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5-1 Solid State Chemistry 5-1

The document discusses the fluorite and antifluorite structures, detailing their ionic arrangements and examples. It also outlines Pauling's Rules regarding crystal structures, including principles for bond strength and coordination. Additionally, it describes types of crystals such as isodesmic, anisodesmic, and mesodesmic, emphasizing the stability of crystal structures based on polyhedral sharing.

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Dilshan Narankotuwa
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© © All Rights Reserved
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17 views8 pages

5-1 Solid State Chemistry 5-1

The document discusses the fluorite and antifluorite structures, detailing their ionic arrangements and examples. It also outlines Pauling's Rules regarding crystal structures, including principles for bond strength and coordination. Additionally, it describes types of crystals such as isodesmic, anisodesmic, and mesodesmic, emphasizing the stability of crystal structures based on polyhedral sharing.

Uploaded by

Dilshan Narankotuwa
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 8

12/18/24

Fluorite structure:

• Compounds with the formula MX2.


• The X ions occupy the eight tetrahedral interstitial sites whereas
M ions occupy the regular sites of a face-centered cubic (FCC)
structure.
• Many compounds, notably the common mineral fluorite (CaF2),
adopt this structure.

Antifluorite structure:

• Compounds with formula M2X.


• In these the locations of the anions and cations are reversed
relative to fluorite (an anti-structure); the anions occupy the FCC
regular sites whereas the cations occupy the tetrahedral
interstitial sites.
• For example, magnesium silicide, Mg2Si, has a lattice parameter
of 6.338 Å with magnesium cations occupying the tetrahedral
interstitial sites, in which each silicide anion is surrounded by
eight magnesium cations and each magnesium cation is
surrounded by four silicide anions in a tetrahedral fashion.

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Pauling's Rules

Linus Pauling studied crystal structures and the types of bonding and coordination
that occurs within them. His studies found that crystal structures obey the following
rules, now known as Pauling's Rules.

Pauling’s first rule, sometimes called the Radius Ratio Principle

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Pauling's Rules

Pauling’s second rule, sometimes called the Electrostatic Valency Principle, says that we can
calculate the strength of a bond (its electrostatic valence) by dividing an ion’s valence by its C.N.
Consequently, the sum of all bonds to an ion must be equal to the charge on the ion.

Pauling's Rules

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Pauling's Rules

The radii of Ti4+ and O2– are 0.69 Å


and 1.32 Å.

• Rc/Ra is 0.52
• As predicted by Rule 1, Ti4+ is in
6-fold (octahedral) coordination.
Each bond has a strength of 4/6
(total charge divided by number of
bonds) = 2/3.

• Since each O2– has a total charge


of -2, it must be bonded to three
Ti4+ to satisfy Rule 2, so O2- is in
triangular coordination.

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Isodesmic Crystals
Most minerals contain more than two elements and
may have many kinds of bonds.
Ø Model of spinel, MgAl2O4
Ø Spinel contains Mg-O and Al-O bonds.
Ø X-ray studies reveal that Mg2+ is in tetrahedral
coordination and Al3+ is in octahedral coordination.
Ø The strength of the bonds around Mg2+ is 2/4 = 1/2
and
Ø the strength of the bonds around Al3+ is 3/6 = 1/2
Ø Compounds such as spinel, in which all bonds
have the same strength, isodesmic. Bond strengths in spinel
Ø They have the same bond lengths and properties
(e.g., cleavage and hardness) in all directions.

Anisodesmic Crystals

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Mesodesmic Crystals

Mesodesmic bonds
joining silicon and oxygen ions

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Pauling's Rules

Crystal structures become less stable when the polyhedra


share edges and even more unstable when the polyhedra
share faces.

This is because the cations are closer together and like


charges repel.
Silica tetrahedra are linked through the oxygens at their
apices.

These are called bridging oxygens.

The same principles apply to octahedra and other polyhedra.


Edge- and even sometimes face-sharing, however is more
common in larger polyhedra than in tetrahedra because there
is more room for cations to stay apart.

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Pauling's Rules

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Pauling's Rules

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Pauling's Rules

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