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In ethers. The solvated electron is know even in aqueous solution.

But is has a very short (~10-3)


lifetime.

These solutions are not mere laboratory curiosities. In addition to being strong bases, they
are also good one-electron redacing agents, for example. Pure samples alkali metal superoxides
may be readily prepared in these solutions:

M+ + e- + O2 M+ + O-2 (10.24)

The superoxide ion is further reducible to peroxide :

M+ + e- + O2 M+ + O3-2 (10.25)

Some metal complexes may also be foread into unusual oxidation states :

[Pt(NH3)42+ + 2M+ + 2e- [Pt(NH3)4] + 2M+ (10.26)

Mo(Co)6 + 6Na+ 6e- Na4[Mo(CO)4] + Na2C2O2 (10.27)

A + M+ + e- M+ + A- (10.28)

The chemistry of metal electrides has been extensively studied and although the
formulation M+ e- is undoubtedly the best, most chemists have the all-too-human emotion of
feeling more secure in their science if they have something more tangible than solutions and
equations on paper. Therefore the isolation and structural characterization of cesium
electride.[Cs(ligand)]+ e- , as single crystals was welcome, indeed. The crystals are dark blue
with a single absorption maximum at 1500 nm, have no likely anions present (the empirical
formula is 1:1, Cs:ligand, with a trace of lithium impurity, an artifact of the synthetic technique),
and are most readily formulated as a complex of cesium electride.

The physical properties of sulfuric acid are listed in table 10.3. The dielectric constant is even
higher than of water, making it a good solvent for ionic substances and leading to extensive
autoionization. The high viscosity, some 25 times that of water, introduces experimental
difficulties ; solutes are slow dissolve and slow to crystallize. It is also difficult to remove
adhering solvent from crystallized materials. Furthermore, solvent that has not drained from
prepared crystals is not readily removed by evaporation because of the very low vapor pressure
of sulfuric acid.

Table 10.3 Physical properties of sulfuric acid

Boiling point 300 oC (with decomposition)


Freezing point 10.371 oC
Density 1.83 g cm-3 (25 oC)
Premittivy (dielectric constant) 110o (20 oC)
Specific conductance 1.04 x 10-2 -1 cm-1 (25 oC)
Viscosity 24.54 g cm-1 s-1 (20 oC)
Ion product constant 2.7 10-4 mol2 L-3 (20 oC)

Autoionization of sulfuric acid results in the formation of the hydrogen sulfate (bisulfate) on and
a solvated proton :
2H2SO4 H2SO4+ + HSO4-
As expected, a solution of potassium hydrogen sulfate is a strong base and may be titrated with a
solution containing H3SO4+ ions. Such a titration may readily be followed conductometrically
with a minimum in conductivity at the neutralization point.
Another method that has proved extremety useful in obtaining information about the nature of
solutes in sulfuric acid solution is the measurement of freezing point depressions. The the
freezing point constant (k) for sulfuric acid is 6.12 kg oC mol-1. For ideal salutions, the
depression of the freezing point is given by
= kmv
Where m is the stoichiometric molality and r is the number of particles formed when one
molecule of solute dissolves in sulfuric acid. For example, ethanol reacts with sulfuric acid as
follows:
C2H2OH + 2H2SO4 C2H5HSO4 + HSO4- + H3O+ v =3
It is found that all species that are basic in water are also basic in sulfuric acid:
OH- + 2H2SO4 HSO4- + H3O+ v=3
NH3 + H2SO4 HSO4- + NH4+ v=2
Likewise, water behaves as a base in sulfuric acid:
H2O + H2SO4 HSO4- + H3O+ v=2
Amides, such as urea, which are nonelectrolytes in water and acids in ammonia accept protons
from sulfuric acid:
NH2C(O)NH3 + H2SO4 HSO4- + NH2C(O)NH3+ v=2
Acetic, such as urea, which are nonelectrolytes in water and acid a strong acid, bad both behave
as bases in sulfuric acid!

Sulfuric acid is a very acidic medium, and so almost all chemical species which react upon
solution do so with the formation of hydrogen sulfate ions and are bases. Because of the extreme
tendency of the H2SO4 molecule to donate protons, molecules exhibiting basic tendencies will be
toveled to HSO4-.

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