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Melting points (approx.) Atom. weights

spec. gravs. Colour, appearance, &c.

Occurrence and preparation

General chemical properties

The molecular weights of these elements are unknown.

'6 (at abt. 500°) increases rapidly as temp. increases. not determined.

5.4

White, lustrous, hard.

Not widely distributed. Oxide occurs in a few rocks. Prepared by reducing fused BeCl2 by Na, not by electrolysis of BeCl2.

Not oxidised in ord.
air; even when heat-
ed in O is only super-
ficially oxidised.
Does not decompose
H2O even at red
heat.
Combines with Cl,
Br, and I, at high
temps.; does not
combine directly
with S.
Dissolves in

KOHAq forming
BeO and H.
Oxide (BeO) basic
but not alkaline.
Distinctly metallic.

full red-heat; above Sr.

25.3

Whitish-yellow; abt. as hard as lead, very ductile, but becomes brittle when hammered. Carbonate, phosphate, sulphate, silicate, &c. very widely diffused in rocks, water, plants, and animals. Prepared by electrolysis of mixture of CaCl2 with SrCl2 and NH4Cl, or by reducing CaCl2 by Zn-Na amalgam. Quickly oxidises in moist air; decomposes cold H2O rapidly; burns in air at red heat.

Combines with Cl, Br, I, P, and S, at high temperatures. Oxide (CaO) strongly basic and alkaline. Strongly positive metal.

above Ba; moderate red-heat.

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397

General formulae and chemical characters of compounds. (M = Be, Ca, Sr, or Ba). MO, MO,H,,MO, (no BeO, known), MS, MS H. (no BeS, H, known), MX, (X=F, Cl, Br, I), MSO, M2NO,, MCO,, &c. The only compounds which have been gasified are BeCl, and BeBr

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398 The oxides MO may be prepared by direct combination of metal with oxygen, or by decomposing the hydroxides (MOH) by heat (BaOH, is not decomposed by heat alone). The hydroxides MOH, where M-Ca, Sr, or Ba, are obtained by combining water with the oxides MO, or by precipitating solutions of salts of M by potash or soda. Beryllium hydroxide, BeO,H,, is prepared by precipitating an aqueous solution of a salt of Be by NH,Aq, and drying at about 100°. The peroxides MO, (M = Ca, Sr, or Ba) are produced by interactions between HO,Aq and solutions of salts of M; the compounds MO,. xHO thus obtained lose water when dried, when M = Ba the drying is conducted over sulphuric acid in vacuo, when M=Sr the hydrated peroxide is dried at 100o, and when M = Ca the temperature is raised to 130°. BaO, is also obtained by heating BaO in oxygen at about 200°; the other oxides MO do not directly combine with oxygen.

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The oxides CaO, SrO, and BaO are somewhat soluble in water; the solubility increases from CaO to BaO. The solutions are alkaline towards litmus paper; they interact with acids to produce salts and water; they precipitate hydrates of iron, copper, manganese, and many other heavy metals, from solutions of salts of these metals; they absorb and combine with carbon dioxide. These oxides combine with water forming hydroxides which are very stable compounds. Beryllium oxide, BeO, is insoluble in water; it does not directly combine with water. This oxide has no alkaline properties; it interacts with acids to form salts and water. None of these oxides, except BeO, is easily reduced, e.g. by heating with C, or in H or CO.

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The hydroxides MO,H,, where M = Ca, Sr, or Ba, are fairly soluble in water; the solubility increases as the atomic weight of M increases; CaO,H, is decomposed by heat (to CaO+ H2O) at 300°-400°; SrO,H, at a higher temperature ; BaOH is not decomposed even at a full red heat. hydroxides do not interact with solutions of the alkalis (potash, soda, ammonia). They form compounds with water (hydrates); the most marked of these hydrates have the composition

These

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MOH.. 8H2O. Beryllium hydroxide, BeO,H,, is easily changed by heat to BeO + H2O; it is insoluble in water and has not an alkaline reaction towards litmus. When freshly precipitated this hydroxide dissolves in KOHAq or NaOHAq, but is reprecipitated on heating. The freshly precipitated hydroxide also dissolves in (NH),CO,Aq and K,CO,Aq; by boiling the solution in (NH),CO,Aq a basic carbonate of beryllium is precipitated. BeOH, forms a number of hydrates the compositions of which vary with small variations in the conditions under which they are prepared; they are all readily decomposed by heat.

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The peroxides MO, (M = Ca, Sr, Ba) shew no alkaline reaction towards litmus; they are insoluble in water, but all form compounds (hydrates) with water. They are all decomposed by heat to MO+O; BaO, is the most stable towards heat. No peroxide of beryllium has been obtained.

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The oxides and hydroxides are all white solids; BeOH, is much more gelatinous than the other hydroxides. The specific gravities of the oxides MO are, approximately, 3.08 for BeO, 3.15 for CaO, 4·5 for SrO, and 5.4 for BaO; of the hydroxides MO,H,, 2.08 for CaO,H,, 3.62 for SrO,H,, and 4.49 for BaOH, The heats of formation of these oxides and hydroxides, in aqueous solutions, from calcium to barium, increase as the atomic weights of the metals increase.

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The sulphides CaS, SrS, and BaS are prepared (1) by 399 heating the oxides MO in a stream of carbon disulphide mixed with carbon dioxide, (2) by heating a mixture of the sulphates MSO, with charcoal; MSO ̧ + 4C = MS + 4CO.

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The hydrosulphides MS,H, are usually obtained by reactions between the hydroxides, generally in aqueous solution, and sulphuretted hydrogen; thus

MO2H ̧ + 2H,S = MS2H, + 2H ̧O,

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These compounds are also formed when the sulphides MS interact with a little water;

2MS+ 2H,O= MSH, + MO2H..

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The sulphides and hydrosulphides are white, or yellowish white, solids; they are more easily decomposed by heat, and by interaction with water, than the corresponding oxygen compounds. Besides the compounds MS and MS,H the following sulphides are known :-CaS, CaS,, SrS, BaS, BaS. H2O.

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Beryllium does not combine directly with sulphur, nor is a sulphide produced by heating BeO in carbon disulphide vapour, or by heating BeSO, in hydrogen or sulphuretted hydrogen. 400 The haloid compounds MX,-where X-F, Cl, Br, or I, and M Ca, Sr, or Ba-are obtained by interactions between the oxides, hydroxides, or carbonates, of the metals and aqueous solutions of the haloid acids HX. The corresponding beryllium compounds, BeCl,, BeBr,, and BeI ̧ are prepared by strongly heating an intimate mixture of beryllium oxide and finely divided carbon in chlorine, bromine, or iodine vapour, respectively; BeO + C + X, BeX, + CO. Solutions of beryllium oxide, or carbonate, in haloid acids yield oxyhaloid compounds on evaporation, e.g. BeO.BeCl,.

401

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The compounds MX, where M is Ca or Sr usually crystallise with 6H2O, ie. the crystals have the composition MX,.6H2O; when M Ba the compounds MX, usually crystallise with 2H,0. The crystallised fluorides however of all the metals Ca to Ba seem to be anhydrous. Hydrates of BeX, crystallise from solutions of the three compounds in the haloid acids HX. The compounds MX, are white solids, which melt at high temperatures; e.g. M.P. of CaCl,=719°, CaBr,=676°, CaI, -631°; M.P. of SrCl = 825°, SrBr, = 630°, SrI, 507°; M. P. of BeCl, = = abt. 600°. BeBr, and BeCl, have been gasified without decomposition. The haloid compounds of Ca, Sr, and Ba, with the exception of the fluorides, are very soluble in water, and are also soluble in alcohol; the Be compounds are not soluble in water. The Be compounds easily form oxyhaloid compounds of more or less complex composition expressible by the general formula BeX,.yBeO; the haloid compounds of Ca, Sr, Ba, form only a few similar compounds, which are obtained by boiling solutions of MX, with the oxides MO. Most of the haloid compounds of Ca, Sr, and Ba, absorb and combine with ammonia, generally producing compounds of the form MX,.6NH,; these are easily decomposed by heat. These haloid compounds, except the fluorides, do not shew any great tendency to combine with other haloid compounds and so produce double salts.

The salts of the metals Be, Ca, Sr, Ba, i.e. the compounds obtained by replacing the hydrogen of acids by these metals, are very numerous. The salts of Ca, Sr, and Ba, as a class are very definite and stable compounds; the oxides and hydroxides of these metals interact with most acids in aqueous

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solutions to form normal salts. With the weak acids, especially with boric acid, these metals also form basic salts: e.g. 3CaO. 5B0,, and 3SrO. BO,. A few double salts are known of these three metals; e.g. CaSO. K.SO. HO; and SrSO,.K.SO. The greater number of these double salts are derivatives of the weaker acids; e.g.

Ba (NH) ASO, and 2CaO. B,O,. Na ̧B ̧0,. 15H ̧0.

The salts of beryllium are less definite compounds than those of the other three metals we are considering: many are basic salts, e.g.

3BeO.CO,; 3BeO.SO,; 2BeO.SO,; 7BeO. 3SeO,. 14H ̧0. The normal Be salts are more easily decomposed by heat, or by heating in presence of water, than the salts of Ca, Sr, and Ba. Beryllium also forms many double salts, e.g. Be (NH) PO; BeSO.K.SO.2H2O; 3BeCO,. 2(NH ̧),CO ̧ ; 3BeSiO,. Al(SiO3)3.

The carbonates MCO, are all decomposed by heat alone to MO + CO; their stabilities towards heat increase as the atomic weight of M increases.

The existence of the gaseous molecules BeCl, and BeBr, indicates that the atom of beryllium is divalent; as the vapour densities of no compounds of the metals Ca, Sr, Ba, have as yet been determined, we cannot be certain as to the valency of the atoms of these elements, but judging from the analogies between these three, and the other, members of Group II., it is probable that the atoms of these elements are divalent.

The three elements, calcium, strontium, and barium, are evidently very closely related; they are much more like each other than any of them is like beryllium.

402

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