CHEMICAL COMPOSITION

Chemical analysis of minerals are obtained by variety of methods which includes:

Wet Analytical techniques: Here, the mineral is dissolved in a solution from which various

insoluble compounds are precipitated by reaction from the weights of the precipitates, one obtains

a gravimetric analysis; “rapid gravimetrical scheme” (offers increase speed of determination at the

expense of accuracy) e.g. X - ray fluorescence, atomic absorption spectroscopy and electron

microprobe analysis. Each of these techniques has its own specific sample preparation

requirements and fairly well defined error ranges.

The most recent analytical techniques for analysis are:

I C P –M S (whole rock analysis – major, trace and REE elements)

I C P – O E S (Water analysis)

I C P – A E S (Soil and stream sediment analysis)

X – Ray fluorescence (X R F) - Trace elements

Atomic Absorption spectroscopy (A A S) used of fictively water analysis. A graphite furnace can

be attached to the AAS for higher chemical analysis.

The results of any analysis procedure are generally represented in form of weight percentage of

the element or as oxide components in the mineral analyzed. Most minerals are chemical

compounds composed of two or many more elements, and the result of quantitative chemical

analysis indicate the atomic proportion of the elements present. A weight percentage analysis in

terms of metals or oxides present gives a listing of element that are present and in which quantities,
but no direct information about how the element (or ions) occur in the structure of the mineral.

From such chemical analyses, formulae of such mineral compounds can be calculated.

Analysis of several specimens of mineral sphalerite (ZnS) show that it is not a pure zinc sulphide

but contain variable quantities of iron as well as cadmium, manganese and that the quantity of

Iron varies widely. The large variation of iron in sphalerite is due to the substitution of iron for

zinc in the same sphalerite structure. This phenomenon is known as solid solution of Iron in zinc

sulphide.

COMPOSITIONAL VARIATION IN MINERALS

Compositional variation in minerals is the result of substitution in a given structure, of an ion or

ionic group for another ion or ionic group. This type of process, referred to as ionic substitution,

or solid solution. These normally occur among minerals that are isostructural. A solid solution is

a mineral structure in which specific atomic site(s) are occupied in variable proportions by two or

more different chemical elements or groups. The types of solid solutions can be discussed in terms

of substitutional, interstitial and omission solid solution mechanism.

Substitutional Solid Solution

This is the common type of ionic substitution. Fe2+ substitute for Zn2+ in the same atomic site of

sphalerite structure; Fe2+ replaces Mg2+ in a specific site of the olivine structure etc. Several factors

influence the extent to which substitution may take place in a crystal structure. These factors are:

1. The size of the ions, atoms or ionic groups that are substituting for each other. Ions of two

elements can readily substitute for each other only if their ionic radii are similar or differ

by less than 15%. If the radii of two ions differ by 15 to 30%, substitution is limited or rare;

if they differ by more than 30%, little substitution is likely to occur. These limits are only
 approximate and are based on empirical data derived from the study of a large number of

mineral systems displaying ionic substitution.

2. The temperature at which the substitution takes place. That is, the temperature at which a

crystal grow. The higher the temperature, the greater the amount of thermal disorder and

the less stringent the space requirements for the structure. Hence, crystal grown at high

temperatures may display extensive ionic substitution that would not have been possible at

lower temperatures. An example is the high temperature form of KAlSi3O8 (sanidine)

which can house much larger amounts of Na (in substitution for K) than can be

accommodated in the lower temperature form (microcline).

3. The charges of the ions involved in the substitution. If the charges are the same, as in Mg2+

and Fe2+, the structure in which the ionic replacement occurs will remain electrically

neutral. If the charges are not the same, as in the case of Al3+ substituting for Si4+, additional

ionic substitutions elsewhere in the structure must take place in order to maintain overall

electrostatic neutrality.

The simplest types of ionic substitution are simple cationic or anionic substitutions. In a compound

of A+ X- type composition, A+ may be in part or wholly replaced by B+. In this instance, there is

no valence change and such a substitution is illustrated by K in the Na position of NaCl. A simple

anionic substitution can be represented in an A+ X- compound in which part or all of X- can be

replaced by Y-. An example is the incorporation of Br- in the structure of KCl in place of Cl-.

An example of a complete solid solution series (meaning substitution of one element by another

over the total possible compositional range, as defined by two end member compositions) is

provided by (Mg,Fe)2 SiO4. Mg2+ can be replaced in part, or in total by Fe2+; the end members of

the olivine series between which there is complete solid solution are forsterite (Mg2 SiO4) and
fayalite (Fe2 SiO4). Intermediate compositions are defined in terms of relative proportions of fo to

fa.

If in the general composition of A2+ X2- , a cation B3+ substitutes for some A2+ ; electrical neutrality

can be maintained if identical amount of A2+ is at the same time replaced by cation C+. This can

be represented by 2A2+ = 1B3+ + 1C+ with identical total electrical charges on both sides of the

equation. This type of substitution is known COUPLED substitution. The plagioclase feldspar

series can be represented in terms of two end members: NaAlSi3O8 (albite) and CaAl2Si2O8

(anorthite). The complete solid solution between these two end members illustrates coupled

substitution: Na+ Si4+ = Ca2+Al3+. This means that for each Ca2+ that replaces Na+ in the feldspar

structure, Si4+ is replaced by Al3+ in the Si – O framework. The total electrical charges on both

sides of the equation are equal and as such the structure remains neutral.

An example of only limited coupled substitution is provided by two pyroxenes, diopside

(CaMgSi2O6) and jadeite (NaAlSi2O6). The coupled substitution can be represented as Ca2+Mg2+

= Na+ Al3+. Although the pyroxene structure is neutral with either type of cation pair, the atomic

sites and coordination polyhedron do not allow for a complete solid solution of this type.

Interstitial Solid Solution

Between atoms or ions, or atomic groups of a crystal structure, interstices exist which are

considered voids. When ions or atoms are located in these structural voids, we speak of interstitial

substitution or interstitial solid solution. In some crystals, these voids may be channel-like cavities

as in beryl (BeAl2Si6O18). In this ring-silicate, large ions as well as gases occupy the tubular
cavities of superimposed rings. Considerable amounts of K, Rb, Cs and H2O as well as He are

reported in beryl analyses, housed interstitially in the hexagonal channels.

Omission Solid Solution

The best known mineralogical example of this type of solid solution is provided by pyrrhotite,

Fe(1-x)S. In pyrrhotite, sulphur occurs in hexagonal closest packing and Fe in 6 coordination with

sulphur. If each octahedral site were occupied by Fe2+, the formula of pyrrhotite would be FeS.

However, in pyrrhotites, there is a variation in the percentage of vacancies in the octahedral sites,

causing the composition to range from Fe6S7 through Fe11S12, close to FeS. The formular is

generally expressed as Fe(1-x)S Fe(1-x)S with x ranging from 0 to 0.2.

Minerals, such as pyrrhotite, in which a particular structural site is incompletely filled are known

as defect structures. When Fe2+ is absent from some of the octahedral site in pyrrhotite, with

sulphur not completely intact, the structure is not electrically neutral. It is possible that some of

the Fe is in the Fe3+ state to compensate for the deficiency in Fe2+. If this is so, a neutral pyrrhotite

formula can be written as (Fe2 (1-3x) Fe3+2x Vx)S1. If x in this example is taken as 0.1, this formulation

means that 0.1 vacancies (v) and 0.7 Fe2+ and 0.2, Fe3+ occur in the structure of pyrrhotite.

EXSOLUTION

The term exsolution refers to the process whereby an initially homogenous solid solution separates

into two (or more possible) distinct crystalline minerals without the addition or removal of material

to form the system; this means that no change in the bulk composition takes place.
Exsolution generally, although not necessarily, occurs on cooling. Exsolution features are best

observed under a high power microscope because the scale of exsolution is generally on about a 1

micron level or smaller (1µ = 10-3 mm).

Exsolution lamellae which separates from originally homogenous host mineral are generally

crystallographically oriented. In alkali feldspars (Na-K) exsolution lamellae can often been seen

in the hand specimen to be approximately parallel to [100]. Such a coarse grained intergrowth of

exolution lamellae in plagioclase feldspars may consist of Na-rich feldspar lamellae in a K-rich

host and is known as PERTHITE. If the exsolution is on a scale that can be resolved only

microscopically, it is reffered to as microperthite; and if by X-ray diffraction techniques are needed

to resolve extremely fine lamella, the intergrowth is known as cryptoperthite.

This type of crystallographically controlled intergrowths resulting from exsolution are common in

many mineral systems eg. alkali feldspars, pyroxenes, amphiboles and oxides of Fe.

The origin of exsolution textures is best illustrated with reference to a schematic temperature –

composition diagram of the type we shall discuss later. These diagrams are known as phase

diagrams.

Exsolution processes take place in the solid state. The temperature – composition (T-X) diagram

depicting the sequence of events leading to exsolution is therefore, generally referred to as a sub-

solidus phase diagram.

The discussion of solid solution to this point has to do with the abundance of the rock forming

mineral elements that are the principal constituents of the Earth’s crust. Only 8 elements compose

well over 90% of the crust leaving the 8-naturally occurring elements of the periodic table in very

low concentrations. These element are often referred to as MINOR or TRACE elements and they
also play an important role. Many of them are of considerable economic importance; others are

diagnostic in the solution of geologic problems. In any case, they may be grouped into two

principal categories. Those that do not easily substitute into the structures of the rock-forming

minerals are called incompatible elements, and those that resembles a major element to the point

that they may proxy for it in rock-forming minerals are called compatible elements. The solution

of a compatible element in a mineral can be described in geochemical terms as CAPTURE when

the proxy element has similar size but greater charge. It can also be described in term of

ADMISSION when the proxy element has similar size but a lower charge. It can also be described

in terms of CAMOUFLAGE which is when the proxy element has similar size and same valence.

An example of capture include the common substitution of Ba2+ for K in potassium feldspars or

the substitution of Cr3+ for Mg in ferromagnesian silicates.

Admission is exemplified by the proxy of Li+ for Mg2+ or by the common substitution of Al3+ for

Si4+ in silicates while the proxy for Ni2+ for Mg2+ or Ga3+ for A13+ are good examples of

camouflage

In the same instances, the similarities between certain elements are so close that the proxy element

is always found within a major element minerals. These elements are referred to as dispersed

element. Good examples for these are Rubidium (Rb+) for K,+ Cd2+ for Zn 2+ , Hf4+ for Zr4+. In

fact, these dispersed element are always found in K, Zn and Zr minerals respectively and only

rarely form minerals on their own.

MINERAL CLASSICATION

Chemical composition has always been the bases for the classification of minerals for a long time

and according to this scheme, minerals are divided into classes:

 Ore/metallic minerals and Industrial/non-metallic minerals.

 Minerals are divided into classes depending on the dominant anion or anionic group

 Oxides, halides, sulphides, carbonates and silicates etc.

There are number of reasons why this criterion is, a valid bases for mineral classification.

Minerals having the same anionic group, dominant in their composition have unmistakably family

resemblances and in general stronger and more clearly marked than those shared by minerals

containing the same dominant cation. Thus, the carbonates resemble each other more closely than

do minerals of copper.

However, it was highly recognized that chemical composition only does not adequately

characterize a mineral. A full appreciation of the nature of a minerals was to wait until X-rays were

used to determine the internal structures. It is now clear that mineral classification must be based

on chemical composition and internal structure, because these two together represents the essence

of a mineral and determines its physical properties. The following are the broad classes based on

these criteria;

(1) Native Elements: About 20 element are found in the native states and these elements can

be divided into:

 Metals

 Semi-metals

 Non-metals
The more common native metals which displays simple structure constitute three groups.

(a) Gold Group: Gold, silver, copper and lead. All these element are iso-structural.

(b) Platinum Group: Platinum, palladium, iridium and osmium.

(c) Iron group: Iron and nickel-iron.

In addition, we have mercury, tantalum, tin and zinc

The native semi-metals form two iso-structural groups.

Arsenic, antimony and bismuth. The less common are selenium and tellurium

The most important native non-metals are: sulphur and carbon (in form of diamond and graphite).

(2) SULPHIDES: The sulphides form an important class of minerals and majority of the

minerals are ore minerals. With them are classed the similar but rarer sulphursenides,

arsenides and tellurides. Most of the sulphide minerals are opaque with distinctive colours

and characteristic coloured streaks. Examples of the sulphides are:

(a) Chalcocite (Cu2S)

(b) Bornite (Cu5FeS4)

(c) Galena (PbS)

(d) Sphalerite (ZnS)

(e) Chalcopyrite (CuFeS2)

(f) Pyrrhetite ( Fe(1-x)S)

(g) Covellite (CuS)

(h) Cinnabar (HgS)

(i) Pyrite (FeS2)

(j) Marcasite (FeS2)

 (k) Molybdenite (MoS2)

(l) Arsenopyrite (FeAsS)

(3) SULPHOSALTS

These comprises a very diverse and relatively large group of minerals is with about 100

species, some of the members are listed below:

 Tetrahedrite (Cu12 Sb4 S13)

 Energite (Cu As S4)

(4) OXIDES AND HYDROXIDES

Oxides are group of minerals that are relatively hard, dense and refractory (can with stand

heat) and generally occur as accessory minerals in igneous and metamorphic rock and as

well as resistant detrital grains in sedimentary rocks. The hydroxides, on the other hand,

tend to be lower in hardness and density. They are found mainly in secondary alteration or

weathering products.

The oxides includes those natural compounds in which oxygen is combined with one or

more metals. They have been grouped as simple oxides and multiple oxides. The most

common oxide SiO2 (quartz) and its polymorphs, is not considered as an oxide here because

the structure of quartz and its polymorphs is mostly related to that of other Si-O

Compounds (silicates). Examples of oxides are: Cuprite (CU2O), Zincite (ZnO), Corundum

(A12O3) Hematite (Fe2O3), Magnetite (Fe3O4), Ilmenite (FeTiO3), Rutile (TiO2) Cassiterite

(SnO2), Spinel (MgAl2O4) and Chromite (FeCr2O4).

 Examples of hydroxides are: Brucite Mg (OH)2, Manganite MnO(OH), Goethite (FeO.OH)

and Bauxite (mixture of diaspora AlO.OH, gibbsite and boehmite).

(5) HALIDES

The chemical class of halides is characterized by the dominance of the electronegative

halogen ions, Cl-, Br-, F- and I-. These ions are large and have a charge of – l and are easily

polarized. Some important halides are as follows: Halite (NaCl), Sylvite ( Kcl), Flourite

(CaF2), Aracamite CU2 Cl (OH)2.

(6) CARBONATES

The triangular carbonate group (CO3)2-are the basic unit of carbonate minerals and are

largely responsible for the properties peculiar to the group. The important member are as

follows:

Calcite Group Aragonite Group

Calcite = CaCO3 Aragonite = CaCO3

Magnesite = MgCO3 Witherite = BaCO3

Siderite = FeCO3 Strontianite = SrCO3

Rhodochrosite = MnCO3 Cerusite = PbCO3

Smithsonite = ZnCO3

Dolomite Group

Dolomite = Ca Mg (CO3)2

Ankerite = Ca Fe (CO3)2

Monoclinic carbonates with OH- include: Malachite = Cu2(CO3)(OH)2 and Azurite = Cu3(CO3)2

(OH)2.
(7) NITRATES

Nitrates are structurally similar to the carbonates. Examples are:

Soda Niter = (NaNO3)

Niter = (KNO3)

(8) BORATES

In this group of minerals, BO3 units are capable of polymerization in the form of chains,

sheets and isolated multiple groups, just like in the silicates.

Examples are:

Kernite = Na2 B4 O6 (OH)2 . 3H2O

Borax = Na2 B4 O5 (OH)4 . 8H2O )

Colemanite = CaB3 O4 (OH)3 . H2O)

(9) SULPHATE and CHROMATES

Anhydrous sulphate and chromate.

Barite Group Hydrous and Basic Sulphates

Barite = (BaSO4) Gypsum = CaSO4 .2H2O

Celestite = (SrSO4) Antlerite = CuSO4(OH)4

Anglesite = (PbSO4) Alunite = KAl3(SO4)2(OH)6

Anhydrite = (CaSO4)

Crocoite = (PbcrO4)
 (10) TUNGSTATES and MOLYBDATES

Examples are:

Wolframite = (Fe, Mn)WO4

Scheelite = (CaWO4).

(11) PHOSPHATE, ARSENATES and VANADATES

For example Apatite Ca5(PO4)3(F,CI,OH) is the most important member.

Apatite occurs in hexagonal form i.e crystallizes in the hexagonal system and commonly occurs in

crystals of long prismatic habits but times short prismatic or tabular. Also massive granular to

compact masses.

Fluor apatite = Ca5 (PO4)3 F) is the most common and more rarely chlorapatite (Ca5(PO4)3Cl) and

Ca5(PO4)3 (OH) hydroxylapatite. F, Cl, and OH can substitute for each other giving a complete

series. (CO3, OH) may substitute for (PO4) giving carbonate apatite and (PO4) can partially be

replaced by SO4 and as well as SiO4.

Cellophane is a name given to the massive cryptocrystalline types of apatite that constitute the

bulk of phosphate rock and fossil bone.

Occurrence of Apatite.

Apatite is widely disseminated and as an accessory constituent in all classes of rocks. They are

also found in pegmatite and veins of rock.

Uses / Industrial Importance of Apatite

Source of phosphorus which can be used in the manufacture of fertilizer (NPK).