420

highest sulphide of chromium known with certainty, but the important sulphides of the other elements are MS, and MS. Again the chlorides of chromium are CrCl, and CrCl, but the chlorides MC, MCI,, and even MC, are characteristic of the other elements of the series.

The oxides MO, are all acidic; but the acidic character becomes less marked as the atomic weight of M increases. This decrease in acidic character is shewn by the production of such a salt as UO,(SO) from the oxide UO,, and by the fact that the most definite and stable molybdates, tungstates, and (probably) uranates, belong to the form XMO.жMO1(X = K2, Ba, &c. ; M = Mo, W, U), whereas the most marked chromates are the normal salts XCrO. In other words, the combination of a relatively large quantity of the acidic oxides MO, with basic oxides seems to be necessary for the production of stable salts when MO, is MoO, WO,, or UO.

4

3

Thio-salts, usually of the composition MXS,(M=K„, Ba, &c. X= Cr, Mo, W), of all the elements except uranium are known.

The salts of molybdenum and tungsten have been so little examined that no generalisations regarding them can be made; salts of chromium and uranium are numerous, many of them are basic, and several form double salts chiefly by combining with salts of the alkali and alkaline earth metals.

The odd-series members of Group VI. are SULPHUR, SELENION, and TELLURIUM. The properties of these elements have been already considered (Chap. XI. pars. 170 to 179); it will suffice to summarise these properties here.

Sulphur and selenion are distinctly non-metallic in their chemical properties; tellurium inclines towards the metals but it is decidedly less metallic than chromium, molybdenum, tungsten, or uranium.

The existence of stable gaseous hydrides MH,; the distinctly acidic functions of the oxides MO, and MO; the non-existence of salts produced by replacing the hydrogen of acids by M; the existence of strong acids HMO, and H.MO, each giving a series of definite salts; these among other properties, mark the non-metallic character of the elements sulphur, selenion, and tellurium.

The negative character of sulphur and selenion is further marked by the fact that these elements exhibit allotropy; by their physical properties; by the possibility of forming oxy

4

chlorides directly from the acids HMO, and H.MO̟; by the slightly acidic functions of the hydrides MH,.

2

3

Tellurium does not exist in more than one form; the acids H.TeО, and H.TeO, are not produced by the direct interactions of the oxides TeO, and TeO, with water; the hydride TeH, shews no acidic properties; the anhydride Teo, combines with some acids (e.g. TeO,.2HCl is known); some of the physical properties of tellurium approximate to those of the metals.

2

The existence of the stable gasifiable tetrachloride TeCl; the formation not only of ditellurates MTe,O,, but also of tetratellurates MTe O, and of salts of the form MTe,O, (M = K, Ba, &c.); the unreadiness to enter into chemical reaction with alkalis or alkaline carbonates of the oxide TeO2; these are some of the properties in which tellurium approaches the higher members (W and U) of the even series of Group VI.

2

OXYGEN is the first member of the even-series of the group now under consideration. Oxygen is a typical non-metallic or negative element both in its chemical and physical properties (s. Chap. VIII.). Nevertheless the properties of some of the compounds of this element suggest the properties of the other elements of the group in which oxygen occurs. Thus oxygen forms two compounds with hydrogen, water H.O and hydrogen peroxide H2O,, but neither is acidic; oxygen combines with the positive elements to form oxides the composition of which is frequently similar to that of the sulphides and selenides of the same elements, compare for instance the formulae MO and MS where M = Cu, Fe, Mg, Ni, Co, Mn, Ca, Ba, Sr, K„, Na, &c.; most of the oxides of positive elements are basic, some however as we have seen are acidic; most of the sulphides of positive elements interact with acids to form salts and hydrogen sulphide, some however interact with alkaline sulphides to form thio-salts.

2

The compounds of oxygen with chlorine CIO, and (?) C1,O, do not resemble the chlorides of the other members of Group VI. in composition, but the oxide OCI, is analogous in composition to MCI, when M = S, Se, Te, Cr, Mo, or W. The compounds of oxygen with chlorine are very easily decomposed by heat and reagents generally; in this they resemble the compounds of sulphur and selenion with chlorine. The existence of the gaseous molecules O, and O,, Se, and Se,, S, and S., emphasises the resemblance between oxygen, sulphur,

421

422

423

and selenion. Oxygen forms a solid, stable, compound with iodine, O,I,; although the composition of this compound is not similar to that of the iodides of the other elements of Group VI., the fact of the existence of this stable compound suggests the existence of the stable iodides of tellurium, chromium, and tungsten. The existence of many definite and stable compounds of oxygen with non-metallic elements (oxides of As, B, C, I, N, P, Si) shews that oxygen is to some extent positive in its chemical properties: the compositions of these oxides are very frequently similar to those of the sulphides of the same elements when sulphides of these elements exist.

Group VI., then, is evidently divided into two well marked sub-groups or families; one of these families consists of the elements chromium, molybdenum, tungsten, and uranium; the other is formed of sulphur, selenion, and tellurium; oxygen, which is the first member of the group, to some extent summarises the properties of both families, but at the same time it differs from all the other members of the group. At the same time the elements of Group VI. taken as a whole more closely resemble one another than they resemble any other elements.

If we now turn to Group V. we shall find a group of ten elements shewing a gradation of properties from the first to the last member; we shall find that the group-character preponderates over the family-character, so that although the evenseries members are on the whole more like each other than they are like the odd-series members, yet it is not possible to divide Group V., as we have divided Group VI., into two distinct sub-groups or families.

The molecular weight of nitrogen is 28.02; the molecular weights of the other elements are unknown. Sp. grs. (approx.) .97 if air=1; 5.5 7(?) liquid; s.G.*885

Appearance, and

general physical properties.

The melting points of most of these elements have not been determined.

In a few minerals, not widely distributed, chiefly as oxides and sulphides.

pressure; liquid
boils at abt.
- 195°.
Combines di-
rectly with few
if any elements
at ordinary
temperatures;
but at very
high tempera-
tures combines
directly with B,
Si, Cr, Mg, V,
and a few other
elements.
If electric dis-
charge is passed
through mix-
ture of N with
O, or H, a very
little NO2, or
NH3, is formed.
Strongly nega-
tive.
Oxides are gene-
rally anhy-

drides.
Hydride, NH3,
is strongly alka-
line.

Atom trivalent
in gaseous

molecules.

* There is some doubt whether the body known as didymium is or is not a mixture of two or more elements; many of the properties of compounds of didymium are probably the properties of mixtures.

Appearance, and general physical properties.

General chemical properties.

425

Many phos-
phates occur
very widely dis-
tributed in
rocks and
waters; also in
bones and in
parts of plants.
Compounds of
P with C, N, and
O occur in nerve
and brain
matter.
Prepared by
heating
Ca(PO3)2 with
charcoal.

Soft wax-like
solid.
Crystalline.
Non-conductor
of electricity.

Burns in air to
P20 and P205.
Combines di-
rectly with Cl,
Br, and I.
Oxidised by
HNO3.

Does not form
salts by inter-
acting with
acids.
Hydride, PH3,
resembles NH3
but is less alka-
line.
Oxides are
anhydrides.
Atom trivalent
and pentavalent
in gaseous
molecules.
Phosphorus
shews allotropy
(s. Chap. XI.,
par. 220).

5.7 500° (under pressure)

13.2

*083

As2O3 and
As2S3 occur;
also compounds
of As with Te
and S, with Ni,
Co, &c. occur in
small quantities
widely distri-
buted.
Prepared by
heating A$203
with charcoal.

Grey, hard,
brittle, solid.
Crystalline.

Fair conductor
of electricity.

Burns in air to
AS203.
Combines di-
rectly with Cl,
Br, and I.
Oxidised by
HNOS.
No salts known
derived from
acids.
Hydride, AsHg,
is scarcely if at
all alkaline.
Oxides are
anhydrides.
Atom trivalent
in gaseous
molecules.
Arsenic exists
in allotropic
forms (s. Chap.
XI, par. 222).

18

⚫053

Chief naturally
occurring com-
pound is Sb2S3;
found in com-
paratively small
quantities in
very various
parts.
Prepared by
heating Sb2O3
with charcoal.

Grey, lustrous,
brittle, very
crystalline,
solid.

Fair conductor
of electricity.

Burns in air to
Sb2O3.

Combines di-
rectly with Cl,
Br, and I.
Oxidised by
HNO3.

A few salts de-
rived from acids
seem to exist.
Hydride, SbHg,
not alkaline.
Oxides are
anhydrides, but
also slightly
basic.

Atom trivalent
in gaseous
molecules.

not determined.
Er203 occurs in
small quantities
in ytterbite, a
Swedish min-
eral.

⚫0308

Bismuth is found native; also Bi203 and BigSg, &c., but not in large quantities.

Metal not yet Prepared by

obtained.

heating BigO3

with charcoal.

Grey, with faintly reddish tinge; crystallises easily; brittle.

Bad conductor of electricity.

Burns in air to Bi203 Combines directly with CI, Br, and I. Oxidised by HNO3, and at same time Bi.3NO, is formed. Many salts known derived from acids. No hydride known.

Oxides are basic; Bi205 shews very slight acidic functions.

Atom trivalent

in gaseous
molecules.

General formulae and chemical characters of compounds of elements of Group V.

Hydrides. MH,; M = N, P, As, Sb.

Oxides. MO; M=N, V. M,O,; M = N, V, Nb, Bi.
MO; Many metal of the group except Nb and Ta.

2

MO;

2

M=N, P, V, Nb, Sb, Ta, Bi. M2O,; Many element of the