evaporator), and the residue is fractionally distilled under reduced pressure to yield the ethynyl alcohol. 

Azninon-. ammonium ammonia, -alaun, m. ammonia alum, ammonium alum, -chlorid, n. ammonium chloride. -eisenalaun, m. unmonium iron alum. -formiat, n. ammonium formate. 

The pH at which basic iron(III) formate begins to precipitate depends upon several factors, which include the initial iron and chloride concentration a high concentration of ammonium chloride is essential to prevent colloid formation. It is important to use an optimum initial pH to avoid a large excess of free acid, which would have to be neutralised by urea hydrolysis, and yet there must be present sufficient acid to prevent the formation of a gelatinous precipitate prior to boiling the solution ideally, a turbidity should appear about 5-10 minutes... 

These materials are essentially combustion improvers and tend to have fairly simple formulations (e.g., 3% copper chloride, 7% manganese chloride, 90% ammonium chloride). They are designed to change the crystalline structure within the clinker crystal lattice and raise the clinker eutectic point, thus minimizing the formation of noncombustible clinker, residual ash, and other deposits. Feed rates are approxiimately 0.5 to 2.0 lb per bone-dry ton. 

The three-necked flask is charged with 750 ml. of formamide, 25 ml. of water, and 50 g. of ammonium chloride (Note 2). The mixture is heated to 180-190° in an oil bath, and 400 g. (3.02 moles) of 4,4-dimethoxy-2-butanone (Note 3) is added dropwise with stirring over the course of 6 hours (Note 4). The flow of cooling water in the reflux condenser should be adjusted to a rate such that the methanol and methyl formate formed during the reaction distil out (Note 5). After all the acetal has been added, heating is continued for 1 hour (Note 6). The mixture is allowed to cool and is poured into 1 1. of IN sodium hydroxide. The resultant solution is extracted with chloroform in a liquid-liquid extractor for 24 hours. The chloroform is separated, dried over sodium sulfate, and removed by distillation through a short column on a steam bath. 

An acidic salt must be present so that the acetal bonds will be hydrolyzed. Other salts, such as ammonium formate, may be substituted for ammonium chloride. 

Reduction of the nitro group in 70 with zinc in hot sodium hydroxide results in formation of pyrrolo[2,l-(f][l,2,5]benzotriazepine 71 by intramolecular coupling of the amino group with the newly formed nitroso group (Scheme 16). If the reduction is carried out under the less rigorous conditions of zinc in aqueous ammonium chloride the intermediate hydroxy compound is formed <96T10751>. 

When hot, ammonia and compounds, which contain nitrogen-hydrogen bonds eg ammonium salts and cyanides react violently with chlorates and alkaline perchlorates. Diammonlum sulphate, ammonium chloride, hydroxyl-amine, hydrazine, sodamide, sodium cyanide and ammonium thiocyanate have been cited. So far as hydrazine is concerned, the danger comes from the formation of a complex with sodium or lithium perchlorate, which is explosive when ground. Many of these interactions are explosive but the factors which determine the seriousness of the accident are not known. 

Wilson, C. G. Tomlinson, E. Davis, S. S. Olejnik, O., Altered ocular absorption and disposition of sodium cromoglycate upon ion-pair and complex coacervate formation with dodecylbenzyldimethyl-ammonium chloride, J. Pharm. Pharmacol. 31, 749-753 (1981). 

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