Professional Documents
Culture Documents
PbO + C Pb + CO
The oxidation state or valence of cadmium (Cd) and oxygen (O) are fixed
as positive 2 (Cd2+ ) and negative 2 (O2-).
So in CdUO4 there are a total of two positive charges (from Cd) and eight
negative charges (from oxygen).
To achieve charge balance the oxidation state of uranium must be
hexavalent of (U6+).
6.0
5.5
5.0
4.5
4.0
3.5
Ca
Sc
Cr
Co
Metal
Ni
Zn
Ion
Size CN =4
()
Size CN=6
()
Mg2+
0.89
Al3+
0.39
0.54
Si4+
0.26
0.40
Tm3+
0.88
Be2+
0.27
0.45
Once the replacements based on size are settled, then for every Be2+ introduced in place of
Si4+, there must be two Tm3+ replacing Mg2+.
As the charge different between Ca2+ / La3+ = 1, and that between W6+ /
Ge4+ = 2, it follows that for every Ge4+ introduced, there must be twice
as many La3+ introduced for charge balance.
Therefore the unit cell volume must be largest at the highest temperature.
This correlation is shown in the table.
None of the answers offered is in accord with the table.
This simple analysis only holds true if there is no change in symmetry. For
calcite R-3c (No. 167) symmetry is maintained across the whole
temperature range.
Temp (K)
Increasing
temperature
Volume (3)
RT
367.6
473
371.0
673
373.3
873
375.0
Increasing
volume
The ellipsoids are drawn to show a 99% probability that the tin and
oxygen will lie within their volumes.
As the temperature increases the atomic vibrations grow larger and the
thermal ellipsoids expand.
Evidentially, the size of the ellipsoids increase from left to right and the
temperatures correspond to (A) room temperature, (B) 470K, (C) 930K
and (D) 1100K.
Notice that the connectivity of the SnO6 octahedron stays the same and
space group symmetry is maintained as P42/mnm (No. 136) over the
entire temperature range.
Site
SOF
Na
16 d
5/8
5/8
5/8
Ca
16 d
5/8
5/8
5/8
Nb
16 c
1/8
1/8
1/8
48 f
0.20
8b
1/2
1/2
1/2
For example in diffraction pattern A, the separation in the vertical , horizontal and diagonal
reflections are fixed distances (d1, d2, d3). This regular separation is a property of the 3D space
groups.
But in diffraction pattern B, the separations (d1, d2) in the diagonal direction are not the same. This
is the primary indication of an incommensurate structure that can only be fully described in 4D, 5D
or 6D.