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CHAPTER XXIII.

THE ELEMENTS OF GROUP VII.

GROUP VII. is unfortunately far from complete; it com

447 prises the four distinctly negative and non-metallic elements fluorine, chlorine, bromine, and iodine, and the element manganese which is usually classed with the metals. We have already considered the inost important properties of chlorine, bromine, and iodine (Chap. xi. pars. 150–159), and also of manganese (Chap. xi. pars. 194—203); it remains therefore to consider fluorine, and to summarise the properties of all the elements of the group.

FLUORINE. This element is not obtained by a process.similar 448 to that whereby chlorine, bromine, and iodine are separated from their compounds. When liquid hydrogen fluoride is electrolysed at a low temperature, a colourless gas is evolved at the positive pole ; crystallised silicon and boron burn in this gas to Sif, and BF%, respectively; the gas interacts with water to form ozone and a solution of hydrofluoric acid. This gas

is very probably fluorine.

The chief naturally occurring fluorine compound is fluorspar which is more or less pure calcium fluoride, CaF,

The compositions of many fluorine compounds are similar to those of the compounds of chlorine, bromine, and iodine ; thus HF, BF3, SbF3, BiOF, CrO,F,, &c. are analogous to HCI, BBr.,, ShI BiỐCI, Cřo,cl, &c. In some cases a stable fluoride is known to which there is no corresponding chloride, bromide, or iodide ; thus PF, exists as a gas, but the highest gasifiable chloride of phosphorus is PCI;. No oxide or oxyacid of fluorine has yet been obtained; but the reactions of the element itself have scarcely been examined as it has only recently been isolated. Hydrogen fluoride, HF, is prepared by the interaction 449 of_sulphuric acid with calcium fluoride CaF,; thus CaF, + H SO, Aq = CaSO, + 2HFAQ (compare preparation of HCI, HBr, and HI, Chap. xl. par. 153). Hydrogen fluoride is a colourless strongly smelling and irritating gas at temps. above 20°, and a light mobile liquid at temps. under 20°. The vapour-density points to the existence of the gaseous molecule HF only at fairly high temperatures, and to the existence of the gaseous molecule H F, at temps. not very far above 20°. Liquid hydrogen fluoride chars organic matter rapidly, and dissolves many bodies which are insoluble in all other acids, e.g. strongly heated silica, titanium oxide, boron, silicon, &c. An aqueous solution of this compound interacts with metals and basic oxides similarly to aqueous solutions of hydrochloric, hydrobromic, and hydriodic, acids ; fluorides,

Ba Bi salts of the form MF (M = K, Na, &c.), are produced.

2' 3' The metallic fluorides shew great readiness to combine with hydrogen fluoride and produce double compounds; e.g. KF.HF, BiFg.3HF, &c. Some of the fluorides of non-metallic elements also combine with hydrogen fluoride; the products in some cases react as acids; thus SiF .2HF is a dibasic acid (H SiFo, fluosilicic acid), and BF.HF is a monobasic acid HBF, fluoboric acid). "A few similar compounds of hydrogen chloride and bromide are known, e.g. HAuCl, and HAuBr, both of which react as monobasic acids (s. par. 441.)

Hydrofluoric acid, HFAq, is an extremely weak acid; its affinity for bases is less than 5 when that of hydrochloric acid is taken as 100 (s. Chap. XIII. pars. 251, 255).

Whether fluorine does or does not interact with water and solutions of alkalis similarly to chlorine, bromine, and iodine, cannot be determined until the properties of fluorine have been more fully investigated.

The chemical properties of Auorine, so far as they have been investigated, shew that this element is very similar to the elements chlorine, bromine, and iodine; but, at the same time, there are fairly marked differences between fluorine and these three elements. No one of the four elements shews any tendencies to react as a metal.

MANGANESE is the second member of the even-series of Group VII. The sketch of the chemical properties of manganese given in pars. 195–199 of Chap. XI. shews that manganese is at once metallic and non-metallic in its chemical functions. The oxides MnO, Mn,,, and Mn,O, are basic; Mno,

450

451

is feebly acidic. A series of manganous salts MnX (X = SO,, 2NO, PO, &c.) exists; a few manganic salts Mn 3X are also known. Permanganic acid, H.Mnog, has been isolated and a number of permanganates have been obtained as definite stable salts, generally isomorphous with perchlorates MCI,O (M=K,, Ba, &c.). Many manganates, MMnO,, are also known; these salts do not correspond in composition with any salts derived from acids of chlorine, bromine, iodine, or fluorine; they are similar to the sulphates, selenates, and tellurates MXO, (M=K,, Ba, &c.; X = S, Se, Te).

Manganese, then, shews very feeble analogies with the other elements which are placed in the same group with it.

If the three generalisations stated in par. 446 are applied 452 to Group VII., they would lead us to expect that the unknown members of the even series of this group should resemble manganese, but should

on the whole be more distinctly inetallic than this element; and that the unknown members of the odd series of the group should resemble the halogen elements, but should be less decisively non-metallic than these elements; the unknown members of series 9 and 11, Group VII., might fairly be expected to form a few salts by the interactions of their oxides with acids.

CHAPTER XXIV.

453

THE ELEMENTS OF GROUP III.

2
4
6
8

10 12 Even series. B=10.9 Sc=44 Y*= 89-6 La=138.5 Yb*=173 Group III.

3
5
7
9

11
Lodd series. Al=27.02 Ga=69 In=1134

TI=20364 Even-series BORON.

SCANDIUM. YTTRIUM. LANTHANUM. YTTERBIUM. elements Atomic weights 10.9

44
89-6
138-5

173
The molecular weights of these elements are unknown.
Sp. grs. (approx.) 2-5

6.2 Atom. weights 4:3

22:3 $, ei. gruvs. Sp. heats •5 (?) not determined. not determined.

0449 not determined. Appearance, and Dark greenish- Not isolated. Grey powder. Steel-grey pow- Not isolated. yeneral physical brown powder.

der; or, when properties. Non-conductor.

compressed, of electricity.

lustrous, greyHas not been

white, hard,par-
melted.

ticles.
Fairly malle-
able and ductile.
Melts at full

red-heat. Occurrence and Chief com- Small quanti- Occurs as sili- Silicate occurs, Small quantipreparation pounds occur- ties of silicate cate in small with silicates of ties of silicate

ring in rocks occur in a rare quantities with Ce, Di, Fe, and occur in a rare
and waters are Swedish mine- silicate of scan- Ca, in a few rare Swedish mine-
boric oxide ral.
dium and ytter- minerals.

ral.
B203 and borax Element has bium.

Prepared by re- Element has not Na2B407; not not been iso- Prepared by ducing LaCl2 been isolated. widely distrilated.

electrolysing by potassium. buted, nor in

fused
largequantities.

Y C13.x Naci,
Prepared by

or by de-
strongly heating

chlorinating the B20, with so

same salt by sodium.

dium. General chemical Burns in air or

Burns when Oxidises in ordiproperties. oxygen to B20.3.

heated in air, nary air to Decomposes

giving Y203. La203. steam at red

Decomposes Decomposes heat forming

water, rapidly cold water B20, and H.

when warmed. slowly, hot waOxidised by

Dissolves in di- ter rapidly, with heating with

lute acids, also evolution of hyHNO3, H.S04,

in hot KOHAq, drogen. molten Kon,

with evolution
or molten

of hydrogen.
KNO3.
Combines di-
rectly with CI,
Br, I, S, and
also with N.
Atom of boron
is tri-valent in
gaseous mole-

cules. * There are still some doubts whether these elements are or are not mixtures of two or more distinct kinds of matter.

Boron is said to exist both as an amorphous powder and as metal-like, hard, lustrous, crystals; but recent investigation shews that the so-called crystalline boron is a compound of boron and aluminium.

General formulae and chemical characters of compounds. 454 The compounds BCI,, BBry, and BF,, have been gasified ; these formulae are molecular. No compounds of the other even-series elements have yet been gasified; the formulae given are the simplest that express the compositions of these compounds. Gaseous aluminium and indium chlorides have the molecular composition MCI, and gallium chloride appears to exist in the gaseous state both as GaCl, and Ga,ci,. There are indications of the existence of a hydride of boron, probably BH,; but the compound has not been isolated. The compounds of the elements of this family, with the exception of those of boron, have not been very fully investigated : there are many points in the chemical history of boron which require elucidation.

Oxides: MO
Haloid compounds: MX.
Sulphides: MS.

Acids: H,BO, H,B,0,H,B,C,; no acids of other elements are known.

Salts: M,3X; X = SO,, 2NO3, 3PO,, &c.; M = Sc, Y, La, Yb, not B.

The oxides M,0,, with the exception of B,0.,, are obtained 455 by adding an alkali to the solution of a salt, and heating the hydrated oxide which is pptd. B,0, is found in waters in various volcanic districts; it is formed by heating boron in oxygen.

Boric oxide, B,0,, is acidic; it dissolves in water, and from this solution crystals of ortho-boric acid, H,BO,, separate on evaporation. By heating ortho-boric acid to 1000 metaboric acid, H.B.0,, is obtained ; and at 160° tetra- or pyro-boric acid, H.B.O is formed. Salts are known derived from each of these acids; borax, one of the most important salts, is sodium tetra-borate Na,B,0,; the ortho-borates are very unstable salts, it is doubtful whether they exist in solution in water. A solution of boric oxide in water reacts as if it contained dibasic metaboric acid, H,B,O, Boric acid is an extremely weak acid. Dilute aqueous solutions of alkali borates precipitate metallic oxides, not borates, from solutions of

many metallic salts; that is to say, these dilute solutions behave as if they contained boric acid and free alkali, pro

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