Metals electropositive

REACTIONS WITH NON-METALS AND WEAKLY ELECTROPOSITIVE METALS... 

A non-metal or weakly electropositive metal X in Group III of the periodic table would be expeeted to form a covalent volatile hydride XHj. In fact, the simplest hydride of boron is BjHf, and aluminium hydride is a polymer (AlHj) . 

Reactions with electropositive metals. Ammonia gas reacts with strongly electropositive metals to form the amide, for example... 

Hydrated nitrates, and anhydrous nitrates of very electropositive metals (for example Na, K), contain the ion NOJ which has the structure ... 

Many metals are oxidised by water. At ordinary temperatures the more electropositive metals, for example, sodium, calcium (or their amalgams with mercury), react to give hydrogen, for example ... 

Many salt-like halides can be prepared by the action of the hydro-halic acid. HX, on the metal or its oxide, hydroxide or carbonate. The halides prepared by this method are often hydrated, particularly when a less electropositive metal is involved, for example zinc, iron. 

The mote electropositive metals react with cryohte, Hberating aluminum or aluminum monofluotide (22,23). The reduction of cryohte by magnesium is a current method for removal of magnesium in the refining of aluminum. Upon contact with strong acids cryohte Hberates hydrogen fluoride. 

It is easy to reduce anhydrous rare-earth hatides to the metal by reaction of mote electropositive metals such as calcium, lithium, sodium, potassium, and aluminum. Electrolytic reduction is an alternative in the production of the light lanthanide metals, including didymium, a Nd—Pt mixture. The rare-earth metals have a great affinity for oxygen, sulfur, nitrogen, carbon, silicon, boron, phosphoms, and hydrogen at elevated temperature and remove these elements from most other metals. 

Dinitrogen has a dissociation energy of 941 kj/mol (225 kcal/mol) and an ionisation potential of 15.6 eV. Both values indicate that it is difficult to either cleave or oxidize N2. For reduction, electrons must be added to the lowest unoccupied molecular orbital of N2 at —7 eV. This occurs only in the presence of highly electropositive metals such as lithium. However, lithium also reacts with water. Thus, such highly energetic interactions ate unlikely to occur in the aqueous environment of the natural enzymic system. Even so, highly reducing systems have achieved some success in N2 reduction even in aqueous solvents. 

The perchlorates of practically all the electropositive metals are known, except for a few cations having low charges. 

Phosphides of the less electropositive metals and the metalloids may be considered more as metal—phosphoms alloys. These are thermally stable... 

The first equation is an example of hydrolysis and is commonly referred to as chemical precipitation. The separation is effective because of the differences in solubiUty products of the copper(II) and iron(III) hydroxides. The second equation is known as reductive precipitation and is an example of an electrochemical reaction. The use of more electropositive metals to effect reductive precipitation is known as cementation. Precipitation is used to separate impurities from a metal in solution such as iron from copper (eq. 1), or it can be used to remove the primary metal, copper, from solution (eq. 2). Precipitation is commonly practiced for the separation of small quantities of metals from large volumes of water, such as from industrial waste processes. 

Thorium metal alloys readily with a large number of metals, including Fe, Co, Ni, Cu, Au, Ag, B, Pt, Mo, W, Ta, Zn, Bi, Pb, Hg, Na, Be, Mg, Si, Se, and Al. Like many electropositive metals, finely divided thorium metal is pyrophoric in air, and bums to give the oxide. Massive metal, chips, and turnings... 

Preparation of Uranium Metal. Uranium is a highly electropositive element, and extremely difficult to reduce. As such, elemental uranium caimot be prepared by reduction with hydrogen. Instead, uranium metal must be prepared using a number of rather forcing conditions. Uranium metal can be prepared by reduction of uranium oxides (UO2 [1344-59-8] or UO [1344-58-7] with strongly electropositive elements (Ca, Mg, Na), reduction of uranium halides (UCl [10025-93-1], UCl [10026-10-5] UF [10049-14-6] with electropositive metals (Li, Na, Mg, Ca, Ba), electro deposition from molten... 

Arsine is formed when any inorganic arsenic-bearing material is brought in contact with zinc and sulfuric acid. The arsenides of the electropositive metals are decomposed with the formation of arsine by water or acid. Calcium arsenide [12255-53-7] Ca2As2, treated with water gives a 14% yield of arsine. Better yields (60—90%) are obtained by decomposing a solution of sodium arsenide [12044-25-6] Na As, in Hquid ammonia with ammonium bromide (14,15). Arsine may be accidentally formed by the reaction of arsenic impurities in commercial acids stored in metal tanks, so that a test should be made for... 

Several aEylation reactions are known, frequently using an organometaEic derivative of the compound being aEylated, or a strongly electropositive metal in conjunction with the reactants. Grignard reactions are in this group. 

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. ... 

The BH4 ion is essentially non-coordinating in its alkali metal salts. However, despite the fact that it is isoelectronic with methane, BH4 has been found to act as a versatile ligand, forming many coordination compounds by means of 3-centre B-H M bonds to somewhat less electropositive metals. " Indeed, BH4 ... 

Reaction of acetylene with electropositive metals in liquid ammonia. 

Attempts to classify carbides according to structure or bond type meet the same difficulties as were encountered with hydrides (p. 64) and borides (p. 145) and for the same reasons. The general trends in properties of the three groups of compounds are, however, broadly similar, being most polar (ionic) for the electropositive metals, most covalent (molecular) for the electronegative non-metals and somewhat complex (interstitial) for the elements in the centre of the d block. There are also several elements with poorly characterized, unstable, or non-existent carbides, namely the later transition elements (Groups 11 and 12), the platinum metals, and the post transition-metal elements in Group 13. 

The metals which form silicate and aluminosilicate minerals are the more electropositive metals, i.e. those in Groups 1, 2 and the 3d transition series (except Co), together with Y, La and the lanthanoids, Zr, Hf, Th, U and to a much lesser extent the post-transition elements Sn", Pb", and Bi ". 

It will be recalled that is 100% abundant and is the heaviest stable nuclide of any element (p. 550), but it is essential to use very high purity Bi to prevent unwanted nuclear side-reactions which would contaminate the product Po in particular Sc, Ag, As, Sb and Te must be <0.1 ppm and Fe <10ppm. Polonium can be obtained directly in milligram amounts by fractional vacuum distillation from the metallic bismuth. Alternatively, it can be deposited spontaneously by electrochemical replacement onto the surface of a less electropositive metal... 

Aqueous perchloric acid solutions exhibit very little oxidizing power at room temperature, presumably because of kinetic activation barriers, though some strongly reducing species slowly react, e.g, Sn , Ti , V and V , and dithion-ite. Others do not, e.g. H2S, SO2, HNO2, HI and, surprisingly, Cr and Eu . Electropositive metals dissolve with liberation of H2 and oxides of less basic metals also yield perchlorates, e.g. with 12% acid ... 

Steady-state potential comparable with Type 2 reversible electrode Potentials of electropositive metals that react with solution to give sparingly soluble salts of the metal. Cu or Ag in NaCl or Ag in HCI giving an M/MX/X type of electrode... 

Metals. It reacts with electropositive metals to evolve H and form metal perchlorates. These... 

Decompositions of oxalates containing the strongly electropositive metals yield an oxide product but the more noble elements yield the metal. Discussion of the mechanisms of these reactions and, in particular, whether metal formation necessarily involves the intermediate production of oxide which is subsequently reduced by CO has been extended to consideration of the kinetics of pyrolysis of the mixed oxalates [32]. 

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