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This page explores the oxidation states (oxidation numbers) shown by the Group
4 elements - carbon (C), silicon (Si), germanium (Ge), tin (Sn) and lead (Pb). It
looks at the increasing tendency of the elements to form compounds in which
their oxidation states are +2, particularly with reference to tin and lead.
Some examples of the trends in oxidation states
The overall trend
The typical oxidation state shown by elements in Group 4 is +4, found in
compounds like CCl4, SiCl4 and SnO2.
Warning: Don't fall into the trap of quoting CH4 as an example of carbon with a
typical oxidation state of +4. Because carbon is more electronegative than
hydrogen, its oxidation state in this instance is -4!
However, as you go down the Group, there are more and more examples where
the oxidation state is +2, such as SnCl 2, PbO, and Pb2+.
With tin, the +4 state is still more stable than the +2, but by the time you get to
lead, the +2 state is the more stable - and dominates the chemistry of lead.
An example from carbon chemistry
The only common example of the +2 oxidation state in carbon chemistry occurs
in carbon monoxide, CO. Carbon monoxide is a strong reducing agent because it
is easily oxidised to carbon dioxide - where the oxidation state is the more
thermodynamically stable +4.
For example, carbon monoxide reduces many hot metal oxides to the metal - a
reaction which is used, for example, in the extraction of iron in a blast furnace.
For example, a solution containing tin(II) ions (for example, tin(II) chloride
solution) will reduce a solution of iodine to iodide ions. In the process, the tin(II)
ions are oxidised to tin(IV) ions.
Note: For simplicity, I am writing this equation (and the next few) as if the
product contained simple tin(IV) ions. In fact, simple tin(IV) ions don't exist in
solution. In these examples, they will usually be a part of a much larger complex
ion. Don't worry about this at this level.
Tin(II) ions also reduce iron(III) ions to iron(II) ions. For example, tin(II) chloride
solution will reduce iron(III) chloride solution to iron(II) chloride solution. In the
process, the tin(II) ions are oxidised to the more stable tin(IV) ions.
Tin(II) ions will also, of course, be easily oxidised by powerful oxidising agents
like acidified potassium manganate(VII) solution (potassium permanganate
solution). This reaction could be used as a titration to find the concentration of
tin(II) ions in a solution.
Note: This reaction is dealt with in some detail in the organic chemistry section
of the site on a page about the preparation of phenylamine.
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follow this link.
. . . and lead(IV) oxide decomposes on heating to give lead(II) oxide and oxygen.
Lead(IV) oxide also reacts with concentrated hydrochloric acid, oxidising some of
the chloride ions in the acid to chlorine gas. Once again, the lead is reduced from
the +4 to the more stable +2 state.
This first chart shows how the total ionisation energy needed to form the 2+ ions
varies as you go down the Group. The values are all in kJ mol -1.
Again, the values are all in kJ mol -1, and the two charts are to approximately the
same scale.
The reasons for all this lie in the Theory of Relativity. With the heavier elements
like lead, there is what is known as arelativistic contraction of the electrons
which tends to draw the electrons closer to the nucleus than you would expect.
Because they are closer to the nucleus, they are more difficult to remove. The
heavier the element, the greater this effect.
This affects s electrons much more than p electrons.
There are only two unpaired electrons. Before carbon forms bonds, though, it
normally promotes one of the s electrons to the empty p orbital.