Mineral/Crystal Chemistry and Classification of Minerals Revisited

Atomic Substitution and Solid Solution, Polymorphism and Isomorphism; Mineral Classes, Subclasses, Groups, Series, Species, and Varieties
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Polymorphism
The same chemical formula applies to two (or more) distinct mineral species.
Chemical composition may not be sufficient to designate a specific mineral species (physically homogeneous and separable portion of a material system). Different polymorphs occur as a result of differing environmental conditions principally temperature and pressure.
Pyrite, FeS2 (Fe+2S2), Cubic Marcasite, FeS2 (Fe+2S2), Orthorhombic
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Polymorphs
Diamond and Graphite (C);

Geobarometer: (determines pressure of formation)

Polymorphs
Quartz, Tridymite, and Cristobolite (SiO2);

Silica mineral phase diagram

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Polymorphs
Calcite and Aragonite (CaCO3);

Isomorphism
Substances with analogous formulas where the relative sizes of cations and anions are similar and crystal structure is closely related
Typically (but not always) the basis for grouping and classification, e.g.
Garnet group, Amphibole group, Mica group, Pyroxene group Galena, PbS Halite, NaCl
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Isomorphism
Anions and cations of isomorphous minerals have
the same relative size the same coordination and crystallize in the same crystal structure

Share similarity of crystal structure but not (necessarily) chemical behavior

Galena, PbS

Halite, NaCl

Isomorphism
Aragonite (orthorhombic) and Calcite Groups (trigonal)

Atomic Substitution/Solid Solution

Homogeneous crystalline solids of variable chemical composition
Many minerals vary in their composition Elements are readily substituted (atomic substitution) for one another in many crystal structures (when ionic radius and charge permits)
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Atomic Substitution/Solid Solution

Requires valences of substituting ions are no more different than 1
Na+1 for Ca+2 *

At room temperature difference in the size of substituting ions must be <15%

*Na+1 IR = .97
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Atomic Substitution/Solid Solution

Some isomorphous minerals occur in complete solid solution i.e. any composition (mixture) may occur between end member compositions
Plagioclase feldspar series: Albite (Na) to Anorthite (Ca) series;

NaAlSi308 to CaAl2Si2O8

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Plagioclase Feldspar Continuous Solid Solution Series

(Ca, Na)(Si,AL)AlSi2O8
Composition of plagioclase feldspar suggests temperature of formation

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Incomplete Solid Solution

Some solid solutions do not have isomorphous (that is they have dimorphic) end members
Sphalerite (Zn, Fe)S (cubic) and Pyrrhotite Fe1-xS (hexagonal)

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Incomplete Solid Solution (atomic substitution) & Temperature Controls

Atomic substitution is greater at higher temperature (crystal lattices are more open) and can accommodate greater ionic radius deviation (than 15%)

Na+1 IR = 0.97 K+1 IR = 1.33 Ca+2 IR = 0.99

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Isomorphism Without/with Minimal Solid Solution

Isomorphism and solid solution are distinct concepts
The carbonate minerals Galena and Halite

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Classification of Minerals
Mineral classes
Mineralogists use crystal chemistry to organize and classify minerals Based on the anion or anionic complexes in the crystal structure

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Classification of Minerals: Mineral Classes

Chemical composition (anion/anionic complex) determines class Types of bonding and structures are the same (or similar) Physical properties can be very similar within classes

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Mineral Classes
(for our purposes)
Mineral Classes (8)
Native Elements Sulfides Oxides Halides Carbonates Sulfates Phosphates Silicates (Hydroxides)

Silicates are complex and subdivided into subclasses:

Tecto Phylo Ino Cyclo Neso Soro-

Silicates

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Hierarchy of Mineral Classification:

Subclasses (mostly otbo structure) e.g. Six silicate subclasses.
Nesosilicates: SiO4, independent silica tetrahedra. Sorosilicates: Si2O7, double silica tetrahedra. Cyclosilicates: SiO3, ring of silica tetrahedra. Inosilicates: Si4O11, chains of silica tetrahedra.

Phyllosilicates: Si2O5, sheets of silica tetrahedra. Tektosilicates: Si02, frameworks of silica 19 tetrahedra.

Hierarchy of Mineral Classification:

Mineral Groups; mineral species with close chemical and structural relationship e.g. (typically due to atomic substitution/solid solution)
Amphibole, Feldspar, Mica, Pyroxene, Garnet, Olivine.

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Hierarchy of Mineral Classification:

Mineral Species within a Group or Solid Solution Series:
naturally occurring homogeneous
crystalline substance of inorganic origin, possessing characteristic physical properties, with either definite chemical composition or range in composition between certain limits e.g.

Albite: NaAlSi308; Anorthite: CaAl2Si2O8. Plagioclase (Series):

(Na,Ca) (Al,Si)AlSi2O8.
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Hierarchy of Mineral Classification:

Mineral Variety: slight variation in trace (non-structural) element content and resultant distinctive physical properties (typically color) e.g.
Corundum > Ruby (red), Sapphire (blue) [AL2O3] Classification tending to move away from species and variety names to names using a modifier of main species e.g.:
Fe in magnesite (MgCO3) > ferroan magnesite

Ruby

Sapphire

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