Modern inorganic chemistry

(Axel Boer) #1

GROUP IV 169
swells because oxygen atoms become attached to some of the carbon
atoms in the rings and distend the layer structure. 'Graphite oxide'
is rather indefinite in composition. With concentrated sulphuric acid
and an oxidising agent a blue solution called 'graphite hydrogen
sulphate' is formed; this has an approximate formula (CJ^HSOJ.
2H 2 SO 4 *.
Amorphous carbon, having a far greater effective surface area
than either diamond or graphite, is the most reactive form of carbon.
It reacts with both hot concentrated sulphuric and hot concentrated
nitric acids in the absence of additional oxidising agents but is not
attacked by hydrochloric acid.


Silicon

Silicon, like carbon, is unaffected by dilute acids. Powdered silicon
dissolves incompletely in concentrated nitric acid to give insoluble
silicon dioxide, SiO 2 :

3Si 4- 4HNO 3 -> 3SiO 2 + 4NO + 2H 2 O

Germanium

The gradual increase in electropositive character down the group
is clearly shown in that, unlike both carbon and silicon, germanium
very readily dissolves in both concentrated nitric and sulphuric
acids; the hydrated germanium(IV) oxide is produced:

3Ge + 4HNO 3 -> 3GeO 2 + 4NO + 2H 2 O
Germanium, however, does not react with either dilute sulphuric or
dilute hydrochloric acid, unlike tin, the next element in the group.

Tin

Tin slowly dissolves in dilute hydrochloric, nitric and sulphuric
acids, and is in fact the only Group IV element to do so. The reac-
tions with more concentrated acid are rapid. With hydrochloric acid,



  • Graphite reacts with alkali metals, for example potassium, to form compounds
    which are non-stoichiometric but which all have limiting compositions (for example
    KnC); in these, the alkali metal atoms are intercalated between the layers of carbon
    atoms. In the preparation of fluorine by electrolysis of a molten fluoride with graphite
    electrodes the solid compound (CF)B, polycarbon fluoride is formed, with fluorine on
    each carbon atom, causing puckering of the rings.

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