Water reaction with alkaline earth

CHLOROACETIC ACID, ETHYL ESTER (105-39-5) Combustible liquid (flash point 147°F/64°C oc also listed at 129°F/54°C). Violent reaction with oxidizers. Reacts with water, forming acetic acid. Violent reaction with alkaline earth metals, alkaline metals. Incompatible with sodium cyanide + heat. Attacks many metals in the presence of moisture, producing hydrogen gas. 

Alkaline earth metal A metal in Group 2 of file periodic table, 31 hydrogen reactions with, 542 oxygen reactions with, 543-544 reactions, 54U, 552q water reactions with, 542... 

The complexes Mg(N03)2 terpy 2H20, Ca(SCN)2 2terpy H20, and Ba(SCN)2 terpyH20 have been reported, but are of unknown structure (455). ESR studies of the terpy radical anion obtained from the reaction of terpy with alkaline earth metals (Mg, Ca, Sr, or Ba) have indicated that a significant interaction occurs between the anion and the cation (79). Spectrophotometric measurements have indicated that magnesium sulfate forms a 1 1 complex with terpy in water, with K = 5.858 + 0.023 mol (185,186). 

Write general equations for reactions of alkaline earth metals with (a) water, (b) phosphorus, and (c) chlorine. Represent the metal as M. 

Compared to the Wurtz method, electrochemical reduction with alkaline-earth metals is a milder alternative coupling reaction with the corresponding organochlorosilane. The silanes that can react with Mg are not preferred for this approach. Regardless of this limitation, the electrochemical method is applicable to phenyl-containing chlorosilane because Mg and Mg-Cu are not reactive when in contact with water and air. The water- and/or air-sensitive reactions are not welcome for technical reasons. 

The reactions of alkaline earth metals with water vary considerably. Beryllium does not react with water magnesium reacts slowly with steam and calcium, strontium, and barium react vigorously with cold water. 

Salt Formation. Salt-forming reactions of adipic acid are those typical of carboxylic acids. Alkali metal salts and ammonium salts are water soluble alkaline earth metal salts have limited solubiUty (see Table 5). Salt formation with amines and diamines is discussed in the next section. 

Properties. Lithium fluoride [7789-24-4] LiF, is a white nonhygroscopic crystaUine material that does not form a hydrate. The properties of lithium fluoride are similar to the aLkaline-earth fluorides. The solubility in water is quite low and chemical reactivity is low, similar to that of calcium fluoride and magnesium fluoride. Several chemical and physical properties of lithium fluoride are listed in Table 1. At high temperatures, lithium fluoride hydroly2es to hydrogen fluoride when heated in the presence of moisture. A bifluoride [12159-92-17, LiF HF, which forms on reaction of LiF with hydrofluoric acid, is unstable to loss of HF in the solid form. 

Difluoroethanol is prepared by the mercuric oxide cataly2ed hydrolysis of 2-bromo-l,l-difluoroethane with carboxyHc acid esters and alkaH metal hydroxides ia water (27). Its chemical reactions are similar to those of most alcohols. It can be oxidi2ed to difluoroacetic acid [381-73-7] (28) it forms alkoxides with alkaH and alkaline-earth metals (29) with alkoxides of other alcohols it forms mixed ethers such as 2,2-difluoroethyl methyl ether [461-57-4], bp 47°C, or 2,2-difluoroethyl ethyl ether [82907-09-3], bp 66°C (29). 2,2-Difluoroethyl difluoromethyl ether [32778-16-8], made from the alcohol and chlorodifluoromethane ia aqueous base, has been iavestigated as an inhalation anesthetic (30,31) as have several ethers made by addition of the alcohol to various fluoroalkenes (32,33). Methacrylate esters of the alcohol are useful as a sheathing material for polymers ia optical appHcations (34). The alcohol has also been reported to be useful as a working fluid ia heat pumps (35). The alcohol is available ia research quantities for ca 6/g (1992). 

Basic oxides of metals such as Co, Mn, Fe, and Cu catalyze the decomposition of chlorate by lowering the decomposition temperature. Consequendy, less fuel is needed and the reaction continues at a lower temperature. Cobalt metal, which forms the basic oxide in situ, lowers the decomposition of pure sodium chlorate from 478 to 280°C while serving as fuel (6,7). Composition of a cobalt-fueled system, compared with an iron-fueled system, is 90 wt % NaClO, 4 wt % Co, and 6 wt % glass fiber vs 86% NaClO, 4% Fe, 6% glass fiber, and 4% BaO. Initiation of the former is at 270°C, compared to 370°C for the iron-fueled candle. Cobalt hydroxide produces a more pronounced lowering of the decomposition temperature than the metal alone, although the water produced by decomposition of the hydroxide to form the oxide is thought to increase chlorine contaminate levels. Alkaline earths and transition-metal ferrates also have catalytic activity and improve chlorine retention (8). 

The stability of the alkali metal ozonides increases from Li to Cs alkaline-earth ozonides exhibit a similar stability pattern. Reaction of metal ozonides with water proceeds through the intermediate formation of hydroxyl radicals. 

The alkah metal phosphides of formula M P and the alkaline-earth phosphides of formula M2P2 contain the P anion. Calcium diphosphide [81103-86-8] CaP2, contains P reaction with water Hberates diphosphine and maintains the P—P linkage. 

BeryUium reacts with fused alkaU haUdes releasing the alkaU metal until an equUibrium is estabUshed. It does not react with fused haUdes of the alkaline-earth metals to release the alkaline-earth metal. Water-insoluble fluoroberyUates, however, are formed in a fused-salt system whenever barium or calcium fluoride is present. BeryUium reduces haUdes of aluminum and heavier elements. Alkaline-earth metals can be used effectively to reduce beryUium from its haUdes, but the use of alkaline-earths other than magnesium [7439-95-4] is economically unattractive because of the formation of water-insoluble fluoroberyUates. Formation of these fluorides precludes efficient recovery of the unreduced beryUium from the reaction products in subsequent processing operations. 

Hydrogen can be prepared by the reaction of water or dilute acids on electropositive metals such as the alkali metals, alkaline earth metals, the metals of Groups 3, 4 and the lanthanoids. The reaction can be explosively violent. Convenient laboratory methods employ sodium amalgam or calcium with water, or zinc with hydrochloric acid. The reaction of aluminium or ferrosilicon with aqueous sodium hydroxide has also been used. For small-scale preparations the hydrolysis of metal hydrides is convenient, and this generates twice the amount of hydrogen as contained in the hydride, e.g. ... 

I have found that a mixture of citral and acetone, if it is subjected, in the presence of water, for a suffieiently long time to the action of hydrates of alkaline earths or of hydrates of alkali metals, or of other alkaline agents, is eondensed to a ketone of the formula CjjH pO. This substanee, which I term Pseudo-ionone," may be produced lor instance in shaking together for several days equal parts of citral and acetone with a solution of hydrate of barium, and in dissolving the products of this reaction in ether. 

Section 20.1 deals with the processes by which these metals are obtained from their principal ores. Section 20.2 describes the reactions of the alkali and alkaline earth metals, particularly those with hydrogen, oxygen, and water. Section 20.3 considers the redox chemistry of the transition metals, their cations (e.g., Fe2+, Fe3+), and their oxoanions (e.g., Cr042-). ... 

The compounds formed by the reaction of hydrogen with the alkali and alkaline earth metals contain H- ions for example, sodium hydride consists of Na+ and H- ions. These white crystalline solids are often referred to as saline hydrides because of their physical resemblance to NaCL Chemically, they behave quite differently from sodium chloride for example, they react with water to produce hydrogen gas. Typical reactions are... 

Because all of the alkaline earth oxides react with water to form basic hydroxides, they are called basic oxides. The reactions and their heats are as follows ... 

Alkaline earth oxides, heat of reaction with water, 382 Alkaline earth sulfates, K,r, 382 Alkanes, 341 naming, 338 Alkyl group, 336 Alloys, 309 Alnico, 406 copper, 71, 309 covalent bonds, and, 305 gold, 71... 

Foreign cations can increasingly lower the yield in the order Fe, Co " < Ca " < Mn < Pb " [22]. This is possibly due to the formation of oxide layers at the anode [42], Alkali and alkaline earth metal ions, alkylammonium ions and also zinc or nickel cations do not effect the Kolbe reaction [40] and are therefore the counterions of choice in preparative applications. Methanol is the best suited solvent for Kolbe electrolysis [7, 43]. Its oxidation is extensively inhibited by the formation of the carboxylate layer. The following electrolytes with methanol as solvent have been used MeOH-sodium carboxylate [44], MeOH—MeONa [45, 46], MeOH—NaOH [47], MeOH—EtsN-pyridine [48]. The yield of the Kolbe dimer decreases in media that contain more than 4% water. 

That eh is the intermediate species and not the H atom has been verified by adding NzO and methanol to water then, N2, not H2, is the principal product. Alkali and alkaline earth metals above Na in the electrochemical series will also generate eh on dissolution in water. Moreover the H/D isotope effect in water containing 50% D is consistent with the reaction 2eh—H2 + 20H (Anbar and Meyerstein, 1966 Hart and Anbar, 1970). 

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