Calcium Fluoride

Calcium fluoride (CaF2) is an insoluble ionic compound composed of

Ca2+ and F− ions. It occurs naturally as the mineral “Fluorite” (also
called fluorspar) and as “Blue-John”. This salt is the source of most of
the world’s fluorine. This insoluble solid adopts a cubic structure
wherein calcium is coordinated to eight fluoride anions and each F− ion
is surrounded by four Ca2+ ions (Fig. 2.13).

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FIGURE 2.13.

The structure is face centered in Ca2+ ions. Cell parameters

are: a = b = c = 3.865 Å, α = β = γ = 60°, cell volume = 40.83 Å3, cell
occupancy is shown in Table 2.34.
TABLE 2.34 .

No Site Atom Multiplicity Wyckoff Site x y z Occupancy

notation symmetry
1 F F 8 c −43m. 1/4 1/4 1/ 1.0
4
2 Ca Ca 4 a m−3m. 0 0 0 1.0
Although the pure material is colorless, the mineral is often deeply
colored due to the presence of “F-centers” (which are electrons
trapped by a vacancy in the crystal structure). Fluorite, the mineral, is
well known and prized for its glassy luster and rich variety of colors.
The range of common colors for fluorite starting from the hallmark
color purple, then blue, green, yellow, colorless, brown, pink, black
and reddish orange is amazing and is only rivaled in color range by
quartz. Intermediate pastels between the previously mentioned colors
are also possible. It is easy to see why fluorite earns the reputation
as “The Most Colorful Mineral in the World”.
Naturally occurring CaF2 is the principal source of hydrogen fluoride, a
commodity chemical used to produce a wide range of materials.
Fluoride is liberated from the mineral by the action of concentrated
sulfuric acid:
CaF2(solid) + H2SO4(liq) ⇒ CaSO4 (solid) + 2HF (gas)
The resulting HF is converted into fluorine, fluorocarbons, and diverse
fluoride materials. As of the late 1990s, 5 billion kilograms were mined
annually.