Ammonium peroxides

Ammonium peroxides.—At —10° C. dry ammonia reacts with a solution of 98 per cent, hydrogen peroxide in absolute ether to form a crystalline precipitate of the formula NH OaH or (NH4)202)H202. It melts at 14° C., and is converted by the prolonged action of ammonia into an oil, (NH4)202, which solidifies at —40° C., begins to decompose about —10° C., and melts at —2° C. It readily loses ammonia, regenerating the parent substance, NB C H.1 A crystalline, hydrated form of the composition (NH4)2O2,2H2O2,]0H2O, has been prepared. Potassium hydroxide decomposes it, with formation of ammonia and potassium peroxide. 

Albrecht M., Ehrler S. andMuhlebachA. (2003), Nanocomposites from Layered Silicates Graft Polymerization with Intercalated Ammonium Peroxides. Macromol Rapid Commun, 24, 3S2-7. 

CH2=CHC = CCH = CH2. a colourless liquid which turns yellow on exposure to the air it has a distinct garlic-like odour b.p. 83-5°C. Manufactured by the controlled, low-temperature polymerization of acetylene in the presence of an aqueous solution of copper(I) and ammonium chlorides. It is very dangerous to handle, as it absorbs oxygen from the air to give an explosive peroxide. When heated in an inert atmosphere, it polymerizes to form first a drying oil and finally a hard, brittle insoluble resin. Reacts with chlorine to give a mixture of chlorinated products used as drying oils and plastics. 

Such reactions can be initiated by free radicals, derived from compounds (initiators) such as benzoyl peroxide, ammonium persulphate or azobis-isobutyronitrile or by ionic mechanisms... 

On a large scale, hydrogen peroxide is produced by the electrolysis of ammonium hydrogensulphate, using a platinum anode and a lead cathode separated by a diaphragm. The essential process occurring is ... 

The ammonium hydrogensulphate is returned to the electrolytic cell. A process such as this yields an aqueous solution containing about 30% hydrogen peroxide. The solution can be further concentrated, yielding ultimately pure hydrogen peroxide, by fractional distillation but the heating of concentrated hydrogen peroxide solutions requires care (see below). 

Electrolysis of the hydrogensulphate of potassium or ammonium can yield a peroxodisulphate and thence hydrogen peroxide. 

It is usually preferable to oxidise the compound directly as follows. Intimately mix 0 02-0 05 g. of the eompound with 3 g. of sodium peroxide and 2 g. of anhydrous sodium carbonate in a niekel erucible. Heat the crueible and its eontents with a small flame, gently at first, afterwards more strongly until the eontents are fused, and eontinue heating for a further 10 minutes. Allow to stand, extract the contents of the crucible with water, and filter. Add exeess of eoneentrated nitrie acid to the filtrate and test with ammonium molybdate reagent as above. A yellow preeipitate indicates the presenee of phosphorus. It must be borne in mind that the above treatment 1 eonvert any arsenie present into arsenate. 

Copper Acetylene and alkynes, ammonium nitrate, azides, bromates, chlorates, iodates, chlorine, ethylene oxide, fluorine, peroxides, hydrogen sulflde, hydrazinium nitrate... 

Elammable liquids Ammonium nitrate, chromic acid, the halogens, hydrogen peroxide, nitric acid... 

Lead Ammonium nitrate, chlorine trifluoride, hydrogen peroxide, sodium azide and carbide, zirconium, oxidants... 

Silver Acetylene, ammonium compounds, ethyleneimine, hydrogen peroxide, oxalic acid, sulfuric acid, tartaric acid... 

Water-soluble peroxide salts, such as ammonium or sodium persulfate, are the usual initiators. The initiating species is the sulfate radical anion generated from either the thermal or redox cleavage of the persulfate anion. The thermal dissociation of the persulfate anion, which is a first-order process at constant temperature (106), can be greatly accelerated by the addition of certain reducing agents or small amounts of polyvalent metal salts, or both (87). By using redox initiator systems, rapid polymerizations are possible at much lower temperatures (25—60°C) than are practical with a thermally initiated system (75—90°C). 

Thermally activated initiators (qv) such as azobisisobutyroaittile (AIBN), ammonium persulfate, or benzoyl peroxide can be used in solution polymeriza tion, but these initiators (qv) are slow acting at temperatures required for textile-grade polymer processes. Half-hves for this type of initiator are in the range of 10—20 h at 50—60°C (13). Therefore, these initiators are used mainly in batch or semibatch processes where the reaction is carried out over an extended period of time. 

In 1973 the Semiconductor Equipment and Materials Institute (SEMI) held its first standards meeting. SEMI standards are voluntary consensus specifications developed by the producers, users, and general interest groups in the semiconductor (qv) industry. Examples of electronic chemicals are glacial acetic acid [64-19-7] acetone [67-64-17, ammonium fluoride [12125-01 -8] and ammonium hydroxide [1336-21 -6] (see Ammonium compounds), dichloromethane [75-09-2] (see Cm.OROCARBONSANDcm.OROHYDROCARBONs), hydrofluoric acid [7664-39-3] (see Eluorine compounds, inorganic), 30% hydrogen peroxide (qv) [7722-84-1] methanol (qv) [67-56-1] nitric acid (qv) [7697-37-2] 2-propanoI [67-63-0] (see Propyl alcohols), sulfuric acid [7664-93-9] tetrachloroethane [127-18-4] toluene (qv) [108-88-3] and xylenes (qv) (see also Electronic materials). 

Bleaches of the simple ammoniacal peroxide type give limited lightening, which can be increased with bleach accelerators or boosters, including one or more per salts such as ammonium, potassium, or sodium persulfate or their combinations. These salts, which are susceptible to decomposition in aqueous solution, are packaged as dry powders and added just before use. In the absence of hydrogen peroxide, however, persulfates do not have any bleaching effect (41). 

Wheieas the BPO—DMA ledox system works well for curing of unsaturated polyester blends, it is not a very effective system for initiating vinyl monomer polymerizations, and therefore it generally is not used in such appHcations (34). However, combinations of amines (eg, DMA) and acyl sulfonyl peroxides (eg, ACSP) are very effective initiator systems at 0°C for high conversion suspension polymerizations of vinyl chloride (35). BPO has also been used in combination with ferrous ammonium sulfate to initiate emulsion polymerizations of vinyl monomers via a redox reaction (36). 

The most common water-soluble initiators are ammonium persulfate, potassium persulfate, and hydrogen peroxide. These can be made to decompose by high temperature or through redox reactions. The latter method offers versatility in choosing the temperature of polymerization with —50 to 70°C possible. A typical redox system combines a persulfate with ferrous ion ... 

Arsenic Peroxides. Arsenic peroxides have not been isolated however, elemental arsenic, and a great variety of arsenic compounds, have been found to be effective catalysts ia the epoxidation of olefins by aqueous hydrogen peroxide. Transient peroxoarsenic compounds are beheved to be iavolved ia these systems. Compounds that act as effective epoxidation catalysts iaclude arsenic trioxide, arsenic pentoxide, arsenious acid, arsenic acid, arsenic trichloride, arsenic oxychloride, triphenyl arsiae, phenylarsonic acid, and the arsenates of sodium, ammonium, and bismuth (56). To avoid having to dispose of the toxic residues of these reactions, the arsenic can be immobi1i2ed on a polystyrene resia (57). 

The peroxodisulfates are made commercially by Akkim (Turkey), Degussa (Germany), PMC, Migas, Peroxid-Chemie, ERB Engineering (India), Sangen (Taiwan), and TokaiDenka (Japan). In 1994 the U.S. price of the sodium salt was 1.92/kg, the potassium salt 2.07/kg, and the ammonium salt 1.68/kg. 

Ammonium carbonate peroxohydrate, (NH 2 02 H2O2, first reported in 1980 (31), is crystalli2ed from a solution of ammonium hydrogen carbonate in aqueous hydrogen peroxide. The vibrational spectmm confirms the presence of molecular hydrogen peroxide. The compound is unstable and unlikely to find commercial appHcation. 

Insoluble iridium dioxide from the sodium peroxide fusion is dissolved in aqua regia, oxidized with nitric acid, and precipitated with ammonium chloride as impure ammonium hexachloroiridate(IV), To purify this salt, it is necessary to redissolve the compound and precipitate out the... 

Some fabrication processes, such as continuous panel processes, are mn at elevated temperatures to improve productivity. Dual-catalyst systems are commonly used to initiate a controlled rapid gel and then a fast cure to complete the cross-linking reaction. Cumene hydroperoxide initiated at 50°C with benzyl trimethyl ammonium hydroxide and copper naphthenate in combination with tert-huty octoate are preferred for panel products. Other heat-initiated catalysts, such as lauroyl peroxide and tert-huty perbenzoate, are optional systems. Eor higher temperature mol ding processes such as pultmsion or matched metal die mol ding at temperatures of 150°C, dual-catalyst systems are usually employed based on /-butyl perbenzoate and 2,5-dimethyl-2,5-di-2-ethyIhexanoylperoxy-hexane (Table 6). 

Disinfection destroys pathogenic organisms. This procedure can render an object safe for use. Disinfectants include solutions of hypochlorites, tinctures of iodine or iodophores, phenoHc derivatives, quaternary ammonium salts, ethyl alcohol, formaldehyde, glutaraldehyde, and hydrogen peroxide (see Disinfectants AND antiseptics). Effective use of disinfected materials must be judged by properly trained personnel. 

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). 

The most suitable oxidizing agent is potassium ferricyanide, but ferric chloride, hydrogen peroxide ia the presence of ferrous salts, ammonium persulfate, lead dioxide, lead tetraacetate or chromate, or silver and cupric salts may be useful. Water mixed, eg, with methanol, dimethylformamide, or glycol ethers, is employed as reaction medium. 

Hair. Hydrogen peroxide is the most satisfactory bleaching agent for human hair. Solutions containing 3—4% hydrogen peroxide, available from dmg stores and supermarkets, are commonly used. In beauty shops, more rapid bleaching is desired and a 5—6% solution is used. Ammonium hydroxide is usually the source of aLkaliuity in both systems (see Cosmetics Hair preparations). 

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