Chapter 6

Systematic Mineralogy-I
Classification and types of native metals
 NATIVE ELEMENTS
The native elements are those minerals formed wholly
from elements which occur in an uncombined state.
No ionic or covalent bonding may join atoms of one
element to atoms of another within the lattice structure of
such a mineral.
Usually only one type of atom is present in the molecular
structure of these species.
The native elements are further categorized into
subgroups containing metals, semimetals, and nonmetals
a) Metals
Metallic elements which are found in the native state
include Au, Ag, Cu, Pb, Fe, Ni, Pt, and the rarer elements
Pm, Ir, and Os. Hg, Ta, Sn, and Zn have also been found.
The uncombined atoms of the metals act as perfect
spheres and are relatively inert; they tend to form
lattices of
face-centered cubic,
body-centered cubic or hexagonal close-packed structure.
b) Semimetals
The native semi-metals include arsenic (As), antimony
(Sb), and bismuth (Bi), as well as the less common
elements selenium (Se) and tellurium (Te).
Natural crystals of all three species are rare.
The semimetals are brittle, and conduct heat and
electricity poorly compared to the metals.
 c. Nonmetals
The native nonmetals include carbon (C), in the form of
diamond and graphite, and sulphur (S).
3. Sulfides, Antimonides, Arsenides, Selenides,
Tellurides, and Sulfosalts

Sulfides
Sulfide minerals are compounds of one or more metal or
semimetal elements with the nonmetallic element sulfur
(S).
In a sulfide, the sulfur anion (S2+) is thus combined with
metallic cations such as (Fe), (Co), (Ni), (Cu), (Zn), (Mo),
(Ag), c (Cd), (Sn), (Pt), (Au), (Hg), (Tl), (Pb), and
the semimetals such as (As), (Sb), and (Bi).
Compounds of sulfur and one of the semimetals are termed
semimetal sulfides.
 Clay Minerals
Clay minerals are an important group of minerals because
they are among the most common products of chemical
weathering, and thus are the main constituents of the fine-
grained sedimentary rocks called mudrocks (including
mudstones, claystones, and shales). 
In fact clay minerals make up about 40% of the minerals
in sedimentary rocks.  In addition, clay minerals are the
main constituent of soils
Based on their structures and chemical compositions,
the clay minerals can be divided in to three main
classes:
•The kandites  based on a structure similar to Kaolinite
•The smectites based on a structure similar to
Pyrophyllite
•The illites based on a structure similar to Muscovite

Each of these are formed under different

environmental and chemical conditions.
 Antimonides, Arsenides, Selenides, Tellurides

The nonmetal (S) and the semimetals (Se) and (Te)

consistently play the electronegative, anionic role in their
compounds.
However, the semimetals (As) and (Sb) may either play the
anionic role often filled by sulfur or else act as a cation by
donating electrons and forming a compound with sulfur.
When the semimeoccupy the role of a nonmetal and
substitute for the sulfur aniontals (Sb), (As), (Se), and (Te),
the minerals formed possess a chemical structure very
similar to that of the sulfides.
These are classified respectively as antimonides,
arsenides, selenides, and tellurides according to which
semimetal is present.
If both a metal and a semimetal such as arsenic or
antimony are present in a compound and there is no sulfur
anion present, then the semimetal replaces sulfur in order
to play the electronegative role.
In this case the mineral is classified as an antimonide,
arsenide, selenide, or telluride.
For e.g, niccolite (NiAs) contains the metal nickel and the
semimetal arsenic, which acts as an nonmetal and provides
the anion. Niccolite is therefore an arsenide.
Sulfosalts
      The rare minerals which are compounds of sulfur (S), a
semimetal such as arsenic (As) or antimony (Sb), and one
or more metals are termed sulfosalts. In these species
the semimetal plays the role of a metal. The mineral
cobaltite, which possesses the chemical formula CoAsS, is
a sulfosalt.
The metallic element is (Co); the semimetal is (As), and
the nonmetal is S receives the electrons donated by both
the cobalt and the arsenic.
Other e.g are: Ag3SbS3, Ag3AsS3.

Typical sulfides and sulfosalts are soft, dark, heavy, and

brittle, possessing a distinct metallic luster and high
conductivity.
Most are opaque, demonstrating the distinctive colors and
colored streak derived from the presence of chromophores
(iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu)).
 4. Oxides and Hydroxides
Simple and Multiple Oxides

Members of the oxide class are minerals in which an

oxygen anion is combined with one or more metals. The
oxides can be divided into two.

1. Simple oxides are compounds of a single metallic

element and oxygen. E.g include zincite (ZnO), tenorite
(CuO), cuprite (Cu2O), rutile (TiO2), uraninite (UO2),

corundum (Al2O3), hematite (Fe2O3), and magnetite

(Fe3O4).
Ice (H2O) provides an unusual example of a simple oxide

in which hydrogen replaces a metal in order to act as the

cation.
Multiple oxides, in contrast, are compounds of oxygen
with two or more metallic elements.
Examples are ilmenite (FeTiO3), spinel (MgAl2O4),

chromite (FeCr2O4), and chrysoberyl (BeAl2O4).

Many of these species are colorful, relatively hard, and
may be used as gemstones.
 Hydroxides
Hydroxides are compounds of metallic elements with
water or the hydroxyl anion (OH)-.
Examples of hydroxides are manganite (MnO(OH)),
goethite (FeO(OH)), and gibbsite (Al(OH)3; one of the

main components of bauxite).

Minerals of the hydroxide class are typically softer than
oxides and are of low to medium density.
 Halides
The halide class is composed of minerals in which an
element of the halogen group such as (F), (Cl), (Br), or (I)
provides the anion.
These elements form relatively large, lightly charged,
easily polarized ions. The halogen ions then bond to large,
weakly polarized cations of (Na), (K), (Mg) or (Ca), and
sometimes (Al), (Cu), or (Ag).
Halides are therefore constructed entirely of ionic bonds.
The halides tend to be soft, brittle, easily soluble in water,
and possess medium to high melting points.
They are poor conductors of heat and electricity when in
solid state but good conductors when molten.
e.g. of the halide class are the mineral species halite
(NaCl; also known as rock salt), sylvite (KCl), fluorite
(CaF2), and chlorargyrite (AgCl, also known as horn silver).
 Carbonates
Mineral species which are members of the carbonate class
are compounds of a metal or semimetal with the carbonate
anion (CO3)2-.

In these substances plane triangular (CO3)2- anion groups

are linked together by various cations.

Minerals of the carbonate class thus react easily with acids
such as hydrochloric acid (HCl). For example, calcite
(calcium carbonate, CaCO3) effervesces when placed in an

aqueous solution of HCl, producing carbon dioxide and

calcium chloride:
CaCO3 (s) + 2HCl (aq) -------> CaCl2 (s) + CO2 (g) + H2O
Anhydrous Carbonates
      The anhydrous carbonates lack both the
hydroxyl anion (OH-) and water (H2O) in their

chemical formulae. These carbonates are divided

into three isostructural groups, called the calcite
group, the dolomite group, and the aragonite
group.
The calcite group contains calcite (CaCO3), magnesite

(MgCO3), rhodocrosite (MnCO3), and siderite (FeCO3).

The dolomite group contains the minerals dolomite
(CaMg(CO3)2) and ankerite (CaFe(CO3)2).

The aragonite group is composed of the orthorhombic

carbonates, of which aragonite (CaCO3), strontianite

(SrCO3) and cerussite (PbCO3) provide examples.

 Nitrates
The nitrates are chemically closely akin to the
carbonates. Nitrogen bonds to three oxygen atoms in a
structure very similar to the carbonate anion group
(CO3)2-. This nitrate radical, (NO3)-, forms the basic

building block of the nitrates

For example, nitratine (or soda niter; NaNO3)

Niter (KNO3, known colloquially as saltpeter

 Borates
The boron atom joins to three oxygen atoms to form the
borate radical, (BO3)3-. After this anion group has formed,

each oxygen atom still has one electron available for

bonding.
Borate radicals may therefore be linked into polymerized
chains, sheets, or multiple groups. The most common
borate minerals are composed of sheets of radicals
which are linked together through the sharing of all three
oxygen atoms.
Two example members of the borate class are borax,
which possesses the chemical formula Na2B4O7•10H2O,

and colemanite, Ca2B5O11•5H2O.

Sulfates
The sulfur anion (S2-) may bond to a positive metallic
or semimetallic ion, receiving two electrons in order to
fill its valence shell.
Mineral species of the sulfide class are compounds of
this nature.
Alternately, the six electrons of sulfur's unfilled valence
shell may be ejected, resulting in the small, highly charged
(S6+) cation.
The sulfur cation may then form very strong bonds with
four oxygen atoms, producing the anion group (SO4)2-. This

sulfate radical forms the basic structural unit of the

minerals of the sulfate class.
 Hydrous Sulfates (Gypsum)
Gypsum (CaSO4•2H2O) is the most prevalent and

important of the hydrous sulfates.

It possesses a sheetlike structure which consists of layers of
calcium ions and sulfate anions separated by water
molecules (H2O).

Gypsum demonstrates perfect cleavage along planes

parallel to its sheetlike layers
. If the water is driven out of the gypsum structure, the
mineral will collapse into the configuration of anhydrite
(CaSO4) with a marked decrease in volume and loss of the

perfect cleavage.
Chalcanthite (CuSO4•5H2O, also known as blue vitriol),

melanterite (FeSO4•7H2O, known colloquially as copperas),

epsomite (MgSO4•5H2O),
 Anhydrous Sulfates
      Anhydrous sulfates contain neither water molecules
(H2O) nor the hydroxyl anion (OH-) within their lattice

structures.
The anhydrous sulfates consist of the barite group and
the mineral species anhydrite (CaSO4).

The members of the barite group include barite (BaSO4),

celestite (SrSO4), and anglesite (PbSO4).

 Chromates
Minerals of the chromate class are compounds of
metallic cations with the chromate anion group (CrO4)2-.

The species of this class of minerals are very rare.

     Crocoite
Due to the strong pigmenting capabilities of chromium,
crocoite is a bright orange-red in color while its streak is
orange.
E.g. lead chromate crocoite (PbCrO4)
 Molybdates and Tungstates
 Just as sulfur and chromium form the anion groups (SO4)2-

and (CrO4)2-, the ions of molybdenum (Mo) and tungsten

(W) bond with oxygen atoms to create the anion groups

(MoO4)2- and (WO4)2-.

These anion groups then bond with metal cations to form

the minerals of the molybdate and tungstate classes.
However, the atomic radii of molybdenum and tungsten are
larger than that of sulfur.
Minerals containing the molybdate or tungstate anion
groups are categorized as members of the molybdate or
tungstate classes. These two classes are then further
subdivided into the wolframite and scheelite groups.
Minerals of either class may be placed into each group
according to the relative size of the metallic cation which
they contain. Species of the molybdate and tungstate
classes are typically heavy, soft, and brittle.
They tend to be dark or vividly colored.
     
 wolframite
Mineral species belonging to the wolframite group
contain small cations such as magnesium, manganese, iron,
cobalt, and nickel.
The tungstates huebnerite (MnWO4) and ferberite (FeWO4)
are considered to be end members of a series of solid
solution in which manganese may substitute for various
quantities of iron and vice versa.
Both huebnerite and ferberite belong to the wolframite
group.
 Scheelite
  Mineral species belonging to the scheelite group form
compounds containing larger ions such as calcium.
The tungstates scheelite (CaWO4) and stolzite (PbWO4)

and the molybdates powellite (CaMoO4) and wulfenite

(PbMoO4) are all members of the scheelite group.

 Tungstates
The tungstates scheelite (CaWO4) and stolzite (PbWO4) and

the molybdates powellite (CaMoO4) and wulfenite

(PbMoO4) are all members of the scheelite group.

Phosphates, Arsenates, and Vanadates
     Like sulfur, the elements phosphorous (P), arsenic (As),
and vanadium (V) form tetrahedral anion groups in
combination with oxygen.
The resulting phosphate radical, (PO4)3-, provides the

basic structural unit of the minerals of the phosphate

class; the arsenate and vanadate radicals (AsO4)3- and

(VaO4)3- form the basic structural units of the arsenate

and vanadate classes.

 Apatite Group
      The apatite group contains mineral species of each of
the phosphate, arsenate, and vanadate classes.
Among the minerals of the apatite group number the three
lead ores pyromorphite (Pb5Cl(PO4)3), mimetite

(Pb5Cl(AsO4)3), and vanadinite (Pb5Cl(VO4)3).

Each of these species contains both lead and chlorine.
The apatite group also contains the three species
fluorapatite (Ca5F(PO4)3), chlorapatite (Ca5Cl(PO4)3), and

hydroxylapatite (Ca5(OH)(PO4)3).
These species are all calcium phosphates, because they
contain the calcium cation (Ca2+) and the phosphate
radical (PO43-).
However, each species contains a different anion.