annual report annual report annual report annual report 2005

RADIOCHEMISTRY, STABLE ISOTOPES,
NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY
67
Table 3. Percentage of the ionic bonding estimated for the transition metal cations relatively to the calcium(II).
* Relatively to the Ca(II)-alginate.
COOH COOM
PIB = ν −ν
ν
COOH −ν
COONa
where ν is the frequency of the asymmetric vibration
of the carboxylate group. The denominator is
the IR frequency shift of the asymmetric C-O vibration
from the typical covalent bonding (carboxylic
acid) to the typical ionic bonding (sodium carboxylate),
whereas the numerator is the frequency shift
of the same vibration when a particular metal ion
is bound. On the basis of the frequencies found in
the FTIR spectra (Table 1), the relative PIB values
for the divalent transition metal cations vs. that for
calcium(II) were calculated (Table 3 and Fig.3).
These values are independent of the cation and
for the first transition metals row – significantly
greater than unity. The observation may be related
Fig.3. PIB values for the investigated species relatively to
the CA.
to the inversed ionic radii, which determine the
ionic charge density being proportional to the cation
hardness. Value for cadmium(II) (of the radius
similar to this of calcium(II)) appears to be close
to that for calcium(II).
The observed lack of PIB dependence on the
cationic radius for the manganese(II), cobalt(II),
nickel(II), copper(II) and zinc(II) complexes may
be explained in terms of the cation hydration. In
the outer-sphere complexes, the cation radii of the
hydrated species are close to each other within the
group and different from those of calcium(II) and
cadmium(II). The latter may probably form the inner-sphere
complexes.
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