« PreviousContinue »
oxides and hydroxides, in the formation of hydroxides by the direct union of water with the oxides, in the great stability of their oxides towards reducing agents, in the stability of their salts and the existence of but few basic salts, in the preparation and properties of their sulphides and hydrosulphides, &c. In its physical character however Mg differs from Ca, Sr, and Ba, and resembles Be, and to some extent Zn and Cd. Beryllium, although occurring in Series 2, is decidedly more like the odd-series, than the evenseries, members of the group; the properties of the oxide and hydroxide of Be are very similar to those of the corresponding compounds of Zn and Cd; in the comparatively large number of basic salts which it forms, and in the readiness with which oxyhaloid compounds of Be are produced, the metal also resembles the odd-series members, especially Hg. Some of the haloid compounds of Be, Zn, Cd, and Hg, are gasifiable without decomposition at workable temperatures ; no pounds of the other elements of the group have been gasified.
Mercury is distinguished from the other members of the group by the fact that it forms two series of compounds, mercurous HgX, and mercuric HgX,,
SO, CO ,
also by its physical properties, &c.
Looked at broadly, Ca, Sr, and Ba, are the most positive members of the group, next to them comes Mg, and Hg is the least positive. It is to be noted that the arrangement of Group II. in accordance with the periodic law shews a gap Series 9; if an element is discovered to fill this gap it will probably resemble mercury on the one hand and zinc and cadmium on the other.
Beryllium to some extent summarises in itself the properties of the other members of the
group. It cannot be said that the even-series members of Group II. form a sub-group or family distinctly marked off from the odd-series members of the group; nor can it be asserted that there is a gradual change of properties from the first to the last member of the group. All the members shew distinct relations to each other; neither the family.character nor the group-character preponderates.
If we now turn to Group VI. we shall find that the 410 first member of the group, oxygen, to some extent summarises in itself, or is typical of, the properties of all the other members; and that the other elements placed in this group fall into two well marked families, one of which contains the even-series members and the other contains the odd-series members of the group.
M. E. c.
THE ELEMENTS OF GROUP VI. 411
W=1836 U=239-9 Group VI.
URANIUM. elements (omitting oxygen) Atomic weights
18.7 Melting points Above 2000°.
Infusible at full Softens and agglom- A full red-heat. white-heat.
erates at white-heat. Sp. heats
*028 Atom, weights
12.9 spec. gravs. Occurrence and Chrome-ironstone, Occurs in small Occurs very sparing. Sparingly distripreparation. (FeoCr203) and lead quantities as oxide ly, as tungstate of buted, as oxide in
chromate, &c. occur and sulphide, also as Ca, of Fe and Mn, pitchblende, as uranin a few rocks; not lead or cobalt mo- and of Pb; also as ite of Ca and of Cu, widely distributed. lybdate.
as carbonate of U Obtained by deoxi- Obtained by reduc- Obtained by reduc- and Ca, &c. dising Cr,03 by C, oring oxide or chloride ing the oxide or chlo. Obtained by reducby action of Kon by H, or the oxide ride in H.
ing the chloride by Cr.Clo, or by elec- by C or KCN.
Na. trolysis of Cr2014
containing CrCla Colour, appear- Very, hard, brittle, Ashen-grey powder; Resembles iron in White, lustrous, ance, fc. powder composed of when compressed, is colour and lustre; metal; softer than
minute brilliant tin- a silver-white, lus- hard and brittle; also steel; malleable, but white crystals. trous, liard, brittle, obtained as a brown cannot be beaten Descriptions differ infusible, metal. amorphous powder. into thin plates; also much; probably the
obtained as a grey. metal has not yet
black powder. been obtained ap
proximately pure. General chemical Burns in stream of Not oxidised in air Burns in air at red- Slowly tarnishes in properties. 0; heated in air is su- at ordinary tempera- heat; unchanged at air; oxidised rapidly
perficially oxidised; ture but burns at low ordinary tempera- in air at 150°—200°. oxidised by molten red-heat.
Combines with C1 KNO3 or KC103. No reaction with Oxidised to W03 by and Br when heated, Easily dissolved by HCIAq, HFAq, or hot HINO3Aq, and very slowly with dilute HCIAq or H.S04Āq; oxidised HCA or H.S04.
hot I vapour. H2SO4Aq, but does by conc. HINO, to Dissolves in hot Dissolves in most not react with hot M003; oxidised by KOHAq to form K aqueous acids with conc. HNO3.
molten KOH. but tungstate and H. evolution of H and Combines readily no reaction with Combines with Cl at formation of salts. with Cl and I when KOHAq.
high-temperatures. Forms two series of heated.
Combines with Ci Does not seem to salts, members of Decomposes steam and Br, but not di- form salts by replace one of which always slowly at a red-heat. rectly with I.
ing I of acids. contain ( in addition Replaces H of acids Salts formed by re- WO3 is an anhy- to U and the acid forming two series of placing H of acids dride, and it also radicle. salts.
by Mo are scarcely combines with other 003 is an anhydride. Croz is an anhy- known.
more negative anhy- Atom of U is tetradride; Cr203 seems M003 is an anhy- drides, e.g. S03. valent in gaseous to form a few salts dride, and also com- Atom of W is penta- molecules. by heating with bines with many
and hexavalent in
more negative anhy- gaseous molecules.
tavalent in gaseous
General formulae and chemical characters of compounds. 412 The compositions of the more important compounds of these four metals are expressed by the following formulae; but representatives of each formula are not known for all the elements, thus sesquioxides, M,0g, of tungsten or uranium have not been obtained, and the formula MX, is represented by WCl, only.
Oxides. MO, M,O2, MO, MOg: hydrates of some of these are known.
Sulphides. MS, MS, MS,, MS,, MSC.
Haloid compounds; chiefly chlorides. MX, MX,, MX, MX, MX,
Acids. HMO, H.M.O.,, &c., H MS,
Salts. MSO, M2NO%, &c.; M,(SO2),*M,(NO3), &c. when M=Cr. M(S0,), M(NỞ), M6,(80.), &c. when M=U. . Salts of Mo and W are scarcely known.
The oxides MO are scarcely known; hydrates of CrO and 413 MoO are obtained by adding a solution of potash in air-free water to solutions of Cr, Cl, and Mo.cl, respectively. These hydrates are rapidly oxidised in the air; neither yields corresponding salts by its reactions with acids.
The sesquioxides M,0, are stable compounds when M = Cr or Mo (chromic and molybdic oxides); no sesquioxide of W or U is known. Cr,0, is prepared by precipitating a solution, of a chromic salt by ammonia, washing, drying, and heating; in the case of Mo, 0g, the hydrated oxide preciptated by potash is heated in hydrogen. Both oxides form dark coloured solids, insoluble or nearly insoluble in acids. Hydrated Cr, O. (Cr, 0,.3HO) dissolves readily in acids forming chromic salts, e.g. Cr 350, This oxide also seems to combine with a few basic oxides, e.g. with Cao. It is therefore basic but also slightly acidic.
The dioxides MO, are dark coloured solids, obtained by reducing the oxides Mo, directly or indirectly. 'Cro, is more easily formed by passing nitric oxide into an aqueous solution of potassium dichromate (K,Cr,0); M00, and Wo, by heating M00, and Wo, in hydrogen to low redness, or by digesting a solution of Moon, or wo, in hydrochloric acid with copper or zinc and then precipitating by ammonia. UO, may be prepared by digesting UCI, with water.
Cro, is decomposed by heat at 300° with evolution of oxygen and production of Cr,Oz; the other oxides MO, are oxidised to MO,, Moo, by heating with nitric acid, wo, by
heating in air, and UO, by the action of air at ordinary temperatures. These oxides Mo, are slightly soluble in acids"; UO, gives salts, e.g. U(SO2),, but no definite salts have yet been certainly obtained corresponding to any of the other oxides MO, although such salts seem to exist.
The trioxides MO, are anhydrides. Cro, is prepared by adding a sufficient quantity of concentrated sulphuric acid to a solution of potassium dichromate, Moo, and W0, are obtained by oxidising the lower oxides, or better from ammonium molybdate and tungstate, respectively, by heating with nitric acid and then washing out the ammonium nitrate formed. UO, is obtained by heating uranyl nitrate
(UO)(NO3), Cro, is very soluble in water forming a markedly acid liquid; under special conditions the hydrate Cr0g.H,0—i.e. H Cro, chromic acidcan be obtained from this liquid.
Cro, interacts with acids to form oxygen and salts corresponding with the oxide Cr, Oy; thus
2Croz + 3H SO Aq=Cr,(SO2), Aq + 3H,0 + 30. This oxide readily parts with part of its oxygen and therefore acts as an oxidiser, e.g. when it is heated, Cr,0, and oxygen are produced.
M00, is much less soluble in water than Cr0,; WO, is only very slightly soluble in water; and UO, is insoluble. Hydrates of these oxides exist and exhibit acidic properties (s. Acids, par. 416), but none of them is obtained by the direct addition of water to the oxide. The oxides Moo, and WO; form various complex compounds with several anhydrides such as SO3, P,05, B, O,, &c. The oxide UO, interacts with a few acids to form salts (s. Salts, par. 417).
The oxides MO, and MO, are on the whole basic; the oxides MO, are acidic, but their acidic character is less marked as the atomic weight of M increases. The change from MO, to MO, is effected the more easily and directly the greater the atomic weight of M. Of the oxides MO, UO, shews the most clearly marked basic character. Of the oxides MO, UO, is the most stable towards heat and reducing agents, and
Cro, is the least stable. 414 The most important sulphides are Cr S,; Mos, Mos,
MOS,; WS, WS,; and Us, Chromic sulphide, Cr, s, is prepared by passing sulphuretted hydrogen over hot chromic oxide (Cr,0z); it is not obtainable by reactions between compounds