The chemistry of thorium phosphate reported in the literature has
been found to be
erroneous. It was reconsidered in terms of careful chemical
preparations and specific
analytical methods. Special attention has been paid to the atom
ratio value referred to r =
thorium/phosphorus, which was experimentally fixed in order to obtain
the correct composition of the final compound. A new compound with the chemical
formula
Th4(PO4)4P2O7,
derived from the crystal structure determination, has been obtained.
The unit cell
parameters were obtained from powder and single-crystal X-ray
diffraction data. It is
orthorhombic (space group Pcam, Z = 2) with the
cell dimensions a = 12.8646(9) Å, b
=
10.4374(8) Å, c = 7.0676(5) Å, and V
= 949.00(9) Å3. The atomic positions were
derived
from Patterson and Fourier methods and the structure was refined to an
R value of 0.039.
The structure consists of layers parallel to (010) containing both
PO4 and P2O7 groups.
These
layers alternate with planes of Th atoms. The coordination sphere
of the two independent
heavy atoms is formed by eight O atoms from five PO4 and
one P2O7 groups. The formula
of thorium phosphate
Th4(PO4)4P2O7
is in good agreement with the elementary composition
derived from electron microprobe analysis, which gave a ratio
r = 2/3. Any other value of
r
(1/2 < r <
3/4) induces the formation of polyphase
systems: Th4P6O23 and ThO2
for r > 2/3;
Th4P6O23 and
ThP2O7 for r <
2/3. The characterization of thorium
phosphate diphosphate by
means of infrared spectroscopy confirmed the presence of diphosphate
groups in the
compound.
The decomposition reactions of two zirconium hydroxide nitrates Zr(OH)2(NO3)2·(4+x)H2O and α-Zr(OH)2 (NO3)2·(1+x)H2O (0≤x≤1) have been studied by thermogravimetric analysis and high-temperature X-ray powder diffractometry (HTXRD), in nitrogen gas environment. The decomposition reaction sequences were clearly displayed by the HTXRD technique. They are different for the two precursors, except the formation of amorphous zirconia at low temperature (200 °C) and crystalline zirconia at about 390 °C. Three modifications of Zr(OH)2(NO3)2·H2O (α,β,γ) were identified. Their X-ray powder diffraction patterns were indexed by the successive dichotomy method. The unit cells are triclinic and present some parametric and volumetric similarities from each other and also with that of their precursor. Moreover, the thermal decomposition sequences of Zr(OH)2(NO3)2·(4+x)H2O and α-Zr(OH)2(NO3)2·(1+x)H2O include the formation of anhydrous oxide nitrate ZrO(NO3)2 and anhydrous hydroxide nitrate Zr(OH)2(NO3)2, respectively.
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