Oxidation and Oxidizing Refining of Metis 208 Theory of Metallurgical Processes

209

Table V. HEATS OF FORMATION OF OXIDES OF IMPURITIES FROM ELEMENTS

AiMoiate Na 3 As0 4 is formed according to the reactions 2Pb -f 0 2 = 2PbO + AZ 3PbO + 2 [As] = (As203) + 3 [Pb] + AZ (As203) + 3 (Na20) = (3NaaO. Asa08) + AZ (3Na 2 0. As203) + 2PbO = (3Na20 As205) -f 2 [Pb] + AZ (81) (82) (83) (84)

Q298 per mole Oxide MeO 52 A 138.0 39.8 82.2 02 104.8 92.0 79.6 166.4 Oxide

Q298 per mole MeO 156.2 167.1 138.8 7.3 02 104.1 111.4 1 138.8 i 14.6

PbO Bi 2 0 3 Cu 2 0 ZnO

As 2 0 3 Sb 2 0 3 Sn0 2 Ag 2 0

iiuiing up equations (82), (83) and (84), we obtain 5PbO + 2 [As] + 3(Na20) (3Na 2 0. As205) + 5 [Pb] + AZ5 (85) BOSe oquilibrium constant is
K c

As the table indcales, silver, bismuth and copper have a lessef affinity for oxygen than lead; therefore, it may be expectod that Zn, As, Sb and Sn are, while Bi, Cu, Ag and Au are not oxidi/.od by the lead oxide. Of the three remaining impurities, the first to oxidize is tin, which forms, together with the lead oxides, a powder- or paste-like (depending on Sb and As contents) mass of a light-yellow (for purely tin skimmings) or dark-yellow (for skimmings with Sb and As) colour. Tin skimmings consist of lead stannates (Sn0 2 -nPbO) and partly of tin and lead antimonates. After tin is removed, As 4 0 6 and Sb 2 0 3 vapours seprate from molten lead, and formed on the bath surface are lead arsenates coloun-tl from lemon-yellow to light-brown, and lead antimonates, colourod from dark-brown to black. The relative amount of arsenates in the dross gradually falls, that of the antimonates rises. After arsenio and antimony are removed, lead oxidizes to litharge, which floata to the surface of the bath as a green-yellow powder. At present, lead is refined not through oxidation by air, but by saltpetre, with the addition of caustic soda to bind the acid and amphoteric oxides by a strong base (Na 2 0), the process being called the alkali refining of lead. The reaction between PbO and Me' (impurities) proceeds onJy at points of contact of the surface layer of oxides with the metal, On heating, saltpetre docomposes with the evolution of atomic oxygen according to the reactions NaN0 3 = NaNO ; + O 2NaN0 2 = Na 2 0 + N 2 + 3 0 Saltpetre is charged by means of a special device which allows tlio molten layer'of alkali and salt to be kept in contact with the crudo lead. Molten lead is pumped from below through the molten saltpetre and alkali. The lead then oxidizes to PbO, which interacty with the impurities (for example, with arsenic); the As 2 0 3 obtained il slagged, forming stable chemical compoundssaltswith Na 2 0.

(Na 3 As0 4 ) a [Pbp [As] 2 lPbOP(Na 2 0)3

AZ = AZ-hAZ + AZ4 een, the thermodynamic potential of the overall reaction (85) lkZl) is numerically much greater than that of reaction (82) (AZ) I M M HUSO it is summed up with the thermodynamic potential of the lifiction of formation of arsenate from oxides (Na 2 0 and As 2 0 3 ). i result, the equilibrium constant of reaction (85) is considerably yniicr than that of reaction (82) and the residual concentration of ni lead drops substantially. Also oxidized are other impurities, Mth nutimonate Na 3 Sb0 4 and stannate Na 3 Sn0 3 being formed. A.s a result, the impurities (As, Sb, Sn, Zn) are efficiently reil and their respective contents drop to a few thousandths of a |il cent. A high rate of the process is attained by the use of saltpetre ii oxidizer, of an alkali for slagging the impurities and the pror mu of a vigorous circulation of lead through a layer of molten di. Oxidation of Components in the Manufacture and Remelting o Alloys Oxidation of alloy components in the manufacture, remelting or IDBcial oxidizing refining of alloys involves the same physico hemical principies as those of the oxidizing refining of metis. A feature of these phenomena is that the concentrations of the rumponents in the alloy are much greater than those of the impurii es in the metal. Uualitatively, the phenomena are basically the same as in oxidiMu',- refining of metis. The oxidation of impurities is of particular Importance to alloys composed oE components far apart in the order l their affinity for oxygen, as in silicon bronzes, brasses, alloys
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