471 472 yellow oily liquid by decomposing one of its alkaline salts by dilute HCIAq. Thio-carbonic acid and its salts are very easily decomposed, to CS, and H2S in the case of the acid, and to H,S and carbonates in the case of the salts. The haloid compounds of the carbon family of the form MX, where X = Cl or Br, are prepared, except in the case of the carbon compounds, by strongly heating an intimate mixture of the oxides MO, and carbon in a stream of chlorine, or bromine; tetrachloride of cerium has not yet been prepared. TiCl, is a liquid boiling at 136°, the other tetrachlorides are solids; they have all been gasified without decomposition. These tetrachlorides all combine with various other chlorides, and in some cases with other compounds, to form double compounds; e.g. TiCl, PCI,; 3Tic,.4NOCI; TiCl. 4NH; ZrCl. 2NaCl; 2ThCl. 8NH,CI. The tetrafluorides MF,, M = Ti, Zr, Ce, or Th, are obtained by dissolving the hydrated dioxides MO,.xH2O in aqueous hydrofluoric acid and evaporating. The tetrafluorides of titanium, zirconium, and thorium form compounds with potassium fluoride of the form 2KF. MF,; as in some cases the corresponding hydrogen compounds 2HF. MF, have been isolated and the potassium compounds have been obtained by neutralising aqueous solutions of these hydrogen compounds, it seems better to regard the compounds in question as the potassium salts of fluotitanic, fluozirconic, and fuothoric acids, H2MF, (M=Ti, Zr, Th). A double fluoride of cerium and potassium is known, but its composition is different from that of the K,MF, salts; it is represented by the formula 2CeF. 3KF.2H2O. 6 6 Cerous chloride, or cerium sesquichloride, Ce,Cl, is obtained by heating in chlorine a mixture of the corresponding oxide, Ce,O,, and carbon. Carbon forms several haloid compounds; CX,, C,X, C.X,, where X = Cl or Br; and CI. Carbon tetrachloride CCI, trichloride CCl, and dichloride C2C1, have been gasified without decomposition. The first of these compounds is obtained by the interaction of chlorine and chloroform, CHCl,; the second by the interaction of chlorine and ethylene dichloride, CHCI,; and the third by reducing C,Cl, by means of hydrogen evolved in contact with the carbon trichloride. Salts. Salts of carbon, i.e. compounds obtained by replacing the hydrogen of acids by carbon, are unknown. Titanium forms two series of salts; titanous salts represented by the sulphate Ti,(SO), which is obtained by dissolving the corresponding oxide Ti2O, in concentrated sulphuric acid and evaporating; and titanic salts obtained by dissolving the dioxide, TiO2, in acids. Most of the titanic salts are basic salts, e.g. TiO.SO.; 5TiO2. NO.жH2O; 2TiO. PO̟îH2O ; &c.; a few normal salts are known, e.g. Ti(SO4)2. 3H,O. Zirconium forms one series of salts, the zirconic salts, represented by the sulphate Zr(SO)2, and one or two others. Most of the zirconium salts are basic salts, e.g. 3ZrO2. SO; 3ZrO,. 2N,O,; 5ZrO2. 4P,O,, &c. The salts of thorium are all thoric salts, e.g. Th(SO4)2; Th(NO3).жH2O; Th ̧(PO).жH2O, &c. The thoric salts are usually normal; a few basic salts are known, e.g. 2ThO,.7SeO, H2O. Cerium resembles titanium in that it forms two classes of salts. The cerous salts Ce,. 3X are numerous; e.g. Ce (SO).xH2O; Ce(NO). H2O; CePO, &c. The chief representatives of the ceric salts are Ce(SO4)2.xH2O, and Ce(NO3). The salts of all the metals of the family form many double salts generally by combination with salts of the alkali, and alkaline earth, metals. Carbon is evidently separated from the other even series 473 members of Group IV. by its distinctly non-metallic character. The other elements are all metals in their physical properties; their oxides are basic, but most of them shew acidic functions. As the atomic weight increases the elements become more distinctly metallic in their chemical properties. In a few respects, e.g. existence of M,O, and corresponding salts, cerium is more closely related to titanium than to any other member of the family. The three elements titanium, zirconium, and thorium exhibit very marked similarities; the existence of the compounds K,MF, is characteristic. 6 General chemical properties. 475 Brown, amorphous K or Al. Amorphous Si burns Soluble in HFAq; Amorphous Si, but Combines directly Combines with seve- Exhibits allotropy. The sulphide is Prepared by reduc- Oxidised to GeO2 by ⚫055 White; crystalline; Prepared by reduc- Burns to SnO2 when Dissolved by dilute ⚫031 White with greyish tinge; soft; crystalline; very malleable; ductile, but not tenacious. Found native in small quantities; chief ore is PbS, widely distributed in fairly large quantities. Prepared by reducing PbO by carbon or potassium cyanide; also by electrolysis of solutions of salts. Oxidised superficially in moist air; heated in air burns to PbO and higher oxides. Dissolved by sulphuric and nitric acids. Combines directly with Cl and S. Atom is divalent and tetravalent in gaseous molecules. General formulae and chemical characters of compounds. Silicon is the only member of the family which forms a compound with hydrogen. Numerous compounds of silicon with carbon, hydrogen, and oxygen, the silico-organic com pounds, are known. The compounds SiCl,, SiBr1, SiL; GeCl,, GeL, GeS; SnCl2, SnCl,; PbCl2, Pb(CH),, have been gasified and their vapour densities have been determined. Oxides: MO, M = any element of the family; MO, M = Ge, Sn, Pb; also Sn,O,, Pb,O,, and PbO4. Hydrates of most of these oxides are known some of them are acidic. Sulphides: MS2, Many element of the family except Pb; GeS, SnS, PbS. Haloid compounds: MX,, Many element of the family except Pb; MCl2, M = any element of the family except Si; Si,X ̧. Salts: salts of Si are unknown; MX, X = SO1, 2NO,, PO, &c.; a few stannic salts Sn. 2X are known. Salts derived from acidic hydroxides; M.XO,, X = Si, Sn, Pb; also many complex silicates, some complex stannates, and probably one or two plumbites M ̧PbO2; (M = K, Na, &c.). Silicon hydride, SiH,, is obtained mixed with hydrogen 476 by decomposing any alloy of magnesium and silicon by hydrochloric acid. The hydride is obtained pure by the interaction between sodium and the compound SiH(OC,H,),. Silicon hydride is a colourless gas, condensing under great pressures to a colourless liquid; it is decomposed by heating to about 400°; it is very inflammable when mixed with air; the gas interacts with an aqueous solution of potash to form potassium silicate and hydrogen; SiH ̧ + 2KOHAq + H2O = K,SiO,Aq + 4H ̧. 2 Oxides. The dioxides SiO, Geo, and Sno, are obtained 477 by strongly heating the elements in air; GeO, and SnO, are more readily obtained by oxidising the elements by concentrated nitric acid. Silica, SiO,, is usually prepared by decomposing an alkali silicate by an acid, evaporating to dryness, heating, and removing the alkali salt of the acid by solution in water. Lead dioxide, PbO,, is obtained by evolving oxygen in contact with a lower oxide of lead in presence of an alkali; the usual method is to suspend PbO in concentrated KOHAq and pass in chlorine, or to boil PbO with KOHAq and KCIOAq. The oxides GeO, SnO, and PbO, are obtained by adding an alkali to solutions of the corresponding chlorides, MCI,, and drying the hydrated oxides so produced. The oxides are all white, or nearly white, solids, insoluble in water. Silicon dioxide, SiO,, when strongly heated is insoluble in ordinary acids except hydrofluoric; GeO, probably forms salts by interacting with acids, but these salts have not 478 yet been isolated; hydrated stannic oxide, SnO,.HO, dis- 2 3 &c. The other hydrated di oxides MO.HO, where M = Sn or Pb, dissolve in concentrated aqueous potash, or in molten potash containing a very little water, and salts are obtained on evaporating in vacuo; these salts belong to the form X,MO, where X = K or Na. The monoxides SnO and Pb0 dissolve in acids to form salts; GeO also dissolves in acids, but no salts have yet been isolated; a few stannous salts and a considerable number of plumbous salts, MX, have been isolated. Plumbous oxide, PbO, dissolves in conc. potash or soda solution; a few salts of the form M,PbO, have been obtained, M = K, Na, or Ag. 2 3 3 3 The sesquioxides Sn20, and Pb0, are obtained by the action of weak oxidisers on solutions of stannous or plumbous salts, MX, in presence of an alkali; SnO, easily oxidises in air to SnO,; Pb,O, interacts with dilute acids as if it were Pbo. Pbo, a plumbous salt (PbX) is formed and PbO, remains. Sulphides. The only sulphide of silicon is SiS,; it is prepared by passing carbon disulphide vapour over a heated mixture of silica and carbon. The sulphides GeS, and SnS are obtained by passing sulphuretted hydrogen into acidified solutions of germanic and stannic chlorides, respectively. GeS is obtained by heating GeS, in hydrogen; and SnS by passing sulphuretted hydrogen into an acidified solution of stannous chloride. When sulphuretted hydrogen is passed into an acidified solution of a lead salt, PbS is pptd. There are indications of the existence of a higher sulphide of lead than PbS, but none has been isolated. Both stannous and stannic sulphide, SnS and SnS,, dissolve in solutions of alkali sulphides to form alkali thio-stannates, M.SnS,; PbS fused with an alkali carbonate probably forms an alkali thio-plumbate; |