Reactions of ammonia

How ever, the Mn(II) ion forms a variety of complexes in solution, some of which may be more easily oxidised these complexes can be either tetrahedral, for example [MnClJ , or octahedral, for example [Mn(CN)f,] Addition of ammonia to an aqueous solution of a manganese(II) salt precipitates Mn(OH)2 reaction of ammonia with anhydrous manganese(II) salts can yield the ion [MnfNH y T... 

The reaction of ammonia and amines with esters follows the same general mech anistic course as other nucleophilic acyl substitution reactions (Figure 20 6) A tetrahe dral intermediate is formed m the first stage of the process and dissociates m the second stage... 

Commercially, urea is produced by the direct dehydration of ammonium carbamate, NH2COONH4, at elevated temperature and pressure. Ammonium carbamate is obtained by direct reaction of ammonia and carbon dioxide. The two reactions are usually carried out simultaneously in a high pressure reactor. Recendy, urea has been used commercially as a catde-feed supplement (see Feeds and feed additives). Other important appHcations are the manufacture of resins (see Amino resins and plastics), glues, solvents, and some medicinals. Urea is classified as a nontoxic compound. 

Amidation. Reaction of maleic anhydride or its isomeric acids with ammonia [7664-41-7] (qv), primary amines (qv), and secondary amines produces mono- or diamides. The monoamide derivative from the reaction of ammonia and maleic anhydride is called maleamic acid [557-24-4] (8). Another monoamide derivative formed from the reaction of aniline [62-53-3] and maleic anhydride is maleanilic acid [555-59-9] (9). 

Extremely high purity ammonium perchlorate can be made by the direct reaction of ammonia and pure perchloric acid solution (8,36) ... 

Etliyleiie oxide [75-21-8] propylene oxide [75-56-9] or butylene oxide [106-88-7] react widi aminonia to produce alkanolainines (Table 1). Etlianolainines, (n = 1, 2,3, mono-, di-, and tri-), are derived from the reaction of ammonia witli ethylene oxide. Isopropanolamines,... 

CH- CHOHCH3 ), (mono-, di-, and tri-), result from the reaction of ammonia with propylene oxide. Secondary butanolamines,... 

Method 7. Alkyl haHde amination reaction of ammonia or alkylamine with an alkyl haHde. 

Olefin Amination (Method 6). The most recent technology for the production of lower alkylamines is olefin amination (14). This is 2eohte-cataly2ed reaction of ammonia with an olefin, eg, isobutylene, and is practiced in a packed-bed reactor system in the vapor phase. 

A number of 2eohtic materials have been claimed to cataly2e this reaction and reaction temperatures are on the order of 200—350°C with pressures as high as 18000 kPa (2600 psi) reported. This is a low conversion process and recycle of the unconverted starting materials is necessary to provide an economical process. Amination of ethylene to produce ethylamines cataly2ed by ammonium iodide is reported, but not beheved to be practiced commercially (15,16). Alkyl Halide Amination (Method 7). The oldest technology for pioducing amines is the reaction of ammonia with an alkyl hahde. This... 

Of major iadustrial importance is the reaction of ammonia and carbon dioxide giving ammonium carbamate [111 1-78-0], CH N202. 

Manufacture. The history of ammonium chloride manufacture is linked to the birth of the soda and synthetic ammonia iadustries. Consequendy this haUde has always been a by-product ia great supply. Production by direct reaction of ammonia and hydrochloric acid is simple but usually economically unattractive a process based on metathesis or double decomposition is generally preferred. 

Several commercial grades are available fine crystals of 99 to 100% purity, large crystals, pressed lumps, rods, and granular material. Double-Decomposition Methods. Double-decomposition processes all iavolve the reaction of sodium chloride, the cheapest chlorine source, with an ammonium salt. The latter may be suppHed directiy, or generated in situ by the reaction of ammonia and a supplementary iagredient. Ammonium chloride and a sodium salt are formed. The sodium salt is typically less soluble and is separated at higher temperatures ammonium chloride is recovered from the filtrate by cooling. 

A.mmonia-Soda Process. Ammonium chloride is made as a by-product of the classic Solvay process, used to manufacture sodium carbonate (12,13) (see Alkali and chlorine products, sodium carbonate). The method iuvolves reaction of ammonia, carbon dioxide, and sodium chloride ia water... 

Manufacture. Ammonium bromide and Ammonium iodide are manufactured either by the reaction of ammonia with the corresponding hydrohahc acid or, more economically, by the reaction of ammonia with elemental bromine or iodine. In the latter reaction, an excess of ammonia must be used. 

Some companies have used the Merseburg process to manufacture ammonium sulfate from gypsum, but the process is only economically attractive where sulfur is unavailable or very expensive (32), and is thus not used in the United States. Ammonium carbonate, formed by the reaction of ammonia and carbon dioxide in an aqueous medium, reacts with suspended, finely ground gypsum. Insoluble calcium carbonate and an ammonium sulfate solution are formed. 

Phosphoms trichloride and pentachloride form sodium chloride and sodium phosphide, respectively, in the presence of sodium. Phosphoms oxychloride, POCl, when heated with sodium, explodes. Carbon disulfide reacts violendy, forming sodium sulfide. Sodium amide (sodamide), NaNH2, is formed by the reaction of ammonia gas with Hquid sodium. SoHd sodium reacts only superficially with Hquid sulfur dioxide but molten sodium and gaseous... 

Benzylarnine, [100-46-9] CgH CH2NH2 (bp, 184°C at 101.3 kPa) produced by reaction of ammonia with benzaldehyde and hydrogenation of the resulting Schiffs base, is used as the raw material for the production of biotin (Vitamin H), as an intermediate for certain photographic materials, and as an intermediate in the manufacture of certain pharmaceutical products. 

Reactions of ammonia and amines with carboxyUc acids result in the formation of a variety of products (47,48). Ammonium salts, RCOONH, are prepared with or without solvent, by reaction with anhydrous ammonia. Ammonium salts readily decompose to acid ammonium salts,... 

Additions. The addition reactions of ammonia and amines to the cyanamide nitrile group have been thoroughly studied (15). For optimum conditions, the reaction should be carried out ia an aqueous medium at about 140°C. Gradual addition of the cyanamide to the amine salt minimises dimerization. 

Two synthesis processes account for most of the hydrogen cyanide produced. The dominant commercial process for direct production of hydrogen cyanide is based on classic technology (23—32) involving the reaction of ammonia, methane (natural gas), and air over a platinum catalyst it is called the Andmssow process. The second process involves the reaction of ammonia and methane and is called the BlausAure-Methan-Ammoniak (BMA) process (30,33—35) it was developed by Degussa in Germany. Hydrogen cyanide is also obtained as a by-product in the manufacture of acrylonitrile (qv) by the ammoxidation of propjiene (Sohio process). 

The fluohmic process is a third process for manufacturing hydrogen cyanide, which is being appHed in Spain and AustraUa. This process involves the reaction of ammonia with a hydrocarbon, usually propane or butane, in a fluidized bed of coke particles. The endothermic heat of reaction is suppHed electrically through electrodes immersed in the fluid bed. Yields from propane and ammonia are reportedly above 85% and the waste gas is essentially hydrogen, but the costs for electricity are high. Thus this process is appHcable only when there is an inexpensive source of power. 

A.mina.tlon. Amination describes the introduction of amino groups into aromatic molecules by reaction of ammonia or an amine with suitably substituted halogeno, hydroxy, or sulfonated derivatives by nucleophilic displacement. Although reaction and operational conditions vary, the process always involves the heating of the appropriate precursor with excess aqueous ammonia or amine under pressure. 

Ammonium sulfate is produced as a caprolactam by-product from the petrochemical industry, as a coke by-product, and synthetically through reaction of ammonia with sulfuric acid. Only the third process is covered in our discussion. The reaction between anunonia and sulfuric acid produces an ammonium sulfate solution that is continuously circulated through an evaporator to thicken the solution and to produce ammonium sulfate crystals. The crystals are separated from the liquor in a centrifuge, and the liquor is returned to the evaporator. The crystals are fed either to a fluidized bed or to a rotary drum dryer and are screened before bagging or bulk loading. 

Ammonium phosphate is produced by reaction of ammonia with phosphoric acid resulting in the formation of the mono or di-basic salts ... 

Reductive amination (Section 22.10) Reaction of ammonia or an amine with an aldehyde or a ketone in the presence of a reducing agent is an effective method for the preparation of primary, secondary, or tertiary amines. The reducing agent may be either hydrogen in the presence of a metal catalyst or sodium cyanoborohy-dride. R, R, and R" may be either alkyl or aryl. 

The most effective preparative routes to hydrazine are still based on the process introduced by F. Raschig in 1907 this involves the reaction of ammonia with an alkaline solution of sodium hypochlorite in the presence of gelatin or glue. The overall reaction can be written as... 

Calculate activation energies for Sn2 reactions of ammonia and trimethylamine with methyl iodide via transition states ammonia+methyl iodide and trimethyl-amine+methyl iodide, respectively. Is attack by ammonia or trimethylamine more facile Rationalize your observation by comparing electrostatic potential maps for the two transition states. Which transition state requires more charge separation Is this also the higher-energy transition state ... 

Despite the increasing information on the photochemistry of 2,4-dienones and other unsaturated ketones, as well as on the ring-chain valence isomerism of halogen-substituted pyran and dihydi opyran systems,the data are still very scarce. The intermediate formation of pyrans valence-isomeric with unsaturated carbonyl compounds in the pyridine syntheses based on reactions of ammonia with aldehydes or ketones, advocated by various authors (cf. Section II,B,2,f), is still rather speculative. (See also Section II,B,2,e for the valence isomerism of 5-chloro-2,4-dienones with pyrylium chlorides.)... 

Hydrogen cyanide may also be produced by the reaction of ammonia and methanol in presence of oxygen ... 

The production of ammonia is of historical interest because it represents the first important application of thermodynamics to an industrial process. Considering the synthesis reaction of ammonia from its elements, the calculated reaction heat (AH) and free energy change (AG) at room temperature are approximately -46 and -16.5 KJ/mol, respectively. Although the calculated equilibrium constant = 3.6 X 108 at room temperature is substantially high, no reaction occurs under these conditions, and the rate is practically zero. The ammonia synthesis reaction could be represented as follows ... 

Production. The technical production of urea is based on the reaction of ammonia with carbon dioxide ... 

For this reason, operation around atmospheric pressures is typical. Space velocity should he high to avoid the reaction of ammonia with oxygen on the reactor walls, which produces nitrogen and water, and results in lower conversions. The concentration of ammonia must he kept helow the inflammahility limit of the feed gas mixture to avoid explosion. Optimum nitric acid production was found to he obtained at approximately 900°C and atmospheric pressure. 

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