Hydrides safety

One of the principal advantages of hydrides for hydrogen storage is safety (25). As part of a study to determine the safety of the iron—titanium—manganese metal hydride storage system, tests were conducted in conjunction with the U.S. Army (26). These tests simulated the worst possible conditions resulting from a serious coUision and demonstrated that the metal hydride vessels do not explode. 

Diborane(6), B2H. This spontaneously flammable gas is consumed primarily by the electronics industry as a dopant in the production of siHcon wafers for use in semiconductors. It is also used to produce amine boranes and the higher boron hydrides. Gallery Chemical Co., a division of Mine Safety AppHances Co., and Voltaix, Inc., are the main U.S. producers of this substance. Several hundred thousand pounds were manufactured worldwide in 1990. 

Use of sodium hydride in DMF to prepare the pyridine acid 3 Safety concerns with use of sodium hydride, and a low yield of acid... 

Although the synthesis of acid 3 developed by our Medicinal Chemistry colleagues proceeded in a single step from commercial starting materials the yield was modest, and there were significant safety concerns about the use of sodium hydride in DMF on a larger scale. After some experimentation it was found that use of the ester in conjunction with just 1 equiv of KHMDS as base gave a clean... 

Employment of sodium hydride in a large scale process would present safety issues, so the choice of base was addressed and tert-butoxide bases were identified... 

Of a series of lithium hydrocuprates Li CuH +i (n = 1-5), only the title compound (when solvated with THF) appeared a more powerful reducant than lithium tetrahydroaluminate. Safety precautions similar to those adopted for the complex aluminium hydride seem appropriate. 

The product of sorbing hydrogen on to hot zirconium powder bums with incandescence when heated in air [1,2], Ignition and combustion properties of pyrophoric zirconium and zirconium hydride powder (< 10 p), and safety measures are discussed [3], Ignition energies for zirconium hydrides, ZrUx x = 0 — 2, in air have been studied in Japan [4],... 

The Meerwein-Ponndorf-Verley (MPV) reduction is generally mediated by aluminum triiso-propoxide, Al(01Pr)3. In MPV reduction, reversible hydride transfer occurs via a six-membered transition state (Scheme 67). By removing acetone from the reaction system, the reversible reaction proceeds smoothly. The advantages of the reduction are the mildness of the reaction conditions, chemoselectivity, safety, operational simplicity, and its applicability to large-scale synthesis. It is reported that the addition of trifluoroacetic acid, significantly accelerates the reduction (Scheme 68) 304,305 in which case a catalytic amount of Al(0 Pr)3 is enough to complete the reaction. 

Safety considerations are paramount in any boron hydride synthesis. The energy yield from the oxidations of boron hydrides is too high for any cavalier treatment of boron hydrides. Exclusion of air is the critical consideration in diborane reactions. Decaborane(14) is less reactive, generally, in a kinetic sense, but the thermodynamic potential is comparable. In addition, all volatile boron hydrides are toxic. The procedures described in the latter two preparations are within our experience non-hazardous. These procedures should be followed in every detail improvisation is not recommended. 

Conclusively, hydrogen has been used and stored safely in the industry for quite a long time as compressed gas or liquefied hydrogen, and it seems that metal hydride storage will be equally safe or even safer. Consideration of future hydrogen applications reveals no safety problems in the industrial and commercial markets. Although hydrogen safety... 

Water has several anomalous features (e.g., density, being the only nontoxic and liquid "hydride" of the non-metals, melting point varying with pressure, etc.). Of direct importance for the aqueous biphasic process are the physiological (entries 2 and 4 of Table 5.1), economic (1,3,6,9), ecological/safety-related (2,3,4,9), process engineering (1,6,7,9,10,11,12), and chemical and physical properties (1,5,6,8,11,13) of water. The different properties interact and complement each other. Thus water, whose high... 

Sodium aluminate, 2 345t, 358-359 analysis, 2 275-276 economic aspects, 2 275 health and safety factors, 2 276 manufacture, 2 274-275 neutralization, 2 424 physical and chemical properties of, 2 273-274 uses of, 2 276-277 in water treatment, 26 111 Sodium aluminosilicate gels, synthetic zeolites prepared from, 16 831t Sodium aluminosilicates, 12 578 Sodium aluminum hydride, 13 621, 623-624... 

The collected papers of a symposium at Dallas, April 1956, cover all aspects of the handling, use and hazards of lithium, sodium, potassium, their alloys, oxides and hydrides, in 19 chapters [1], Interaction of all 5 alkali metals with water under various circumstances has been discussed comparatively [2], In a monograph covering properties, preparation, handling and applications of the enhanced reactivity of metals dispersed finely in hydrocarbon diluents, the hazardous nature of potassium dispersions, and especially of rubidium and caesium dispersions is stressed [3], Alkaline-earth metal dispersions are of relatively low hazard. Safety practices for small-scale storage, handling, heating and reactions of lithium potassium and sodium with water are reviewed [4],... 

For most phase-transfer catalysed reactions, the rate-determining step is the interaction of the reactive substrate with the anionic species in the organic phase and, compared with the corresponding interfacial reaction in the absence of the catalyst, rate enhancements of 107 are not uncommon. The virtual absence of water from the organic phase under strongly basic liquiddiquid or soliddiquid two-phase conditions allows for the formation of water-sensitive anions, such as carbanions (Chapter 6), and obviates the need for strictly anhydrous conditions and the use of bases such as sodium hydride or sodamide, etc. The phase-transfer catalytic process consequently has lower safety risks and is environmentally more friendly. 

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