Edison A.

Limbaga October 10, 2022

Problem Set # 2
Subject: CER E 201
Instructor: Assoc. Prof. Lori-Ann I. Cabalo

A. Compare and contrast structures of TeO2 , UO2 and Rutile (TiO2).

a. Structure of TeO2

Tellurium dioxide (TeO2) is a solid oxide of tellurium. It is encountered in two different

forms, the yellow orthorhombic mineral tellurite, β-TeO2, and the synthetic,
colourless tetragonal (paratellurite), α-TeO2. Most of the information regarding
reaction chemistry has been obtained in studies involving paratellurite, α-TeO2. TeO2
is barely soluble in water and soluble in strong acids and alkali metal hydroxides. It is
an amphoteric substance and therefore can act both as an acid or as a base depending
on the solution it is in. It reacts with acids to make tellurium salts and bases to make
tellurites. It can be oxidized to telluric acid or tellurates. Paratellurite, α-TeO2,
converts at high pressure into the β-, tellurite form. Both the α-(paratellurite) and β-
(tellurite forms) contain four coordinate Te with the oxygen atoms at four of the
corners of a trigonal bipyramid. In paratellurite all vertices are shared to give a rutile-
like structure, where the O-Te-O bond angle are 140°. α-TeO2 In tellurite pairs of
trigonal pyramidal, TeO4 units, sharing an edge, share vertices to then form a layer.
The shortest Te-Te distance in tellurite is 317 pm, compared to 374 pm in
paratellurite. Similar Te2O6 units are found in the mineral denningite. TeO2 melts at
732.6 °C, forming a red liquid. The structure of the liquid, as well as the glass which
can be formed from it with sufficiently rapid cooling, are also based on approximately
four coordinate Te. However, compared to the crystalline forms, the liquid and glass
appear to incorporate short-range disorder (a variety of coordination geometries)
which marks TeO2 glass as distinct from the canonical single-oxide glass-formers such
as SiO2, which share the same short-range order with their parent liquids.

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 Figure 1 Crystal Structure of TeO2

b. Structure of UO2
Uranium dioxide or uranium(IV) oxide (UO2), also known as urania or uranous oxide,
is an oxide of uranium, and is a black, radioactive, crystalline powder that naturally
occurs in the mineral uraninite. It is used in nuclear fuel rods in nuclear reactors. A
mixture of uranium and plutonium dioxides is used as MOX fuel. Prior to 1960, it was
used as yellow and black color in ceramic glazes and glass. The solid is isostructural
with (has the same structure as) fluorite (calcium fluoride), where each U is
surrounded by eight O nearest neighbors in a cubic arrangement. In addition, the
dioxides of cerium, thorium, and the transuranic elements from neptunium through
californium have the same structures. No other elemental dioxides have the fluorite
structure. Upon melting, the measured average U-O coordination reduces from 8 in
the crystalline solid (UO8 cubes), down to 6.7±0.5 (at 3270 K) in the melt. Models
consistent with these measurements show the melt to consist mainly of UO6 and UO7
polyhedral units, where roughly 2⁄3 of the connections between polyhedra are corner
sharing and 1⁄3 are edge sharing. The UO2 crystal structure was first determined by
neutron diffraction on a single crystal. At high temperature, it was better refined by
allowing the oxygen atoms to relax from their regular positions in the Fm3̅m space
group. This description was further improved by an anharmonic description of oxygen
thermal motion. Starting from one uranium atom located at the (0, 0, 0) position and
one oxygen atom located at the (1/4, 1/4, 1/4) position, a UO2 crystalline cell can be
built by applying symmetries of a Fm3̅m space group. Thus, each uranium atom is at
the center of a cube, having oxygen atoms at its corners. With such crystalline
symmetry, the UO distance is proportional to the UU distance and also to the cell
parameter. In 2014, Skinner et al. published new experimental results that contradict
this assumption using synchrotron X-ray diffraction. The diffraction pattern was
treated by Fourier transformation to get the corresponding atomic pair-distribution
function (PDF), from which the UO and UU distances were derived. The UO distance
was shown to decrease with increasing temperature, while the UU distance increased
with increasing temperature from room temperature to the UO 2 melting
temperature. This discrepancy was explained by the existence of atomic disorder,
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 which may be a satisfactory interpretation at high temperature near the melting point
but which is in contradiction with previously published neutron diffraction data for
lower temperatures. Three authors measured the UO2 neutron diffraction pattern at
1300 K, and all agreed on the description of its crystalline structure using the Fm3̅m
space group, leading to an increase of the UO distance as a function of the
temperature. However, at 1300 K, Skinner et al. already measured a shortening of the
UO distance.

Figure 2 Crystal Structure of UO2

c. Structure of TiO2
Rutile is an oxide mineral composed of titanium dioxide (TiO2), the most common
natural form of TiO2. Rarer polymorphs of TiO2 are known, including anatase,
akaogiite, and brookite. Rutile has one of the highest refractive indices at visible
wavelengths of any known crystal and also exhibits a particularly large birefringence
and high dispersion. Owing to these properties, it is useful for the manufacture of
certain optical elements, especially polarization optics, for longer visible and infrared
wavelengths up to about 4.5 micrometres. Natural rutile may contain up to 10% iron
and significant amounts of niobium and tantalum. Rutile derives its name from the
Latin rutilus ('red'), in reference to the deep red color observed in some specimens
when viewed by transmitted light. Rutile was first described in 1803 by Abraham
Gottlob Werner. utile has a tetragonal unit cell, with unit cell parameters a = b = 4.584
Å, and c = 2.953 Å. The titanium cations have a coordination number of 6, meaning
they are surrounded by an octahedron of 6 oxygen atoms. The oxygen anions have a
coordination number of 3, resulting in a trigonal planar coordination. Rutile also
shows a screw axis when its octahedra are viewed sequentially. When formed under
reducing conditions, oxygen vacancies can occur, coupled to Ti3+ centers. Hydrogen
can enter these gaps, existing as an individual vacancy occupant (pairing as a hydrogen
ion) or creating a hydroxide group with an adjacent oxygen. Rutile crystals are most
commonly observed to exhibit a prismatic or acicular growth habit with preferential
orientation along their c axis, the [001] direction. This growth habit is favored as the
{110} facets of rutile exhibit the lowest surface free energy and are therefore
thermodynamically most stable. The c-axis oriented growth of rutile appears clearly
in nanorods, nanowires and abnormal grain growth phenomena of this phase.

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 Figure 3 The unit cell of rutile. Ti atoms are gray; O atoms are red.

d. Similarities and Differences

The oxides are similar with the space group number and structural representation in
the unit cells, fluorite structure, as such the Cations of the oxides have 4+ charges and
oxygen of 2-. Since the ionic or atomic radii of the atoms differ, their bond distance
also differ from each other, though they follow the same crystal structure. Which
results in different properties and different phase transitions during melting. Their X-
ray diffraction data also differ in their spacing since the structure within differ due to
their bond distances because of the atomic radii of each elements. And so, these
oxides can be used together or incorporate either two of the oxides to better the
structure and properties of a material, via doping or by mixing the compositional
elements may it be in composites or ceramic applications.

References:
[1] Wikipedia contributors. (2022, July 31). Tellurium dioxide. Wikipedia.

https://en.wikipedia.org/wiki/Tellurium_dioxide

[2] Mark Winter, University of Sheffield and WebElements Ltd. (n.d.). WebElements Periodic

Table » Tellurium » tellurium dioxide. Copyright 2022 Mark Winter, from

https://webelements.com/compounds/tellurium/tellurium_dioxide.html

[3] Desgranges, L., Ma, Y., Garcia, P., Baldinozzi, G., Siméone, D., & Fischer, H. E. (2016).

What Is the Actual Local Crystalline Structure of Uranium Dioxide, UO2? A New

Perspective for the Most Used Nuclear Fuel. Inorganic Chemistry, 56(1), 321–326.

https://doi.org/10.1021/acs.inorgchem.6b02111

[4] Wikipedia contributors. (2022b, October 2). Rutile. Wikipedia.

https://en.wikipedia.org/wiki/Rutile