2022

CRYSTALLOGRAPHY & MINERALOGY GLO 1103

MINERALOGY SECTION:
Lecturer: Mrs. Peggy K. Kalegga

Has three credit units. It is a core course, forming the second part of Crystallography & Mineralogy (GLO1103).

Course Description:
The course introduces students to various types of minerals as well as their physical properties and classification.
Students ought to have background knowledge on crystallography in order to understand this course properly. It
acts as a foundation for more advanced courses like petrology, optical mineralogy (mineral optics),
igneous/sedimentary /metamorphic petrology, e. t. c.

Course Objectives:
At the end of the course, the student is expected to:
- Describe the crystal forms and shapes of various rock-forming minerals.
- Discuss the physical characteristics of minerals.
- Relate physical properties of minerals to their crystal structures & economic uses.
- Identify different minerals using their physical properties.

Course outline
I - Introduction:
a) Definition of minerals
b) Nomenclature of minerals
c) Why minerals are studied
d) Types of minerals
e) Economic importance of minerals
f) Mineral chemistry
- Fundamental principles
- Formation of minerals
- Mineral environments
- Compositional variation in minerals
- Solid solution
- Exsolution
- Isomorphism
- Polymorphism
- Analytical techniques used in chemical analysis of minerals
- Recalculation of chemical analyses of minerals
- Graphic representation of mineral compositions

II - Physical properties of minerals:

a) Mechanical properties: Habit, Hardness, Cleavage, Fracture, Parting, Tenacity & Specific gravity
b) Optical properties: Streak, Lustre, Transparency/opacity /diaphenity, Colour, Luminescence, asterism,
chatoyancy, opalescence, adularescence, iridescence, play of color ± pleochroism ± double refraction
c) Electrical properties: Piezoelectricity & Pyroelectricity
d) Magnetic properties: Ferromagnetism, Diamagnetism & Paramagnetism
e) Other properties: Melting point, Radioactivity, Solubility in acids, Senses (taste, smell, feel/touch)

III - Classification of minerals with some common examples from each class:
Native elements, Sulphides & sulphor-salts, Halides, oxides and hydroxides, Carbonates, Nitrates, Tungstates
& Molybdates, Phosphates, Arsenates & Vanadates, Sulphates & Chromates, Borates & Silicates.

IV – Practicals on the different classes of minerals

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Assessment criteria: Students will be assessed in three ways i.e. assignments & tests (20%), practicals (20%),
and final examination (60%). Note that the assessment includes tasks on both mineralogy and crystallography.

Selected References:
- Battey, M.H. (1981): Mineralogy for students; Second edition; Longman Scientific & Technical; 355pp.
- Hefferan, K. & O'Brien, J. (2010):  Earth Materials;  1st Edition; Wiley-Blackwell.
- Haldar, S. K. & Tisljar, J. (2020):   Introduction to Mineralogy and Petrology; Second Edition; Elsevier Inc.;
USA.
- Hurlbut, Jr. C. S & Klein, C. (1993): Manual of Mineralogy; 21 st edition; after James D. Dana; John Willey &
Sons Inc.; 681pp.
- Internet
- Klein, C. & Phillpotts, A. (2017): Earth Materials: Introduction to mineralogy and Petrology; Cambridge
University Press; 616pages.
- Nesse, W. D. (2016): Introduction to Mineralogy 3rd Edition; Oxford University Press.
- Mineralogy journals and magazines e.g. Contributions to Mineralogy and Petrology by Springer.com, European
journal of mineralogy, Australian journal of mineralogy, Mineralogical Magazine (published by the
Mineralogical Society of Great Britain), American Mineralogist (published by the Mineralogical Society of
America), e. t. c.
- Press, F. & Siever, R. (1986): Earth; fourth edition; W.H. Freeman and company, New York; pp.61-80.
- Wenk, H. R. & Bulakh, A. (2017): Minerals: Their Constitution and Origin; 2nd Edition
- Winter, J.D (2014): Principles of Igneous and Metamorphic Petrology; 2nd Edition; Pearson education Limited.
- Zussman, J., Deer,W. & Howie, R. A. (2013): Introduction to the Rock-Forming Minerals; third edition; John
Willey & Sons Inc., New York.

INTRODUCTION

Definition:
A mineral is a naturally occurring homogenous solid with a definite (but generally not fixed) chemical
composition and a highly ordered atomic arrangement.
Minerals are mainly formed by inorganic processes such as evaporation, plutonism, metamorphism, weathering,
volcanism, e.t.c. although some minerals could be formed by organic processes for example calcite occurs in
igneous and metamorphic environments but may be formed by organisms to form shells.
+ Naturally occurring = formed by natural processes.
Minerals may be formed by different geologic processes as outlined below:
- Magmatism e.g. magnetite, diamond, graphite, apatite
- Sublimation e.g. sulphur
- Weathering e.g. clays, bauxite, magnesite
- Diagenesis e.g. clays, sulphates during authigenesis
- Evaporation e.g. salts and carbonates
- Metamorphism e.g. kyanite, graphite, corundum, e.t.c.
- Sedimentation e.g. gypsum & anhydrite

In order to be a mineral, a chemical compound must occur naturally somewhere and be stable enough to study in
the lab. We can make many compounds in the lab that are not minerals unless they are found in nature.
+ Homogenous solid = consists of a single solid substance that cannot be subdivided into simpler chemical
compounds. Note that, minerals are chemically homogenous down to the atomic scale!
+ Solid = excludes gases & liquids (hence water as ice in a glacier is a mineral but liquid water is not; like wise,
liquid mercury (Hg) found in some Hg deposits is excluded; the same for petroleum and gases, e.t.c. Such
natural substances that are like minerals in chemistry and occurrence but usually amorphous are called
mineraloids.
+ Definite, but not fixed, chemical composition = can be expressed by a specific chemical formular.

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Minerals have chemical formulae determined by the atomic structures. Symmetry requires atoms to occur in
simple, specific, integer ratios. However, for a given mineral, substitution of similar elements is possible.
+ Ordered atomic arrangement = an internal framework of atoms or ions arranged in a regular geometric pattern.
Minerals are crystalline solids. Crystals are a periodic array of atoms. Atoms achieve their lowest energy by
having each different type of atom/element in an identical environment.
* Examples of minerals include: gold, silver, diamond, graphite, pyrite, marcasite, sphalerite, halite (salt), calcite,
apatite, olivine, garnet, zircon, pyroxene, amphibole, mica, quartz, feldspar , zeolite, e.t.c.
* However, the following natural solids are not minerals:
- granite, basalt & limestone are rocks (composed of minerals).
- wood & coal are organic non-crystalline solids.
- obsidian & pumice are glassy & amorphous/non-crystalline solids
* Hence, mineralogy in the study of natural crystalline solids.

Nomenclature (naming) of minerals:

Minerals are given names on the basis of some physical property or chemical aspect or may be named after a
locality, a public figure, a mineralogist or any other aspect considered appropriate. Some examples of mineral
names and their derivations are:
- Albite (NaAlSi3O8 ) from the latin ‘albus’ (white): an illusion of its color .
- Rhodonite (MnSiO3) from the Greek Rhodon (a rose) : an illusion of its characteristically pink color .
- Chromite (FeCr2O4) because of the presence of the large amount of chromium in the mineral.
- Magnetite (Fe3O4) because of its magnetic properties .
- Franklinite ( ZnFe2O4) after a locality , Franklin , New Jersey , where it occurs as the dominant Zinc mineral .
-Sillimanite (Al2SiO5) after prof. Benjamin Silliman of Yale University (1779-1864) .
- 'Feldspar' is derived from a German word meaning, roughly, 'field rock' in reference to its abundance.
* The stem of the names may be derived from some physical characteristic of the mineral e.g. orthoclase (straight
fracture), Azurite (blue).
* Others are named from the places where they are found e.g. montmorillonite (Montmorillon, France).
* Others from notable persons include goethite, bunsenite, smithsonite.
* Some names indicate their chemical compositions e.g. beryl and borax.
In general, minerals are given names ending with '-ite' from the Greek word 'lithos' (rock).
The International Mineralogical Association, in cooperation with member societies in many countries, is
responsible for the validity of mineral species and their names. Professional mineral journals periodically report
decisions of the association regarding new mineral names and new data.

Note that: Though minerals are vastly simpler, chemically, than living things, the variations in appearance
among different specimens of the same mineral are almost overwhelming. Therefore, several mineralogy books
should be used as a study guide.
Only after much study and examination of known minerals is it possible to go into the field and make
positive identification of minerals. It's also essential to observe relationships among minerals in rocks and
between the rocks themselves because it's from this that we can understand the origin of rocks and the geologic
processes affecting them.

Why Study mineralogy?

Mineralogy is primarily a tool for understanding the Earth.
All of the solid parts of the universe are composed of minerals and we cannot hope to understand it without some
knowledge of mineralogy.
The study of minerals helps us explain the physical–chemical and historical aspects of the earth.
- Minerals are products of geological processes and from these, we can draw conclusions as to the nature of the
processes themselves. Minerals are the primary recorders of ancient earth processes. If you are interested in
studying any past earth process, and if you can identify a mineral that formed in response to that process, then
you can potentially use that mineral to learn about the process or event of interest. Thus helping us to deduce the
Earth’s history.

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In order to understand the processes that go on in the earth, it’s oceans, and deep interior since minerals form in
response to a diverse array of Earth processes (igneous, metamorphic, sedimentary) from high to low-
temperature, from Earth’s surface to its deep interior, and from terrestrial to marine.
- It’s possible to replace most minerals in the laboratory under controlled conditions of T, P, and chemical
environment . This enables the explanation of the stability range of the minerals and hence the conditions under
which the rocks containing them were formed .
Since minerals are the solid compounds that make up most rocks, and yet rocks compose most of the earth,
geologists must learn mineralogy so that they know the properties of the rocks they are studying and can make
reasonable inferences about how those rocks will behave under different conditions.
-To trace the migration, sorting-out, concentration or dispersal of the elements and to know their temporally
resting places in animal or plant tissues. All the above is the basic stuff of the earth’s history and from it we try
to understand the changing environments through geologic time”.
Minerals play important roles throughout the earth system. Minerals influence and respond to physical,
chemical, and biological processes operating throughout the Earth. This includes tectonism, volcanism, erosion,
weathering, climate, the environment, and the very origins of life.
Minerals have societal & environmental relevance.
- Minerals represent some of earth’s most important natural resources including industrial minerals, ores, and
gems due to their great economic value. The very infrastructure of our society is made from these mineral
resources (e.g. copper wires, gold jewelry, diamond rings, aluminum cans, steel bridges, plaster walls, cell
phones, nuclear reactors, and more).
- The geologically controlled geographic distribution and mining of these societally relevant mineral deposits can
have significant, and sometimes disastrous, environmental and human consequences.

Academic preparation & graduate school in geosciences

-Mineralogy is a foundational course for students with broad geosciences interests. It is a recommended pre-
requisite for structural geology, petrology & other geoscience courses.
- Mineralogy is a required class for many geological field excursions/ field works.
- Mineralogy is a required undergraduate coursework for applicants to many geosciences post-graduate
programs.

Mineralogy is valuable, and often expected, background for many non-academic geosciences careers including
environmental consulting firms, geotechnical firms, materials industry, mining industry, the oil & gas industry,
geological surveys and other government agencies as well as NGO’s.

Types of minerals
a) Economic minerals: These are subdivided into:
(i) Ores &
(ii) Industrial rocks and minerals
b) Rock-forming minerals
c) Others include accessory, essential, gangue, felsic and mafic minerals.

Ores:
An ore is a natural deposit in which a valuable (metallic) element(s) occurs in high enough concentrations to
make mining economically feasible.
It can also be defined as a metalliferous mineral or an aggregate of metalliferous minerals (rock) more or less
mixed with gangue from which one or more metals can be extracted at a profit.
Examples of ores include: Pyrite ( for iron), cassiterite (for tin), galena (for lead), corundum (for aluminium),
e.t.c. However the word ore is sometimes used loosely to include a few non-metallic minerals such as fluorite.

Industrial Minerals and rocks:

These are minerals or rocks that are (of economic value) used as raw materials for industry (rather than as a
source for particular element).

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In simple terms, industrial minerals refer to minerals (& mineraloids) or rocks or other naturally occurring
substances of economic value that are used as raw materials for industries excluding metallic ores, mineral fuels
(e.g. coal + petroleum), gemstones & water.
Examples of industrial minerals and rocks include: Limestone, Phosphates, Vermiculite, Clays, Gypsum, Rock
salt (halite), Diatomite (diatomaceous earth), Dimension stone, Aggregate stone, Glass sand, Feldspars, Sand &
gravel, Diamond, Fluorite, Baryte/ barite, e.t.c.
Despite the definitions given above, there is some considerable overlap between the four types of commodity:
fuel, metal ore, industrial mineral and gemstone hence some minerals might have uses within a number of
different applications. The example given below emphasizes this. Examples of this case are a number of metal
ores that are also used as industrial minerals e.g. rutile, bauxite and chromite.

Industrial minerals include all minerals that are being mined for the physical properties that they have, or that
they impart on products in which they are being used rather than for their metal-contents. They are generally low-
priced commodities when compared to most metals and are sold in bulk. The most important industrial
mineral/rock applications and some commodities for these applications are:
- Abrasives - silica sand, garnet, staurolite
- Agricultural industry - phosphates, natural zeolites, agricultural lime and dolomite, micas, gypsum
- Brick-making, ceramic, glazing and glass raw material - silica sand, quartzite, feldspar, talc, pyrophyllite,
nepheline syenite, limestone and wollastonite, kaolinitic clay, soda-ash
- Construction industry - normal and light-weight aggregates, sand and gravel, cement, dimension stone,
insulation, gypsum, pigments

Rock forming minerals:

These are minerals commonly found in & forming a large percentage of a rock . About 6 minerals make up ~90%
of the minerals known in the Earth crust i.e. feldspars, pyroxenes, amphiboles, olivine, micas & quartz . 20 other
minerals make up less than 20%. Rocks are composed of minerals.
There are over 8000 known different minerals. Only about 50 minerals are rock-forming. The rest occur as
accessory minerals i.e. as traces (in very minor amounts).
The most-common rock-forming minerals are listed below according to their classes:
a) Ortho-and ring silicates
- Olivine group: olivine , tephroite, knebelite, monticellite
- Humite group; chrondrodite, humite, clinohumite, Norbergite
- Zircon
- Sphene
- Garnet group: Pyrope , almandine, spessartine (≡PYRALSPITE), Uvarovite, grossular, andradite
(UGRANDITE) ± vesuvianite (idocrase)
- Sillimanite, mullite, andalusite , kyanite
- Topaz
- Staurolite , chloritoid
- Datolite , sapphirine
- Larnite, merwinite , spurrite, Eudialyte (Eucolyte), Rosenbuschite.
- Epidote group: zoisite, clinozoisite, epidote, piemontite, allanite.
- Lawsonite , pumpellyite
- Melilite group: Gehlenite, melilite, akermanite
- Rankinite, Tilleyite, lavenite, catapleite
- Beryl, cordierite, tourmaline, Axinite
b) Chain Silicates
- Pyroxene group:
i) Orthorhombic minerals (MgSiO3- FeSiO3) ≡ Enstatite- orthoferrosilite ± Hypersthene
ii) Monoclinic minerals (have wide range of chemical composition):
- diopside-Hedenbergite- Johannsenite
- Augite –Ferroaugite
- Pigeonite
- Aegirine – (aegirine- augite)
- Spodumene
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- Jadeite
- Wollastonite, pectolite, rhodonite, Bustamite, pyroxmangite,
- Amphibole group:
i) Orthorhombic: Anthophyllite, gedrite
ii) monoclinic: cummingtonite, grunerite, tremolite- ferroactinoilite, hornblende, Kaersutite, barkevikite,
glaucophane, riebeckite, richterite, katophorite, eckermannite, arfvedsonite, Aenigmatite, astrophyllite.
c) Sheet silicates
- Mica group: Muscovite, paragonite, glauconite, phlogolite, biotite, lepidolite, zinnwaldite, margarite,
clintonite, xanthophyllite
Pyrophyllite, Talc, Chlorite, Serpentine
- Clay minerals:
*Kandite group: kaolinite, dickite, nacrite, halloysite
*Illite group: illite, phengite, glauconite, celadonite, hydro-micas
* smectite group: montmorilonite, beidellite, nontronite, saponite, hectorite, sauconite.
*vermiculite
*Palygorskite group: Palygorskite, attapulgite, sepiolite
- Apophylite,
- Prehnite

d) Frame work silicates

i) Feldspar group:
*Alkali feldspars: albite, anorthoclase, sanidine, orthoclase, microcline ± perthite
- potassium feldspars: sanidine, orthoclase, microcline, adularia
- sodium feldspars: albite (low & high temp)
*Plagioclase: Albite, oligoclase, Andesine, Labradorite, Bytownite, Anorthite
± *Barium Feldspars: Celsian, Hyalophane
ii) Silica group: Quartz, Tridymite, Cristobalite, coesite, stishovite
iii) Feldspathoid group: Nepheline, Kalsilite, petalite, leucite
iv) Sodalite group: sodalite, Nosean, Hauyne, Helvite, danalite, genthelvite
- Cancrinite, vishnevite, scapolite
- Analcite,
v) Zeolite group: natrolite, mesolite, endingtonite, and thomsonite ± scolecite, phillipsite, Gismondine,
Gonnardite, Harmotome, Garronite, chabazite, heulandite, stilbite, laumontite, e.t.c.
e) Non-silicates:
- Oxides: Periclase, Cassiterite, Corundum, hematite, Ilmenite, rutile, anatase, brookite, perovskite, spinel group
(magnetite and chromite)
- Hydroxides: Brucite, gibbsite, diaspore, boehmite, goethite, lepidocrocite
- Sulphide: pyrite, pyrrhotite, chalcopyrite, sphalerite, galena
- Sulphates: Baryte, Celestine, gypsum, anhydrite.
- Carbonates: calcite, magnesite, rhodochrosite, siderite, dolomite, ankerite, huntite, aragonite, strontianite,
witherite
- Phosphates: Apatite, monazite
- Halides: Fluorite, Halite.
The minerals underlined are the most common rock forming minerals.

Gangue minerals:
Gangue is the unwanted material (minerals or rock with which ore minerals are usually inter grown.
Raw ore → mineral dressing (separation plant) → crushed → separate ore minerals (by say magnetic and/or
chemical processes, e.t.c.) → Gangue (waste) .

Accessory minerals:
These occur in small amounts (usually less than 1%) and are not important in the classification or rock; e.g.
Zircon hence their absence or presence does not affect the rock diagnosis.

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CRYSTALLOGRAPHY & MINERALOGY GLO 1103

Essential minerals are the abundant minerals in a given rock and so are very important in the classification of
rocks.

Other terminologies used are:

Felsic minerals: light coloured minerals. e.g. quartz, feldspar, calcite, nephheline, etc.
Mafic minerals: dark colored minerals e.g. biotite, amphibole, tourmaline, olivine, e.t.c.

Economic Importance of minerals

Everything we have and everything we use comes from our natural resources. If it's not grown, it's mined. Most
of the items we use and consume are actual mineral products or they are manufactured from or grown with
mineral products. Even agricultural products are produced with the use of mineral products - from fertilizing to
harvesting to packaging and, finally, distribution to the consumer.
Virtually no aspect of our lifestyle could be sustained without minerals. Minerals are used in every facet of our
daily living from food production and processing, building, providing shelter/housing to transport,
communications, medicine and leisure activities.
Therefore, we must explore for and efficiently develop our natural mineral resources.

Today, there is hardly any avenue of human endeavor that is not in some way dependant on the
substances/materials that minerals produce. Since minerals are the most important materials of industrial
activity, those countries abundantly supplied with mineral resources have become the great industrial nations and
consequently this has resulted in their being superior both economically and politically .
The quest for minerals has caused strife and war & it has given rise to voyages of discovery and settlement of
new lands. Modern civilization as we know it, would not be possible without mineral products. These products
are indispensable to the welfare, health and standard of living of modern man.
Mineral resources are the most valued and most ‘jealously guarded’ of all the natural resources of any nation.
We depend on mineral products for comfort (utensils, machines, transport), protection (houses, weapons, drugs)
and adornments (jewellery), e.t.c. Thus the use of minerals is inexhaustible!

The usefulness and interest of any mineral depends on 3 factors :

1 – it’s natural beauty (gem quality).
A gem mineral is any mineral, which if cut and polished, has sufficient beauty to be used as an adornment or for
jewelry. Examples include diamond, beryl, corundum, turquoise, spinel, zircon, garnet, quartz, topaz, e.t.c.
2- it’s value as an ore. This resides in the chemical composition which determines what elements may be got
from it by smelting or breaking down the structure in some other way, e.g. Galena (PbS) for lead (Pb) ; Hematite
(Fe2O3) for iron (Fe) ,Cassiterise (SnO2) for tin (Sn).
3- It’s unique structural pattern, i.e. properties of the mineral as a crystalline material e.g. diamond is the hardest
mineral known and hence can be used as an abrasive while it’s adamantine luster and conchoidal fracture favour
it’s use as a jewel; graphite is used as a lubricant due to it’s greasy feel but it’s black streak and black colour
favour it’s use in lead pencils. This also includes properties like piezoelectricity (generation of an electric charge
by stressing a crystal), which makes quartz useful in pressure gauges and electric oscillators.

MINERAL CHEMISTRY
- Minerals are the natural crystalline materials that form the Earth.
- Minerals are the constituents of rocks.
- Rocks make up the entire inorganic, solid portion of the Earth.
Fundamental principles:
- Like all matter, minerals are composed of minute particles called atoms.
- The kinds of atoms in minerals and the patterns in which these atoms are arranged determine the composition
and characteristics of minerals.
- Atoms are the building blocks of matter. Atoms are very minute particles and are made up of 3 kinds of even
smaller particles; protons, neutrons, electrons. Protons have a positive charge of fixed magnitude (+1).
Neutrons have no charge . Electrons revolve around the nucleus and carry a negative charge (-1) equal in
magnitude to the charge of the proton.

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- A single, isolated atom is electrically neutral [its number of electrons (negative charges ) are equal to its
number of protons [positive charges].
- Elements are the fundamental substances, each having atoms of a particular kind.
- The identity of an element is determined by its atomic number (the number of protons in the nucleus of an
atom) e.g. the carbon atom has 6 protons. The number of neutrons in a given element vary e.g. the carbon atom
has 5 to 10 neutrons but whatever the number, the atom remains chemically the same.
- Atomic weight is the number of the protons and neutrons in an atom.
- Isotopes are atoms of the same element with different atomic weights (hence different number of neutrons).
Some isotopes are stable . Others are not stable (thus radioactive) and disintegrate at a fixed rate into other
isotopes e.g. Carbon 14 [6C14] → Nitrogen 14 (7N14) .
- Electron configuration describes the distribution of electrons in an atom. It also explains why the atoms of
some elements react with others and why others do not react at all. Electrons occupy space near the nucleus in
well-defined energy levels ( represented by concentric shells). Electrons in the level nearest the nucleus have the
lowest energy while those farthest from the nucleus have the highest energy. Each level can hold a given number
of the electrons- the innermost may contain 2 electrons, 8 in the second shell, 18 in the third and each succeeding
shell may contain as many as 32 . Elements are very stable if the outer energy levels of their atoms have 8
electrons (stable octet). Elements react easily if the outer shells of their atoms are not filled. The atoms of these
elements tend to react with other atoms and lose, gain or share the number of electrons necessary to fill the outer
shell or obtain the stable octet.
- Electronic structures are shown by means of concentric shells with electrons in orbits around the nucleus.
- Electronic orbitals define the locations of the electrons in statistical terms.
An electron in the s- subshell of any electronic shell is most likely in a spherical volume of space about the
nucleus at any given time. Hence the spherical s-orbital defines the space in which it is probable that the electron
is located. Only two electrons with opposite spins may be in the s-orbital of the a given electron shell. An
electron in the next higher subshell is most likely in the volume of space defined by the ‘dumbbell’ p-orbital.
Electrons in the d-sub shell occupy the ‘double dumbbell’ orbital volume while those in the f-subshell occupy
even more complex orbitals.
- The periodic table arranges elements in a way that shows relationships among them as groups and periods e.g.
the alkali metals ( Li, Na , K, Rb, and Cs) are very metallic and their atoms tend to lose their electrical neutrality,
becoming ions with one positive charge. The halogens are very non-metallic and their atoms form ions with a
negative charge each. Elements in vertical columns [groups] have similar characteristics while those in rows
[periods] have characteristics that grade from left to right due to the electronic configurations of the outer levels
of their atoms.
* Elements on the left side are metals and attain a stable octet by giving up electrons and becoming positive
charges. Those on the right side are called non-metals and attain a stable octet by gaining electrons and
becoming negative ions.
* When a metal atom and a nonmetal atom are brought together, the metal atoms gives up one or more electrons
which the nonmetal accepts and the resulting oppositely charged ions are held together by a strong electrostatic
force called the ionic bond. Elements on opposite sides of the periodic table form ionic crystals & the farther
apart they’re, the more ionic character will the bond be e.g. KCl, NaF. In ionic bonds, the attractive forces are
exerted in all directions so that every cation is surrounded by anions and vice versa hence resulting into closely
packed crystal structures with the total number of positive charges in the in the crystal equal to the total number
of negative charges. Such ionic crystals are poor conductors but dissolve in water to form ions.
* When metal atoms are brought together, neither holds the outer electrons strongly, so a metallic crystal is
formed with free electrons moving among the atoms (metallic bond). A metallic bond binds together atoms of
metallic elements i.e. the first, second and third groups of the periodic table as well as the transition elements. In
metallic crystals, atoms are packed together tightly, but the outer electrons are attached to no atom in particular
hence are free to move through the structure. The metallic bond imparts certain very distinct characteristics to
the crystals.
The atoms in metal crystals are packed together to occupy the maximum amount of space hence resulting
into 3 common metal structures: the face-centered cubic (as in copper), the close-packed hexagonal (as in zinc,
representing the most dense packing possible) & the body-centered cubic (as in iron, that’s only slightly less
dense).
Because the free electrons can move thru the structure, an electric potential or heat applied across the
crystal results in high electrical & thermal conductivity.
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Likewise, metallic crystals are ductile and malleable because shearing forces applied to them cause
gliding along atomic planes without brittle fracture.
Metallic luster and opacity are caused by interaction of light with the free electrons. However, there are
few metallic crystals in the crust of the earth because metals easily lose their outer electrons and there are
abundant nonmetals available to accept them e.g. oxygen & sulphur hence metal oxides and sulphides are
common minerals.
* If non metal atoms are brought together, both atoms attract extra electrons strongly by sharing their outer
electrons thereby forming free neutral molecules with a covalent bond.
Note: Atoms that form covalent bonds with other atoms will participate in the formation of crystals of five types,
depending on the number of covalent bonds the atoms can form:
i) Molecular crystals, consisting of distinct covalently bonded molecules held together by van-der-waals forces
[very weak forces due to small residual charges on the surface of the molecules ] e.g. solidified gases like CO 2,
chlorine and many organic compounds.
ii) Ionic crystals are formed by complex ions that are held together by covalent bonds and carry charges e.g.
[ NH4]+1 & CO3-2 are covalent and are bonded to Cl- & Ca2+ by ionic forces in NH4Cl (sal ammoniac) and CaCO3
(calcite).
iii) Crystals with chain structures (like in the semimetals- selenium and tellurium) have atoms linked together
with covalent bonds in infinite chains. The chains are held together by van der waals and metallic bonding
forces.
iv) Crystals with sheet structures have atoms linked together with covalent bonds in infinite layers . The layers
are held together by van der waals forces e.g. graphite.
v) Crystals with frame work structures form if an atom can share electrons with four adjacent atoms . e.g.
diamond . Bonding is infinite in all three dimensions and the crystal can be considered a molecule of infinite
size.
Since covalent bonds are very strong, their distribution determines the characteristics of a crystal. e.g. it explains
the splitting of graphite into flaky layers, the hardness of diamond, the low melting point of dry ice, poor
conduction in sulphur and the formation of complex ions in solution like NH 4+& HCO3-1
* When semimetals are brought together, their atoms form crystals that have properties between metals and non
metals with an intermediate bond. Intermediate bonds lie between the 3 extremes represented by metallic,
covalent and ionic bonds.
Crystals having chemical bonding intermediate between covalent and metallic (in the central part of the periodic
table) are particularly important in solid state electronics e.g. silicon is a semi-conductor [conducts electricity
only above a certain voltage, when doped with small impurities and in only one direction which makes silicon
useful in transistors. Therefore, bond types should be understood clearly since the physical and chemical
behaviour of minerals is directly related to the bond type.
* Transition metals are chemically similar to other metals in the same period. Their outer levels have about the
same electronic configuration but their inner levels differ.
* The hydrogen bond is a special bond formed only between the hydrogen atom and other atoms. It’s a weak
polar bond. In minerals, the hydrogen bond is virtually limited to compounds containing the water molecule
(hydrated compounds) or the hydroxyl ion (OH-1) - hydrous compounds. The effects of water and hydroxyl ion
on the mineral structure are pronounced . Their absence or presence in minerals is due to varying conditions of
formation and provides valuable clues to geologic environments. The hydrogen bond is the force that holds water
molecules together as ice and it contributes to bonding in any hydrous mineral.
- Crystals have always been of great interest because of their intrinsic beauty. To mineralogists, they also provide
clues to the arrangement of atoms within a mineral and offer an important means of mineral identification. Only a
few minerals such as opal and silica glass lack a crystal structure.

Chemical bonds in crystals and their influence on physical properties

The forces that bind atoms into crystalline solids are electrical in nature. These binding forces are
known as chemical bonds. To a great extent, the bonding type and strength determines the physical and chemical
properties of minerals. Hardness, cleavage, thermal and electrical conductivity, etc. are directly related to
chemical bonds. There are five principal bond types: Covalent, ionic, metallic, van der Waals, and hydrogen
bonding.
• Covalent bond is the strongest of the chemical bonds. Minerals with covalent bonds are usually
insoluble, very stable, have very high melting points, and non conductive.
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• Minerals with ionic bonds usually have moderate hardness, high melting point, poor conductors,
due to the stability of ions.
• Minerals with metallic bonds are usually soft, malleable, and highly conductive.
• The hydrogen bond is weaker than ionic or covalent bonding, but considerably stronger than the van der Waals
bond. Hydrogen bonding is common in hydroxides. It also occurs in some layer silicates containing hydroxyl
groups.
• The van der Waals bond is the weakest of the chemical bonds.

Formation of minerals:
Minerals can form by any of the following processes:
- Precipitation from a fluid like H2O or CO2.  This can take place within the Earth by hydrothermal
processes, diagenesis, and metamorphism, and at or near the Earth's surface as a result of evaporation,
weathering, or biological activity.
- Sublimation from a vapor.  This process is somewhat more rare, but can take place at a volcanic vent, or
deep in space where the pressure is near vacuum.
- Crystallization from a liquid.  This takes place during crystallization of molten rock (magma/lava) either
below or at the Earth's surface.
- Solid - Solid reactions.  This process involves minerals reacting with other minerals in the solid state to
produce one or more new minerals.  Such processes take place during metamorphism and diagenesis due
to changing temperature and pressure conditions.
- Oxidation and weathering of rocks exposed to the atmosphere or within the soil environment.
Thus, the processes of mineral formation and growth are highly varied.
No matter what process is involved, a particular mineral cannot form unless the chemical ingredients necessary to
make the mineral are present.  Thus, the most common minerals are minerals that have a chemical composition
made of the common elements found in their environment.  Since the environment where most observable
minerals occur is the Earth's crust, we must first explore the chemical composition of the Earth's crust.

Composition of the Earth crust:

Geophysical studies have revealed that the Earth has a layered structure. Major layers are the
crust, the mantle and the core. The crust is where we can directly get samples from, both through
fieldwork and through deep sea drilling projects. Geochemical investigations have determined
that the crust contains all the naturally-occurring elements in the periodic table. However, 99
weight percent of the crust is made of eight elements: O, Si, Al, Fe, Ca, Na, K, and Mg. Oxygen
and Silicon are the most dominant elements in the crust. The crust consists almost entirely of
oxygen compounds, especially silicates but also oxides and carbonates.
Thus, the Earth's crust is made up of about 95% igneous and metamorphic rocks, 5% sedimentary rocks (4%
shale, 0.75% sandstone, and 0.25% limestone).  The continental crust has an average composition that
approximates granodiorite (a medium grained siliceous igneous rock), whereas the oceanic crust has an average
composition that is basaltic (a basic igneous rock). Based on information compiled by Clarke  and Washington in
1924, the average composition of the continental crust is as follows:

Element Wt% Atomic%

O 46.60 62.55
Si 27.72 21.22
Al   8.13   6.47
Fe   5.00   1.92
Ca   3.63   1.94
Na   2.83   2.34
K   2.59   1.42
Mg   2.09   1.84
Total 98.59 100.00
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Note that 8 elements make up over 98% of the Earth's crust and that Oxygen is the most abundant element.  This
becomes even more evident if the elements are determined on an atomic basis, where we can see that about 63
out of every 100 atoms in the crust are Oxygen. 
Because of the average composition of the crust, the most common minerals found in the crust are silicates and
oxides.  Of the silicates, the aluminosilicates, like the feldspars and clay minerals are the most common.
Other minerals, containing the other elements in the periodic table are found in the crust.  But, in order for these
minerals to occur, special geologic conditions are necessary to concentrate these less abundant elements so that
they occur in high enough concentrations to form a separate mineral. 
Elements that occur in concentrations less than about 0.1% (usually measured in parts per million or parts per
billion) are called trace elements [or dispersed elements]. A complete listing of the abundances of all elements in
the Earth's crust can be found at http://www.science.co.il/PTelements.asp?s=Earth

Mineral Occurrences and Environments In

addition to physical properties, one of the most diagnostic features of a mineral is the geological environment in
which it is occurs. Learning to recognize different types of geological environments can thus be very helpful in
recognizing the common minerals. Note that geologic environments are diverse! However, for the purposes of
aiding mineral identification, we have developed a very rough classification of geological environments as:

1. Igneous: Minerals in igneous rocks must have high melting points and be able to co-exist with, or crystallize
from, silicate melts at temperatures above 800 º C. Igneous rocks can be generally classed according to their
silica content with low-silica (<< 50 % SiO 2) igneous rocks being termed basic or mafic, and high-silica igneous
rocks being termed silicic or acidic. Basic igneous rocks (BIR) include basalts, dolerites, gabbros, kimberlites,
and peridotites, and abundant minerals in such rocks include olivine, pyroxenes, Ca-feldspar (plagioclase),
amphiboles, and biotite. The abundance of Fe in these rocks causes them to be dark-colored. Silicic igneous rocks
(SIR) include granites, granodiorites, and rhyolites, and abundant minerals include quartz, muscovite, and alkali
feldspars. These are commonly light-colored although color is not always diagnostic. In addition to basic and
silicic igneous rocks, a third igneous mineral environment representing the final stages of igneous fractionation is
called a pegmatite (PEG) which is typically very coarse-grained and similar in composition to silicic igneous
rocks (i.e. high in silica). Elements that do not readily substitute into the abundant minerals are called
incompatible elements, and these typically accumulate to form their own minerals in pegmatites. Minerals
containing the incompatible elements, Li, Be, B, P, Rb, Sr, Y, Nb, rare earths (lanthanides), Cs, and Ta are typical
and characteristic of pegmatites.

2. Metamorphic: Minerals in metamorphic rocks have crystallized from other minerals rather than from melts
and need not be stable to such high temperatures as igneous minerals. In a very general way, metamorphic
environments may be classified as low-grade metamorphic (LGM) (temperatures of 60 º to 400 º C and pressures
<< .5 GPa (=15km depth) and high-grade meta morphic (HGM) (temperatures > 400 º and/or pressures > .5GPa).
Minerals characteristic of low- grade metamorphic environments include the zeolites, chlorites, and andalusite.
Minerals character istic of high grade metamorphic environments include sillimanite, kyanite, staurolite, and
amphiboles.

3. Sedimentary: Minerals in sedimentary rocks are either stable in low-temperature hydrous environments (e.g.
clays) or are high temperature minerals that are extremely resistant to chemical weathering (e.g. quartz). One can
think of sedimentary minerals as exhibiting a range of solubilities so that the most insoluble minerals such as
quartz, gold, and diamond accumulate in the coarsest detrital sedimentary rocks, less resistant minerals such as
feldspars, which weather to clays, accumulate in finer grained siltstones and mudstones, and the most soluble
minerals such as calcite and halite (rock-salt) are chemically precipitated in evaporite deposits. Accordingly, I
would classify sedimentary minerals into detrital sediments (DSD) and evaporites (EVP). Detrital sedimentary
minerals include quartz, gold, diamond, apatite and other phosphates, calcite, and clays. Evaporite sedimentary
minerals include calcite, gypsum, anhydrite, halite and sylvite, plus some of the borate minerals.

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4. Hydrothermal: The fourth major mineral environment is hydrothermal and includes minerals precipitated
from hot aqueous solutions associated with emplacement of intrusive igneous rocks. This environment is
commonly grouped with metamorphic environments, but the minerals that form by this process and the elements
that they contain are so distinct from contact or regional metamorphic rocks that it is useful to consider them as a
separate group. These may be sub-classified as high temperature hydrothermal (HTH), low temperature
hydrothermal (LTH), and oxydized hydrothermal (OXH). Metals of the center and right-hand side of the periodic
table (e.g. Cu, Zn, Sb, As, Pb, Sn, Cd, Hg, Ag) most commonly occur in sulfide minerals and are termed the
chalcophile elements. Sulfides may occur in igneous and metamorphic rocks, but are most typically
hydrothermal. High temperature hydrothermal minerals include gold, silver, tungstate minerals, chalcopyrite,
bornite, the tellurides, and molybdenite. Low temperature hydrothermal minerals include barite, gold, cinnabar,
pyrite, and cassiterite. Sulfide minerals are not stable in atmospheric oxygen and will weather by oxidation to
form oxides, sulfates and carbonates of the chalcophile metals, and these minerals are characteristic of oxidized
hydrothermal deposits. Such deposits are called gossans and are marked by yellow-red iron oxide stains on rock
surfaces. These usually mark mineralized zones at depth and are very common in Busia gold field (eastern
Uganda) & Colorado (U.S.A).

Flush back! 
The origin of the chemical elements:
The Universe that we perceive is thought to have begun in a "Big Bang" approximately 15 billion years ago. This
cosmic explosion produced among other particles, protons, neutrons, and electrons which rapidly became
organized into the elements hydrogen (1 proton, 1 electron), and helium (2 protons, 2 neutrons, and 2 electrons),
plus trace amounts of deuterium (1 proton,1 neutron, and 1 electron), 3He (2 protons, 1 neutron, 2 electrons),
and lithium (3 protons, 3 neutrons, 3 electrons). Most of the mass of this primordial material is carried in the
protons and neutrons (baryons).
As the gas of these primitive elements expanded, gravitational instabilities caused parts to
coalesce into huge clouds that eventually became galaxies and clusters of galaxies. Further, gravitational
instabilities within each galaxy caused further collapse of the gas into primitive stars where the very high
temperatures caused by gravitational collapse ignited the fires of thermonuclear fusion in which the nuclei of the
primitive light elements combined to form heavier elements. In the largest of these stars, the fusion reactions
proceeded in stages producing successively heavier elements. The final reaction in which Si combines to form Fe
proceeds so rapidly once ignited that the star explodes in what we call a supernova. Our own solar system
coalesced from the remnants of one or more of these supernova explosions.
As the gas that formed our solar system collapsed from gravitation it formed a rotating disk of gas that first
heated and then cooled. As the gas cooled the heavy elements began to precipitate solid particles of dust. The
first precipitates were crystals (minerals) of platinum-group metals, Os, Ru, and Ir, followed by aluminum
oxides, metallic nickel-iron, and Mg silicates. This was followed by more complex silicates, then various sulfides
of heavy metals. We can see this precipitation sequence preserved in primitive meteorites. Before temperatures
cooled sufficiently in the inner solar system so that the most volatile elements (H, C, N, and the noble gases)
could condense, H fusion in the sun ignited and blew these elements to the outer solar system where they are
enriched in the outer planets, Jupiter, Saturn, Uranus, and Neptune. The Earth accreted from these early
solid particles called chondrules, and these refractory elements are enriched in the Earth relative to their
abundance in the Sun. As the proto Earth grew from the influx of solid particles it got hot enough to melt so that
the dense Ni-Fe metal together with elements soluble in the metal sank to the center and formed the core, and the
lighter oxygen-bearing minerals (mostly silicates) formed the mantle. Today the lower mantle is entirely solid
and has been throughout most of Earth's history, whereas the core comprises a liquid metal outer core and a
solid metal inner core. So, except for the oceans and atmosphere, the Earth
today is made up of solid minerals to a depth of about 2900 km. The physics and chemistry of the solid phases of
the Earth control much of the physics and chemistry of our environment. Unlike fluids, minerals preserve the
records of Earth's history. Further minerals contain the wealth of natural resources of the planet. Therefore
understanding the physics and chemistry of the solid materials of the earth (mineralogy) is central to much of the
Earth Sciences.

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COMPOSITIONAL VARIATION IN MINERALS:

Very few minerals occur as pure substances. In nature, most minerals display extensive variation in chemical
composition, usually resulting from substitution of an ion or ionic group in a given structure by another ion or
ionic group. This is termed ionic substitution or solid solution and it’s more common in isostructural minerals
(those related to each other by analogous [similar] structures & having a common anion) such as aragonite &
calcite groups of carbonates & barite group of minerals from sulphates; stishovite (SiO2) & rutile (TiO2) are both
tetragonal and in both, the cation (Si 4+, Ti4+) is surrounded by 6 oxygens in octahedral packing. Such ionic
substitution is dependent on 3 factors:
a) Comparative sizes of the ions, atoms or ionic groups substituting for each other; in which case the difference
in their sizes should be about 15 % but if it’s >30 %, very little substitution is likely. If the radii of the two
elements differ by 15- 30 % substitution is rare or limited e.g. Mg 2+ & Fe2+.
b) Charges of ions involved in substitution; should be the same so that the structure remains electrically neutral
after replacement e.g. if Al 3+ is to substitute for Si 4+ (as in Cristobalite, the high temperature form of SiO 2),
more substitution in the crystal (in form of Na + occupying large openings in the cristobalite lattice) should
take place elsewhere in the structure to obtain overall electrical neutrality in the structure involved.
c) Temperature of substitution; should preferably be higher since greater thermal vibrations in the structure
favour larger available atomic sites.

The property of increased atomic substitution at higher temperatures provides a means of determining the
temperature of mineral formation (geological thermometry). If for a specific mineral the degree of atomic
substitution has been determined for different temperatures, the composition of the naturally occurring mineral
may indicate the temperature of formation. Thus the amount of titanium in solid solution (in magnetite) as a
function of temperature is known from laboratory investigations. Magnetite is a common ore mineral. Provided
the ore-forming solutions contained enough titanium to saturate the magnetite, the titanium content of the mineral
will indicate the temperature conditions during ore formation.
Diadochy describes the ability of different elements to occupy the same lattice position in a crystal e.g. Mg, Fe &
Mn are diadochic in the dolomite structure.

SOLID SOLUTION:
Minerals are commonly thought of in terms of a simple chemical formular that’s fixed and unchangeable.
Forsterite, for example, is Mg2SiO4; anhydrite, CaSO4. These formulae, however, rarely express the exact
chemical compositions; they are only approximations. Compositions of most minerals are not fixed, but vary
between definite limits. This variation is referred to as solid solution or diadochy.
In a crystal, an element occupies a particular position because of its characteristics, notably the size of its ion or
the type of chemical bonding. Many elements have atoms with electronic configurations similar to those of other
elements and so are chemically similar hence either element may be stable in the same structural position. In
silicates, for example, the position occupied by the silicon ion may also be occupied by the aluminium ion,
which is nearly the same size and has the same electronic configuration. But it is important to remember that the
proportion of silicon and aluminium in this position is not fixed, but depends on how much of each element was
present during the mineral’s crystallization. Similarly, magnesium [Mg] and iron [Fe] may be present in a
number of minerals in identical positions, and the Mg:Fe ratio may have any value. Regardless of the Mg:Fe
ratio, however, the crystal structures of minerals with variable amounts of Mg and Fe are essentially identical.
The elements of Mg and Fe are said to be ‘substituting’ for one another in the structure. Minerals with identical
structures, but with differing chemical compositions are said to be isomorphous.
Solid solution can be:
 a complete reaction as in olivines, cordierites & amphiboles;
 limited as in alkali feldspars, sulphates (anhydrite and barite), pyroxenes or
 coupled as in feldspars (sodic and calcic), melilites, plagioclase feldspars.

COMPLETE SOLID SOLUTION occurs when two elements can substitute for one another completely in a
mineral. Olivines are excellent examples of this type of solid solution. Forsterite, Mg 2SiO4, and fayalite, Fe2SiO4,
have identical structures because the ions Mg 2+ and Fe2+ are very nearly the same size and are chemically similar.
If both iron and magnesium are present in the environment of crystallization, a single mineral with a composition
intermediate between forsterite & fayalite will form. This mineral is considered to be a ‘solution’ of fayalite in

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forsterite. Because minerals with all possible intermediate compositions can be formed, the formula is written
(Mg,Fe) 2SiO4, and the general name, regardless of Mg:Fe ratio, is olivine. The olivines are referred to as
members of a complete solid solution series between the Mg end member, forsterite, and the Fe end member,
fayalite. Mg-rich olivines are light green, and Fe-rich olivines are dark green or black. Olivines with intermediate
compositions are intermediate in color. Their other physical characteristics also vary between those of the end
members. In such minerals, either pure end member is seldom found, though they may be synthesized in the
laboratory. Solid solution may be complete if substituting ions are nearly the same size and are chemically
similar. If substituting ions are much larger or smaller, the structure is distorted and weakened hence, only
limited substitution is possible. The limits of solid solution increase with increasing temperature. Solid solutions
of certain compositions, as 50-50, tend to order. These order crystals have properties like compounds rather than
intermediates. Disordered solid solutions have properties intermediate between those of the end members.

LIMITED SOLID SOLUTION occurs in a mineral when two elements that substitute for one another do not
form all possible proportions. Solid solution in the olivines is complete because iron & magnesium ions are
nearly the same size. But in many other minerals, only limited amounts of one ion can substitute for another
because the two ions are of different sizes. Anhydrite , CaSO 4, & barite , BaSO 4 , are chemically similar , but
have different structures because the Ba +2 ion is considerably larger than the Ca +2 ion. Chemical analyses ,
nevertheless , show that anhydrite can contain up to 8% BaSO 4 , and barite can contain up to 6% CaSO 4 .
Substitution of more ions cannot take place without disrupting the structure at either end of the series. The
amount of solid solution is thus limited to narrow ranges of composition at each end . Similarly , potassium
feldspar (KAlSi3O8) and sodium feldspar (NaAlSi 3O8) don’t form complete solid solutions except at high temps.
To sum up, the extent of solid solution is governed by the relative sizes and chemical similarly of the substituting
elements and by the temp.

COUPLED SUBSTITUTION involves simultaneous substitutions that balance one another . It results in a more
complex type of solid solution, either complete or limited , that occurs in the some minerals . The feldspars are
an example. Calcium feldspar (anorthite , CaAl 2Si2O8) and sodium feldspar (albite, NaAlSi 3O8) have the same
basic structure . The calcium ions (Ca+2) in calcium feldspar are in the same positions as the sodium ions (Na +) in
sodium feldspar yet the aluminum ions (Al +3) and silicon ions (Si+4) occupy identical positions in both minerals ,
but occur in different proportions. Because the Ca +2 ion and Na+ ion are nearly the same size and can substitute
for each other, a complete solid solution series is possible between the two minerals. But b’se Ca +2 and Na+ have
different charges, the substitution of one for the other would unbalance the neutrality of the overall structure and
could therefore not occur . It becomes possible, however, because Al +3 and Si+4 can also substitute for one another
. When both substitutions occur simultaneously neutrality is maintained. The “ exchange” can be written Ca +2 +
Al+3: Na+ + Si+4 i.e. 5 charges replacing 5 charges . Feldspars with all possible Ca:Na ratios can be found , with
the Al:Si ratio varying accordingly . Members of this complete solid solution series are all similar in appearance
& are called plagioclase feldspars.
Solid solution is important in the following minerals:
- OLIVINES- Substitution of Mg+2, Fe+2 and Mn+2
Forsterite – Fayalite: Mg2SiO4-Fe2SiO4 (complete)
Forsterite- Tephroite: Mg2SiO4- Mn2SiO4 (complete)
- CORDIERITES- Substitution of Fe+2 for Mg+2
18 (complete)
Cordierite – Iron Cordierite : Mg Al (Si Al)O - Fe Al (Si Al)O
2 3 5 18 2 3 3
+4 +2 +3
- MELILITES – coupled substitution of Si + Mg for 2Al
Gehlenite –Akermanite: Ca2Al(SiAl)O7- Ca2 MgSi2O7 (complete)
- PYROXENES- substitution of Mg+2 & Fe+2
Diopside –Hedenbergite : CaMg(SiO 3)2 – CaFe(SiO3)2 (complete) but Ca:(Mg ,Fe) varies over limited
range
Intermediate compositions are called pigeonite.
Augite is intermediate but has Al+3 in composition.
+2 +2
- AMPHIBOLES – substitution of Mg & Fe (complete)
Tremolite –Ferroactinolite : Ca2Mg5 (Si8O12)(OH) 2- Ca2Fe5(Si8O12)(OH)2 (Complete)
Intermediate compositions are called ferrotremolite, tremolite-actinolite, or simply actinolite
+2 +3
- MICAS- Coupled substitution of 3Fe for 2Al + a vacancy

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Muscovite-Annite: KAl2(Si3Al)O10(OH) 2- KFe3(Si3Al)O10(OH) 2

Biotite is K(Mg,Fe)3(Si3Al)O10(OH) 2 with Mg:Fe less than 2:1
Phlogpite is K(Mg,Fe3(Si3Al)O10(OH) 2 with Mg:Fe greater than 2:1
- PLAGIOCLASE FELDSPARS – coupled substitution of Ca + Al for Na + Si
+2 +3 + +4

Albite–anorthite: NaAlSi3O8 - CaAl2Si2O8 (complete) but intermediate compositions are called plagioclase.
- ALKALI FELDSPARS – Substitution of K & Na
+ +

Microcline (sanidine) – Albite: KAlSi 3O8 - NaAlSi3O8 (Complete above about 670°C). However, at ordinary
temperatures there’s about 20% substitution of Na+ in microcline and about 5% substitution of K + in Albite).

Solid solution (ionic substitution) is defined as a mineral structure in which specific atomic site(s) are occupied
in variable proportions by two or more different chemical elements (or groups). In some cases, solid solutions
are termed as mixed crystals, which implies the presence of molecules of two or more substances in a single
homogenous crystal i.e. homogenous crystalline solids of variable composition. For example olivine is a solid
solution of Mg2SiO4 (forsiterite;Fo) and Fe2SiO4 (fayalite;Fa) and hence the precise composition of any sample of
olivine may be stated in terms of these end- members such as Fo 85Fa15 i.e. (Mg0.85Fe0.15)2SiO4. Similarly, in the
plagioclase series [albite (NaAlSi 3O8) to anorthite (CaAl2Si2O8)], Ca2+ substitutes for Na+ and electrical
neutrality is maintained by the coupled substitution of Al 3+ for Si4+. Even in diopside (CaMgSi2O6), Mg2+ & Si4+
may be replaced in part by Al3+ &Al3+ respectively. The amphibole group also shows extensive solid solution
between its members. Such coupled substitutions are common in silicate minerals and made the interpretation of
their composition exceedingly difficult before this phenomenon was recognised and understood.
There are 3 main types of solid solution i.e. substitutional, interstitial & omission but each of these could be
limited, complete or coupled.

1. Substitutional solid solution may be of 3 different kinds:

a) Simple cationic:
e.g. Rb+ = K+ (in KCl or biotite)
Mg2+ = Fe2+ (complete) Mg2+(6)=0.72A
Fe = Mn (complete)
2+ 2+
Fe2+(6)=0.78A
Na+ = K+ (partial) Mn2+(6)=0.83A
Mg = Mn (partial)
2+ 2+
Na+(8)=1.18A
K+(8)=1.51A

b) Simple anionic:
Br- = Cl- (complete) Br-(6)=1.96A
I- = Cl- (partial) Cl (6)=1.81A
-

I-(6)=2.20A

Thus, complete binary solid solution i.e. replacement of one element by another over possible compositional
range may occur among cationic series like in olivine [Forsiterite (Mg 2SiO4) = Fayalite(Fe2SiO4)] and in
carbonates [rhodochrosite (MnCO3) = siderite (FeCO3)] or among anionic series like KCl = KBr in several
minerals. Hence simple cationic or anionic substitution may be recognised in minerals as illustrated in the
reactions above.

c) Coupled cationic:
The extent of solid solution is:
- Complete at high temperatures as in plagioclase i.e.
Na+Si4+ (albite) = Ca2+Al3+ (anorthite);
- Limited as in the pyroxene group (e.g. omphacite) i.e.
Ca2+Mg2+ (diopside) = Na+Al3+ (jaedite);
- Extensive as in:
i) spinel group i.e. Mg2+Al23+ = Fe22+Ti4+
ii) Amphibole group as in arfvedsonite and tremolite i.e.
Si4+ = Na+Al3+

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Crystal structure investigations have also revealed two other types of solid solution besides that due to atomic or
ionic substitution (whereby atoms or ions replace atoms or ions in the structure). These are:

2 Interstitial solid solution: This occurs when atoms/ions/ionic groups fit into interstices (or voids) in the lattice
of a given structure. It’s very common in metals that take up small atoms like hydrogen, carbon, boron and
nitrogen. For substances with an open structure, it may take place even with atoms/ions of considerable size e.g.
in crystobalite where Al3+ replaces Si4+ while Na+ occupies large openings in the lattice to maintain electrical
neutrality. In Beryl (Be3Al2Si6O18), the channel-like cavities can accommodate K +, Rb+, Cs+, H2O, and CO2. The
zeolites accommodate water molecules by hydrogen bonding to the Al-Si framework, which may be removed by
heating.

3. Omission solid solution:

This is associated with defect lattices, in which some of the atoms are missing, leaving vacant lattice positions.
Here, a highly charged cation replaces two or more other cations for charge balance; usually in one atomic site
leaving the others vacant or omitted. Examples are:
i) In amazonite (blue-green variety of microcline, KAlSi 3O8), Pb2+ substitutes for two K= but occupies only one
creating a lattice vacancy , which becomes a color centre i.e. 2K + = 2Pb2+ +
ii) Pyrrhotite Fe(1-x)S [x = 0-0.2]; Here particular structural site is incompletely filled i.e. Fe 2+ is absent and hence
some Fe is in form of Fe3+ to compensate for the deficiency of Fe 2+ i.e. 3Fe2+ = 2Fe3+ + , which creates a
vacancy.
iii) Maghemite (-Fe2O3) is Fe-deficient spinel and it’s an oxidation product of magnetite.

IMPORTANCE OF SOLID SOLUTION

Solid solution is great because most minerals exhibit it at least to a limited extent.
Variations in composition 1provide valuable clues to temperaturess and chemical environments during formation .
Solid solution 2explains why some elements are nearly always found in trace amounts in minerals and there by
“camouflaged.”
Analyses of trace elements in rocks 3can lead to the discovery of concentrations of valuable elements in other
nearby rocks.

Exsolution: Is a process whereby an initially homogenous solid solution seperates into two (or possibly more)
distinct crystalline minerals without addition or removal of material to or from the system [i.e no change in bulk
composition]. Complete solid solution can be achieved at high temperatures in the alkali (K-Na) feldspar series
i.e. NaAlSi3O8 & KAlSi3O8 and also between the pyroxenes, between the amphiboles (e.g. cummingtonite
lamellae in glaucophane host) and between the iron oxides.
As mentioned above, the extent of solid solution is sometimes dependent on temperature and pressure since the
sizes of ions and the sizes of the crystallographic sites can change with temperature and pressure.   Thus, some
minerals show complete solid solution under one set of temperature/pressure conditions, and only limited solid
solution under different temperature/pressure conditions. When the conditions change to those where limited
solid solution is favored, the mineral exsolves or unmixes.  But, because the process is taking place in the solid
state, exsolution or unmixing cannot easily form two separate phases, because the ions must diffuse through the
solid.  In fact, what happens is that two separate phases form in discrete domains within a single mineral grain.  
These domains are crystallographically oriented, so they appear as lamellae [or lines across the mineral grain].
- Perthite is where the Na-rich feldspar (albite) lamellae are exsolved from the K-rich host
(microcline/orthoclase). In the case of perthite, the exsolution lamellae are often large enough to see with the
naked eye.  In other systems, the exsolution lamellae can only be observed with either a petrographic microscope
hence termed microperthite or XRD thus termed cryptoperthite.
- The scale of exsolution lamellae is a good indicator of the cooling rate of the rock in which this intergrowth
texture occurs. Hence slowly cooled rocks have coarser exsolution textures while in extremely quickly cooled
(quenched) rocks, the high temperature, homogenous, dissolved mineral may be preserved in a metastable state
yet in slower (rapid) cooling, very fine exsolution textures may develop.

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ISOMORPHISM
Is a phenomenon applied to substances with analogous formulas having closely related crystal structures. Its
based on the fact that anions and cations of the relative sizes (same coordnation) and in the same numbers tend to
crystallize in the same structural type. C.f . isostructural or isotypic. Isomophous minerals include:
- the spinel group,
- the garnet group
- the amphibole group.
- anhydrous carbonates of bivalent elements [which form 2 isomophous groups i.e. orthorhombic (minerals
with cations greater than calcium) & trigonal ( minerals with cations smaller than calcium). Calcite can
crystallize in either structure and hence polymorphic.
- Soda niter (NaNO3) is isomophous with calcite CaCO3
- niter ( KNO3) is isomophous with aragonite CaCO3;
- Berlinite (AlPO4) with quartz (SiSiO4);
- tantalite (FeTa2O6) with brookite [TiO2(TiTi2O6];
- forsterite Mg2SiO4 with fayalite Fe2SiO4;
- Halite NaCl – sylvite KCl;
- periclase MgO & galena PbS;
- gold Au & silver Hg;
- quartz SiO2 & berlinite AlPO4;
- muscovite & biotite; e.t.c.
The important factor in isomorphism is the similarity in size relations of the different ions rather than any
chemical similarity.
Sometimes there may be crystalline solution (solid solution) but sometimes not!
Therefore, minerals with same structure and different compositions are isomorphs.

Polymorphism is where an element or compound can exist in more than one crystal form. Such substances have
different physical properties and crystal structures but the same composition.
Two minerals with the same composition but different structures are different minerals for example:
- diamond and graphite are both pure carbon but are different minerals.
- Quartz, tridymite, cristobalite, coesite & stishovite are all polymorphs of silica (SiO2).
- Calcite & aragonite are both CaCO3.
This is why we use mineral names rather than chemical formulars.
Different polymorphs of the same substance are formed under different conditions of pressure , temperature and
chemical environment. Hence, the presence of one polymorph in a rock will often tell something about the
conditions under which the rock was formed e.g. marcasite can only be formed from acid solutions at temps
below 450 degrees centigrade hence the presence of marcasite in a deposit thus puts some limits on the conditions
of origin.
Polymorphs are distinguished according to whether the change from one form to another is reversible and takes
place at definite temp and pressure:
*Enantiotropy e.g. quartz ↔Tridymite & diamond ↔graphite or
*Monotropy e.g. marcasite → pyrite.
The natural occurrence of diamond in igneous rocks implies an origin at considerable depths in the earth where
the temp & pressure is with in the diamond stability field. The high temp polymorphs of a substance is usually
more open –packed than a low temp form. High pressures compact structures.
In conclusion, isomorphs have same structure but different composition while polymorphs have same
composition but different structure.

*Read about the analytical techniques used in the chemical analysis of minerals.

Some Methods of Chemical Analysis

While the common minerals are made up mostly of the abundant elements in the Crust, and we can
express the chemical composition of such minerals by a simple (and sometimes not so simple) chemical
formula, all minerals exhibit some chemical variation.  In fact pure minerals (those with a chemical

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composition exactly the same as the chemical formula) are rarely found in nature.  For now, it is
sufficient to say that if we had a technique for measuring even the smallest concentrations of elements,
we would see that any given mineral probably contains every stable element in the periodic table.   Of
course most of these elements would occur in very low concentrations (parts per million; ppm: [10 -6] or
parts per billion; ppb: [10-9] or parts per trillion [10-12]), nevertheless they are present. 
Various methods have been used to perform chemical analyses of rocks and minerals.  We will discuss
some of these techniques here. 
Chemical tests and blow–pipe analyses are time–honored aids in mineral identification but require
detailed explanation to be useful and are therefore not included here but read about them.

Analysis of minerals is quite different from analysis of rocks.  Chemical analysis of rocks involves
analyzing an aggregate (group) of minerals.  So, in most cases, the rock can be ground to a fine powder
and subjected to one of the methods discussed here.  Analysis of a mineral is more complicated because:

1. Individual minerals are much smaller than rocks and it is therefore difficult to obtain enough
sample of a mineral to perform the chemical analysis.
2. In cases where a single mineral is too small to provide enough sample, several grains of the
same mineral can be separated from a rock and analyzed as a single sample.  But, this involves
extensive work in separating the mineral from all other minerals, and still does not tell us if there
is any chemical variability between individual grains.  (The electron microprobe technique
described below is an exception, because it allows for analysis of small areas of single grains).
3. Individual minerals may be chemically zoned.  That is there may be differences in the chemical
composition of the mineral from its center to its rim.  Chemical analysis of single mineral grains
or aggregates of mineral grains will not reveal this chemical zonation.  (Again, the electron
microprobe technique is an exception).

Here we discuss only the more commonly used methods of mineral analysis.
Wet Chemical Analyses: Prior to about 1960 classical wet chemical analysis was the only means of
determining the chemical composition of minerals.  Such analyses were limited by the factors discussed
above in terms of sampling size, although techniques were developed for analyzing very small samples. 

Wet chemical analysis always involves dissolving the mineral into an acidic solution.  In order for the
dissolution to take place completely, the mineral is usually first ground into a fine powder (to increase
surface area) and the appropriate acid must be used.  Wet chemical analysis  can be classified into three
different types:

 Gravimetric Analyses- In this case the element of interest is precipitated as a compound.  The
precipitate is then weighed to determine its proportion in the original sample.

 Volumetric Analyses - In this type of analysis, titration is used to determine the amount of
reagent that is added in order for a specific chemical reaction to occur that involves the element
of interest.  From the volume of reagent added, the concentration of the element can be
calculated. 
 Colorimetric Analyses - A reagent is added to the solution that reacts with the element of interest
to produce a color change in the solution.  The intensity of the color is proportional to the
concentration of the element of interest, and thus when compared to standard solutions in which
the concentration is known, the concentration of the element in the unknown solution can be
determined.

Generally all elements cannot be determined by the same wet chemical methods and different methods
are more sensitive for different elements.  Thus, complete wet chemical analysis usually involves a
combination of methods.  Wet chemical analyses require a skilled analytical chemist, and are usually
very time consuming.
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Inductively Coupled Plasma - Mass Spectrometry (ICP-MS) 

ICP-MS combines two instruments, an inductively coupled plasma spectrometer and a mass
spectrometer to simultaneously measure most elements in the periodic table and determine concentration
down to the sub part-per trillion (ppt) level. The sample of mineral or rock must first be powdered and
put into solution in acid.  This solution is then injected into a plasma as an aerosol where the atoms in the
sample are ionized.  The plasma is produced by passing Ar gas into an energy field induced by a
radiofrequency (RF) generating coil.  The RF energy field causes collisions between the Ar atoms,
generating a high energy plasma. The sample aerosol is instantly decomposed in the plasma (temperature
of 6,000 - 10,000 K) to form analyte atoms which are simultaneously ionized. The ions produced are
extracted from the plasma into a mass spectrometer which is held at high vacuum.   The mass analyzer
then separates the ions based on their mass/charge ratio. The  mass analyzer is essentially four parallel
molybdenum rods to which a combination of RF and DC voltages are applied. The combination of these
voltages allows the analyzer to transmit only ions of a specific mass/charge ratio. Finally, the ions are
measured using an electron multiplier, and are collected by a counter for each mass number. The mass
spectrum generated is extremely simple. Each elemental isotope appears at a different mass (i.e.. 27Al
would appear at 27 amu) with a peak intensity directly proportional to the initial concentration of that
isotope. The proportionality is determined using standard solutions with known concentrations of
elements.  

Small parts of solid mineral samples can also be analyzed using the ICP-MS with an attached laser.  The
laser is focused on the part of the sample of interest and the power is increased to cause melting of that
small part of the sample  (this is called laser ablation).  The melt is then injected into the plasma and the
rest of the analysis is similar to that described above.  This is a relatively new technique that is
continually improving in terms of detection limit and reproducibility.  

X-ray Fluorescence (XRF) Spectrometry 

XRF spectrometry uses some of the principles X-ray diffraction.  It is a technique now used mainly for
the analysis of rocks because it requires relatively large amounts of sample (about 1 gram).  It can be
used to measure all of the major elements in a rock or mineral as well as a wide variety of trace
elements.  Sample preparation involves grinding the rock or mineral to fine powder and either pressing
the powder into a pill or melting and quenching the sample to make a glass disk.
 
When  an electron is be dislodged from an
inner electron shell, outer shell electrons
fall in to take its place resulting in the
production of X-rays with a  wavelength
that is characteristic of the element
involved.  In X-ray diffraction, a beam of
electrons is used to dislodge the inner
shell electrons and to produce X-rays of
known wavelength in the anode target of
the X-ray tube.  In XRF, however, we use
the X-rays from the X-ray tube to dislodge
the electrons in atoms of an unknown
sample.
 

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Just like in the X-ray tube, inner shell electrons that are dislodged
from  atoms in the unknown sample result in the production of X-
rays of characteristic wavelength for each of the different atoms in
the sample.  For each atom in the sample, the intensity of the
characteristic X-rays will be proportional to the number of atoms in
the sample.  Thus, if we can measure the intensity of characteristic
X-rays for each element, we can compare the intensity to that of a
standard with known concentration, and determine the
concentration of the element in the unknown. 

The instrument used for such measurements is called

an X-ray Fluorescence Spectrometer.  It consists of
an X-ray tube to produce X-rays capable of
dislodging inner shell electrons of all elements of
interest in the sample These have to be high energy
X-rays, so Cr, Mo, W, and Au targets are used as the
anode.  The X-rays that are produced in the sample
are then sent through a collimator to produce a
coherent beam.  These are then  diffracted through a
crystal of known d-spacing.  Using the Bragg
equation (n = 2dsin) we can determine the
angle that X-rays of known wavelength will be
diffracted through the crystal.  Thus, the crystal and
detector are set up to diffract only X-rays of the
particular wavelength of interest into the detector.
Intensities of characteristic X-rays for each element of interest are determined by rotating the crystal and
detector to the angle  required for diffraction of the characteristic X-ray wavelength.  X-ray intensities
are then measured for each element in the unknown and for each element in a standard that has known
concentrations.  The following equations are then used to determine the concentration of each element in
the unknown:

Cistd = kIistd

Ciunk = kIiunk

where Cistd = the concentration of element i in the standard,

          Iistd = the intensity of X-rays of element i in the standard,

          Ciunk = the concentration of element i in the unknown,

           Iiunk = the intensity of X-rays of element i in the unknown, and 

           k = a proportionality constant.

The proportionality constant, k, can be determined from the first equation:

k = Cistd/Iistd

This can then be substituted into the second equation to solve for the concentration of element i in the

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unknown:

Ciunk = (Cistd/Iistd) Iiunk

In practice, this is only true if  all elements in the standard and the unknown occur in about the same
concentration.  This is often difficult to attain, so a wide variety of standards are used to figure out all of
the interfering effects and make a calibration curve which relates concentration in the unknown to a
more complex equation involving the concentration and intensities in the standard.

Electron Microprobe (EMP) Analysis

The electron microprobe is an instrument that uses principles similar to XRF. The main difference is that
instead of using X-rays to dislodge inner shell electrons of elements in the unknown, an electron beam is
used.  The electron beam can be focused down to a spot size of about 1 m (1m = 10 -6m), and thus the
X-rays in the sample will only be generated within a very small volume of the sample.  Thus, one can
measure the concentrations in small parts of single mineral grains, and chemical zoning patterns or
changes in the concentration of elements through an individual grain can be determined.   The sample can
either be a highly polished thin section of a rock or mineral or can be grain mounts wherein individual
grains are mounted in epoxy and polished to a smooth surface.

The instrument consists of a large tank that is evacuated to

produce a vacuum.  At the top is an electron gun that has a
filament, similar to that in an X-ray tube, that generates
electrons.  The electron beam is accelerated down to a
sample stage that is moveable.  The electron beam is
focused to a diameter of about 1 m by a series of
magnets along its path.  Most electron microprobes have
at least 3 X-ray spectrometers inside, so that more than
one element can be measured at once.  A microscope with
binocular viewfinders allows the user to focus the electron
beam anywhere on the sample, as shown in the
inset.  This can be accomplished by moving the sample
stage.

Electrons striking the small area of the sample produce X-rays with wavelengths characteristic of the
elements in the sample.  The spectrometers consist of curved crystals of known d-spacing.  These
crystals diffract X-rays of each element into the detectors at the diffraction angle .  Several elements
can be measured at once, then the spectrometers are set to new angles to measure the X-ray intensities of
several more elements.  
Just like in XRF analyses, standards have to measured to determine the proportionality constants or
calibration curves, and equations similar to those used in the XRF method are used to determine element
concentrations in the unknowns.  

Electron microprobe analysis is useful for determining the major element concentration in small parts of
minerals.  But, it is much less sensitive than the XRF in terms of trace element concentrations.

X-Ray Crystallography
Prior to the discovery of X-rays by Conrad Roentgen in 1895, crystallographers had deduced that
crystals are made of an orderly arrangement of atoms and could infer something about this orderly
arrangement from measurements of the angles between crystal faces.  The discovery of X-rays gave
crystallographers a powerful tool that could "see inside" of crystals and allow for detailed determination
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of crystal structures and unit cell size.  Here we discuss the application of X-rays, not so much in terms
of how they are used to determine crystal structure, but how they can be used to identify minerals.
Nevertheless, we still need to know something about X-rays, how they are generated, and how they
interact with crystalline solids.

X-rays and the Production of X-rays: X-rays are electromagnetic radiation with wavelengths between
about 0.02 Å and 100 Å (1Å = 10 -10 meters).  They are part of the electromagnetic spectrum that includes
wavelengths of electromagnetic radiation called visible light which our eyes are sensitive to (different
wavelengths of visible light appear to us as different colors).  Because X-rays have wavelengths similar
to the size of atoms, they are useful to explore within crystals.

 
The energy of X-rays, like all electromagnetic radiation, is inversely proportional to their wavelength as
given by the Einstein equation:

E = h = hc/

where E = energy
h = Planck's constant, 6.62517 x 10-27 erg.sec
 = frequency
c = velocity of light = 2.99793 x 10 10  cm/sec
 = wavelength

Thus, since X-rays have a smaller wavelength than visible light, they have higher energy.  With their
higher energy, X-rays can penetrate matter more easily than can visible light.  Their ability to penetrate
matter depends on the density of the matter, and thus X-rays provide a powerful tool in medicine for
mapping internal structures of the human body (bones have higher density than tissue, and thus are
harder for X-rays to penetrate, fractures in bones have a different density than the bone, thus fractures
can be seen in X-ray pictures).

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X-rays are produced in a device called an X-ray tube.  Such a tube is

illustrated here.  It consists of an evacuated chamber with a tungsten
filament at one end of the tube, called the cathode, and a metal target at
the other end, called an anode.  Electrical current is run through the
tungsten filament, causing it to glow and emit electrons.  A large
voltage difference (measured in kilovolts) is placed between the cathode
and the anode, causing the electrons to move at high velocity from the
filament to the anode target.  Upon striking the atoms in the target, the
electrons dislodge inner shell electrons resulting in outer shell electrons
having to jump to a lower energy shell to replace the dislodged
electrons.  These electronic transitions results in the generation of  X-
rays.  The X-rays then move through a window in the X-ray tube and
can be used to provide information on the internal arrangement of atoms
in crystals or the structure of internal body parts.
Continuous and Characteristic X-ray Spectra

When the target material of the X-ray tube is bombarded with electrons accelerated from the cathode
filament, two types of X-ray spectra are produced.  The first is called the continuous spectra. 

The continuous spectra consists of a range of wavelengths of X-

rays with minimum wavelength and intensity (measured in counts
per second) dependent on the target material and the voltage across
the X-ray tube.  The minimum wavelength decreases and the
intensity increases as voltage increases.

The second type of spectra, called the characteristic spectra, is

produced at high voltage as a result of specific electronic transitions
that take place within individual atoms of the target material.

 
This is easiest to see using the simple Bohr
model of the atom.  In such a model, the nucleus
of the atom containing the protons and neutrons
is surrounded by shells of electrons.  The
innermost shell, called the K- shell, is
surrounded by the L- and M - shells.  When the
energy of the electrons accelerated toward the
target becomes high enough to dislodge  K- shell
electrons, electrons from the L - and M - shells
move in to take the place of those dislodged.

 
Each of these electronic transitions produces an X-ray with a wavelength that depends on the exact
structure of the atom being bombarded.  A transition from the L - shell to the K- shell produces a K  X-
ray, while the transition from an M - shell to the K- shell produces a K  X-ray.  

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These characteristic X-rays have a much higher intensity than those

produced by the continuous sprectra, with K  X-rays having higher
intensity than K X-rays.  The important point here is that the
wavelength of these characteristic x-rays is different for each atom
in the periodic table (of course only those elements with higher
atomic number have L- and M - shell electrons that can undergo
transitions to produce X-rays).  A filter is generally used to filter
out the lower intensity K X-rays.

For commonly used target materials in X-ray tubes, the  X-rays have the following well-known
experimentally determined wavelengths:

Element K Wavelength () Å

Mo 0.7107
Cu 1.5418
Co 1.7902
Fe 1.9373
Cr 2.2909
 

 
X-ray Diffraction and Bragg's Law

Since a beam of X-rays consists of a bundle of separate waves, the

waves can interact with one another.  Such interaction is termed
interference.  If all the waves in the bundle are in phase, that is their
crests and troughs occur at exactly the same position (the same as
being an integer number of wavelengths out of phase, nn = 1,
2, 3, 4, etc.), the waves will interfere with one another and their
amplitudes will add together to produce a resultant wave that is has a
higher amplitude (the sum of all the waves that are in phase. 

If the waves are out of phase, being off by a non-integer number of

wavelengths, then destructive interference will occur and the
amplitude of the waves will be reduced.  In an extreme case, if the
waves are out of phase by an odd multiple of 1/2 [(2n+1)/2 ], the
resultant wave will have no amplitude and thus be completely
destroyed.
The atoms in crystals interact with X-ray waves in such a way as to produce interference.  The
interaction can be thought of as if the atoms in a crystal structure reflect the waves.  But, because a
crystal structure consists of an orderly arrangement of atoms, the reflections occur from what appears to
be planes of atoms.  Let's imagine a beam of X-rays entering a crystal with one of these planes of atoms
oriented at an angle of  to the incoming beam of monochromatic X-rays (monochromatic means one
color, or in this case 1 discreet wavelength as produced by the characteristic spectra of the X-ray tube).

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Two such X-rays are shown here, where the spacing

between the atomic planes occurs over the distance,
d.  Ray 1 reflects off of the upper atomic plane at an
angle  equal to its angle of incidence.  Similarly,
Ray 2 reflects off the lower atomic plane at the same
angle .  While Ray 2 is in the crystal, however, it
travels a distance of 2a farther than Ray 1.  If this
distance  2a is equal to an integral number of
wavelengths (n), then Rays  1 and 2 will be in
phase on their exit from the crystal and constructive
interference will occur.
If the distance  2a is not an integral number of wavelengths, then destructive interference will occur and
the waves will not be as strong as when they entered the crystal.  Thus, the condition for constructive
interference to occur is

n = 2a

but, from trigonometry, we can figure out what the distance 2a is in terms of the spacing, d, between the
atomic planes.

a = d sin 

or 2a = 2 d sin 

thus, n = 2d sin 

This is known as Bragg's Law for X-ray diffraction.

What it says is that if we know the wavelength , , of the X-rays going in to the crystal, and we can
measure the angle  of the diffracted X-rays coming out of the crystal, then we know the spacing
(referred to as d-spacing) between the atomic planes.  

d = n /2 sin 

Again it is important to point out that this diffraction will only occur if the rays are in phase when they
emerge, and this will only occur at the appropriate value of n (1, 2, 3, etc.) and . In theory, then we
could re-orient the crystal so that another atomic plane is exposed and measure the d-spacing between all
atomic planes in the crystal, eventually leading us to determine the crystal structure and the size of the
unit cell.

The X-ray Powder Method: In practice, this would be a time consuming operation to reorient the
crystal, measure the angle , and determine the d-spacing for all atomic planes.  A faster way is to use a
method called the powder method.  In this method, a mineral is ground up to a fine powder.  In the
powder, are thousands of grains that have random orientations.  With random orientations we might
expect most of the different atomic planes to lie parallel to the surface in some of the grains.   Thus, by
scanning through an angle of incident X-ray beams form 0 to 90o, we would expect to find all angles
where diffraction has occurred, and each of these angles would be associated with a different atomic
spacing.

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The instrument used to do this is an x-ray

powder diffractometer.  It consists of an
X-ray tube capable of producing a beam
of monochromatic X-rays that can be
rotated to produce angles from 0 to 90o. 
A powdered mineral sample is placed on
a sample stage so that it can be irradiated
by the X-ray tube.  To detect the
diffracted X-rays, an electronic detector is
placed on the other side of the sample
from the X-ray tube, and it too is allowed
to rotate to produce angles from 0 to 90o. 

The instrument used to rotate both the X-ray tube and the detector is called a goniometer.  The
goniometer keeps track of the angle , and sends this information to a computer, while the detector
records the rate of X-rays coming out the other side of the sample (in units of counts/sec)  and sends this
information to the computer.

After a scan of the sample the X-ray intensity can be

plotted against the angle  (usually reported as 2
because of the way older diffractometers were made)
to produce a chart, like the one shown here.  The
angle 2 for each diffraction peak can then be
converted to d-spacing, using the Bragg equation.

One can then work out the crystal structure and associate each of the diffraction peaks with a different
atomic plane in terms of the Miller Index for that plane (hkl).

A group known as the Joint Committee on Powder Diffraction Standards (JCPDS) has collected data
such as this on thousands of crystalline substances.  This data can be obtained as the JCPDS Powder
Diffraction File.  Since every compound with the same crystal structure will produce an identical powder
diffraction pattern, the pattern serves as kind of a "fingerprint" for the substance, and thus comparing an
unknown mineral to those in the Powder Diffraction file enables easy identification of the unknown.
What is Bragg's Law and how can it be used to identify minerals?

 
Recalculation of chemical analyses of minerals:
Please read through pages 240-244 in Klein & Hurlburt (1993) for five good examples on how actual chemical
formulae of different minerals can be derived from results of quantitative analyses in terms of weight
percentages of the elements present (as either metals or their oxides) in any given mineral. These examples
clearly illustrate the role played by solid solution in altering the presumed chemical formulae of different
minerals and hence also that of the chemistry of the rocks in which they occur depending on the nature of the
existing chemical environments.

Graphic representation of mineral compositions:

For simple compositional variation it is often convenient to visualize the compositions in some kind of graphical
form.  Most chemical analyses of oxide and silicate minerals are reported in weight % oxide components.   In
weight percent because the classical technique of chemical analyses was once gravimetric, and in oxide
components because it is difficult to obtain concentrations of Oxygen, so in oxides and silicates it is assumed
that there is enough Oxygen to balance the cationic charges.

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If the composition of a mineral can be expressed with 2 components, then a linear scale can be used as a
graphical representation of composition.  For example, chemical analysis of the mineral kyanite shows that it is
composed of about 36 weight % SiO2 and 64 weight % Al2O3.
We can plot this on a linear scale as shown here in the upper diagram.  Note that in this two component
compositional diagrams, 0%  plots at the same point as 100 % .

We could divide each of these weight percentages by the molecular weight of each of the oxides and recalculate
in the analysis in terms of molecular %.  But the chemical formula of Kyanite - Al2SiO5 - tells us that kyanite is
made up of 1Al2O3  + 1SiO2 . So in molecular percent 50% of kyanite is  Al2O3 and 50% is SiO2, as shown in the
lower diagram above.
Similarly, olivine can be thought of as a mixture of forsterite, Fo (Mg 2SiO4) and fayalite, Fa (Fe2SiO4).  If these
are the only two components involved, then note again that 100% Fo corresponds to 0% Fa, and vice versa.

An olivine solid solution that has 50% of the Mg +2 ions replaced by Fe+2 ions would be said to have a composition
Fo50 or Fa50. Note that it could be expressed either way, because both ways indicate the same composition.  The
chemical formula for such a composition would be written as MgFeSiO 4.  Similarly, for an olivine composition
where 20% of the Fe+2 ions are replaced by Mg+2 ions, the composition could be expressed as Fa20 or Fo80.  
If there are three components that need to be plotted, a triangular graph can be used.   Such a graph for the three
components MgO, CaO, SiO2 is shown below.

Each of the corners of the triangular graph represent 100% of the component plotted at that corner, and 0% of the
other two components.  Lines parallel to the sides of the triangle in this case are marked off in 10% increments,
so that the horizontals lines represent the % of CaO starting from 0% at the bottom to 100% at the CaO corner.  
Lines parallel to the SiO2 - CaO side of the triangle represent the %MgO starting from 0% at the SiO 2 - CaO join
to 100% MgO at the MgO corner.  Lines parallel to the MgO - CaO side of the diagram represent the % SiO 2.
Note that the composition 33%MgO, 33%CaO, 33%SiO2 plots at the exact center of the triangle.
Minerals that only contain 2 of the three components plot along the sides of the triangle, with the scale being
similar to the 2-component graphs discussed above.  So, for example if we are using molecular percentages,  
- CaSiO3 (wollastonite) which can also be written as 1CaO + 1SiO 2, plots 50% of the way between CaO and SiO2.

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- MgSiO3 (enstatite) can also be written as 1MgO + 1SiO2, and plots 50% of the way between MgO and SiO2.
- CaMgSi2O6 (diopside) can also be written as 1CaO + 1MgO +2SiO 2.  There are a total of 4 molecules, with 1/4
as CaO, 1/4 as MgO, and 2/4 as SiO2.  So diopside plots at 25%CaO, 25%MgO, and 50%SiO2.
Triangular diagrams are often used to show the compositional ranges in minerals.  We here look at 2 examples.
The feldspars can be looked at in terms of the three components Albite (Ab) - NaAlSi 3O8, Orthoclase (Or) -
KALSi3O8, and Anorthite (An) - CaAl2Si 2O8.  At high temperature, complete solid solution exists between Ab
and Or, to form the alkali feldspar solid solution series.  But, as shown in the diagram, the alkali feldspar solid
solutions can contain up to 5% of the An component.  Similarly a complete solid solution series exists between
Ab and An, to form the plagioclase solid solution series.  Plagioclase can contain up to about 5% of the Or
component.

Another example is shown by the pyroxene minerals.  These plot in the three component system Enstatite (En) -
MgSiO3,  Wollastonite (Wo) - CaSiO3, Ferrosilite (Fs)  - FeSiO3.  Wo does not have a pyroxene structure 
Complete solid solution exists between Diopside, Di,  (CaMgSi2O6) and Hedenbergite, Hd,  (CaFeSi2O6).  These
pyroxenes are monoclinic and are thus called the clinopyroxenes.  Augite is also a clinopyroxene, but note that it
is depleted in the Wo component relative to the Di - Hd series.  En - Fs also forms a complete solid solution
series.  These minerals are orthorhombic, so the series is often referred to the orthopyroxenes..   Pigeonite is a
monoclinic pyroxene that has slightly more of the Wo component than the orthopyroxenes.

PHYSICAL PROPERTIES OF MINERALS

Physical properties of minerals are a direct result of their chemical and structural characteristics. These
properties are very important because they help us identify the different minerals. They can be recognized by
sight or determined by simple tests. Careful identification of minerals requires highly specialized techniques such
as XRD, XRF, optical microscopy, chemical analysis, measurement of physical properties, e.t.c.
Minerals have distinguishing physical properties that in most cases can be used to determine the identity of the
mineral.  However, alterations of mineral properties may occur as result of weathering or tarnishing on exposure
to the atmosphere. Therefore, it’s required that each of these properties be noted on ‘fresh’ minerals.
In this course, you will develop a systematic approach to using the physical properties of minerals as identifying
tools.  If you follow this approach you should be able to identify most of the common minerals, or at the least be
able to narrow the possibilities to only a few. 
Identification tables have been designed is several texts to provide a systematic methods for identifying minerals
by considering each of several properties in sequence and thus narrowing the possible choices e.g. first lustre,
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which is either [i] metallic or non-metallic then cleavage and one can eventually arrive at the correct identity. But
the primary difficulty with such tables is that somewhere in the process, it’s probable that a property cannot be
evaluated. Hence these tables have been left out but you are urged to look at many standard mineralogy texts that
have them.
-Getting familiar with minerals is somewhat like getting acquainted with people. Though minerals are much less
complex chemically (than people), they occur in many variations. Because most of the properties are so variable,
the only practical way of learning to recognize minerals is to study a large variety of each species until the
variations are recognizable.
-It is obviously necessary to have access to mineral collections in which the identifications have already been
made. Many cities have museums with good mineral collections. Many colleges and universities (particularly
those with geology and mineralogy departments), geological surveys and mineral clubs have excellent
collections. The staff of museums, geology and mineralogy departments and amateur collectors are willing to
assist the beginner in the identification of specimens and to provide other information. So, get time to visit these
places so that you can appreciate the great diversity of minerals as well as their physical characteristics.

We will first discuss each of the physical properties that can be used, then develop a methodical approach to the
identification of minerals using these physical properties.  Among the properties we will discuss are: crystal
habit, cleavage, hardness, specific gravity, luster, streak, color, tenacity, e.t.c., which have been grouped into
mechanical, optical, electrical & magnetic properties as discussed below.

Mechanical properties:
1. Crystal habit (external form):
This refers to the appearance/shape of individual crystals or aggregates of crystals.
In nature perfect crystals are rare.  The faces that develop on a crystal depend on the space available for the
crystals to grow.  If crystals grow into one another or in a restricted environment, it is possible that no well-
formed crystal faces will be developed.  However, crystals sometimes develop certain forms more commonly
than others, although the symmetry may not be readily apparent from these common forms.  The term used to
describe general shape of a crystal is habit.
The following terms are used to express the appearance or habit of individual crystals, or of groups (aggregates)
of crystals:
1. When a mineral consists of isolated and distinct crystals, the following terms may be used:
a) Acicular - slender need-like crystals e.g. Natrolite.

b) Capillary or filiform - hair-like or thread like crystals.

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c) Bladed – elongated crystals flattened like a knife blade e.g. Kyanite.

d) Cubic - cube shapes

e) Octahedral - shaped like octahedrons

f) Equant - a term used to describe minerals that have all of their boundaries of approximately equal length.

2. When a mineral consists of a group of distinct crystals, the following terms are used:
a) Dendritic/arborescent - slender divergent branches (tree-like) e.g. crystallized gold and copper

b) Reticulated/Lattice–like - having veins, fibres or lines crossing like the threads or fibres of a network group of
slender crystals.

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c) Divergent/radiated – radiating crystal groups from a common center e.g. Wavellite

d) Drusy- surface is covered with a layer of small crystals.

3. When a mineral consists of parallel or radiating groups of individuals the following terms are used:
a) Columnar- stout column-like individuals (individuals crystals are fairly large and proximately equidimensional
in cross-section ) e.g. calcite , some tourmaline .

b) Fibrous – slender fibrous aggregate of crystals are so small that they are effectively fibres e.g. some gypsum,
asbestos.

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c) Stellated - radiating individuals forming star-like groups.

d) Globular – Radiating individuals forming spherical or hemispherical groups e.g. Smithsonite.

e) *1Botryoidal – When the globular/bulbous crystal forms are in groups like a “bunch of grapes” e.g. hematite.

f) *2Reniform- Kidney–like e.g. hematite i.e. individuals terminate in rounded masses resembling a kidney in
shape.

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g) *3Mammillary- Large rounded masses resembling mammae that are formed by radiating individuals.

h) Colloform – Because it is difficult to distinguish between aggregates represented by the last three terms ( *123),
the word colloform has been proposed to include all the more or less spherical forms.

4. When a mineral consists of scales or lamellae, the following terms are used:
a) Foliated- When a mineral separates easily into plates or leaves e.g. muscovite mica.

b) Micaceous- Similar to foliated but the mineral can be split into exceedingly thin sheets like in the micas.

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c) Tabular or Lamellar - when a mineral consists of flat plate-like (rectangular) individuals superimposed upon
and adhering to each other. Similar to foliated but the plates are not separable e.g. aragonite.

5. When a mineral consists of grains the following term is used:

Granular – When a mineral consists of an aggregate of large or small grains

6). Miscellaneous:
a) Stalactitic – When a mineral occurs in pendent cylinders or cones e.g. calcite and aragonite.

b) Concentric - Consisting of more or less circular layers superimposed upon one another about a common center.
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c) Pisolitic – A mineral consisting of rounded masses about the size of peas.

d) Oolitic – A mineral aggregate formed of small spheres.

e) Banded- When a mineral occurs in narrow bands of different colour e.g. lime stone.

f) Massive – a mineral composed of compact material with an irregular form, without any peculiar appearance
like those described above.

g) Amygdaloidal- When a mineral[/rock, such as basalt], has numerous gas cavities (vesicles) that have been
filled with secondary minerals e.g. zeolites in basalt.
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h) Concretionary- Roughly spherical masses formed by deposition of material on a nucleus e.g. pyrite.

Note:
 This list is not exhaustive but the other terminologies will be covered during the practicals.
 Some minerals characteristically show one or more of these habits, so habit can sometimes be a powerful
diagnostic tool.

2. Hardness (H):

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Is the resistance that a smooth surface of a mineral offers to scratching . Its dependant on the strength of atomic
bonding in the mineral . A series of 10 common minerals was chosen ( by an Australian mineralogist called F.
Mohs, 1824) as a scale , by comparison , with which the relative hardness of a mineral can be determined. The
following minerals arranged in order of increasing hardness comprise what is known as the Mohs scale of
hardness:
2. Talc
3. Gypsum
4. Calcite
5. Fluorite
6. Apatite
7. Orthoclase
8. Quartz
9. Topaz
10. Corundum
11. Diamond
In addition to the above scale, the following materials may serve as a quick determinative criterion for
the hardness of a mineral:
Material Hardness
Fingernail Just over 2 i.e. 2+
Copper coin Over 3 i.e. 3+
Steel pocket knife Little over 5 i.e. 5+
Window glass 5½
Steel file 6½

In order to determine the relative hardness of a given mineral, it is necessary to find which of these minerals it
can and which it cannot scratch. The degree of hardness is determined by observing the relative ease or difficulty
by which one mineral is scratched by another. Hence it’s usually the scratch hardness that is determined.
Hardness is determined by scratching the mineral with a mineral [or substance] of known hardness. This should
be done progressively, starting with test samples of lower hardness to those of higher hardness on any mineral
sample. Hardness is a relative scale, thus to determine a mineral's hardness, you must determine that a substance
with a hardness greater than the mineral does indeed scratch the unknown mineral, and that the unknown mineral
scratches a known mineral of lesser hardness. Therefore, in our practicals, we shall give hardness as a range
between two successive numbers i.e. a range between the time when the last scratch was removed to a time when
the first true scratch remained e.g. 4-5, 6-7 or 9-10. Several
precautions are necessary for performing the hardness test: a)* Always use a fresh
surface of a mineral for this test. Some minerals have surfaces that are altered to a different substance that may
be softer than the original mineral. A scratch in this softer alteration product will not reflect the true hardness of
the mineral. Always use a fresh surface to perform the hardness test.
b)* Always try to scratch minerals A by mineral B and then reverve the test by
scratching B by A. Sometimes the habit of the mineral will make a difference. For example aggregates of
minerals may break apart leaving the impression that the mineral is soft. Or, minerals that show fibrous or
splintery habit may break easily into fibers or splinters. It is therefore wise to always perform the hardness test in
reverse i.e. reverse the test. If one mineral appears to scratch another mineral, make sure that the other mineral
does not scratch the apparently harder mineral before you declare which of the minerals is harder.
*c) Make sure a true scratch has been obtained i.e.
a true scratch is permanent while a temporary mark is rubbed off. If you attempt to scratch a soft mineral on the
surface of a harder mineral some of the softer substance may leave a mark of fine powder on the harder mineral.
This should not be mistaken for a scratch on the harder mineral. A powder will easily rub off, but a true scratch
will occur as a permanent indentation on the scratched mineral. *d) Crystals of minerals
may show varying degrees of hardness depending on the directions in which they are scratched since hardness is
a vectorial property. When there is significant difference in hardness in different directions, it can be a very
diagnostic property of the mineral. It is thus wise to perform the hardness test by attempting to scratch the
mineral in different directions. e.g.
a) Kyanite has H= 5 parallel to the length and H=7 across the length of the crystal. b) Calcite has

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H= 3 on all surfaces except the form {0001} where H=2 *e) The test cannot be
performed on gemstones as this spoils their beauty.
Hardness is given as number or range of the numbers on the Moh’s scale and applies to clean
[unweathered ] single crystals.

3. Cleavage:
The tendency of minerals to break smoothly parallel to (along) atomic planes in the structure . This is a
manifestation of the weaker bond strength across those planes than in other directions in the structure . Such
planes are always parallel to the possible crystal faces.
Crystals often contain planes of atoms along which the bonding between the atoms is weaker than along other
planes. In such a case, if the mineral is struck with a hard object, it will tend to break along these planes. This
property of breaking smoothly along specific planes is termed cleavage.
Cleavage is studied by observing the regular systems of cracks within transparent crystals[e.g. fluorite, calcite ]
or the smooth reflecting surfaces that result from breaking the grains e.g. feldspars, galena, pyroxene].
Note: Please do not attempt to cleave the minerals in the laboratory. Many of the specimens you examine cannot
be readily replaced. Cleavage is usually induced in the mineral when it is extracted from the rock when it is
found, and can usually be seen as planes running through the mineral. Therefore, you do not have to break the
mineral in order to see its cleavage.
- The cleavage can be described in terms of the quality of the break, i.e., if it cleaves along perfect planes it is
said to be perfect, and if it cleaves along poorly defined planes it is said to be poor [e.g. native copper], good
cleavage e.g. in micas or completely absent [e.g. in quartz].
- It’s also described by the following terms according to the ease with which the mineral breaks along the regular
planes.
a) Eminent : extreme ease of breaking so that it is hard to prevent it e.g. molybdenite.
b) Perfect: easily broken e.g. fluorite , calcite, baryte.
c) Distinct: e.g. hypersthene.
d) Imperfect e.g. apatite
e) Excellent e.g. diamond.
- Cleavage can also be described by general forms names, i.e., shape of the break for example if the mineral
breaks into square shaped pieces it is said to have cubic cleavage (3 cleavage directions), if it breaks into
prismatic shapes, it is said to have prismatic cleavage (2 cleavage directions), or if it breaks along basal pinacoids
(1 cleavage direction) it is said to have pinacoidal cleavage or plate-like cleavage [e.g. graphite & the micas].  It
can also break into octahedrons hence said to have octahedral cleavage e.g. fluorite.

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- From the above example, we also realize that cleavage could be described according to the number of
directions in which the breaking occurs e.g. one directional cleavage in micas, two directional cleavage either at
right angles as in pyroxenes and galena or not at right angles as in amphiboles, three directional cleavage either at
right angles as in calcite or not at right angles as is calcite, e.t.c.

4. Fracture
This is the way a mineral breaks when it does not yield along cleavage or parting surfaces or
the tendency of a mineral to break in a direction other than a cleavage plane.
If the mineral contains no planes of weakness, it will break along random directions called fracture. The
following terms are used to describe the different types of fracture patterns:
a) Conchoidal: Smooth curved fracture resembling the interior surface of a shell e.g. obsidian (volcanic rock),
glass, quartz .
b) Splintery (Fibrous)
c) Hackly: Jagged fractures with sharp edges.
d) Uneven / irregular : Fractures producing rough and irregular surfaces.
e) Even: Fractures producing smooth surfaces.

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5. Parting:
It’s the tendency of minerals to break along planes of structural weakness, usually resulting from pressure or
twinning .
Parting is also a plane of weakness in the crystal structure, but it is along planes that are weakened by some
applied force.  It therefore may not be apparent in all specimens of the same mineral, but may appear if the
mineral has been subjected to the right stress conditions.
Resembles cleavage in that it is parallel to rational crystallographic planes, and differentiated from it by the fact
that every mineral possesses cleavage in general while parting is only displayed by those minerals have been
subjected to proper pressure or are twinned. It’s not absolutely repeatable or reproducible like cleavage hence not
consistent but when seen it can be an aid in mineral identification. Most parting is seen as fracture lines that are
incomplete i.e. the crystal continued to grow and sealed the break or may appear as striations or planes of
concentrated inclusions. Some mineralogists have suggested that parting is nothing more than very poor
cleavage.
Terms used to describe parting are:
- Octahedral e.g. magnetite, chromite, pentlandite
- Basal e.g. pyroxene, tourmaline, monazite, parasite, zincite
- Rhombohedral e.g. corundum (ruby),
- Cubic in cryolite,
- Two directions in hematite, e.t.c.

6. Tenacity:
It’s the resistance that a mineral offers to breaking, tearing, or bending i.e. the cohesiveness of a mineral. Terms
used to describe tenacity in minerals are:
- Brittle: Breaks and powers easily e.g. anglesite PbSO 4
- Malleable: can be hammered into thin sheets e.g. native metals Cu, Ag, Au.
- Sectile: can be cut into thin shavings with a knife e.g. Cerargyrite (horn silver –AgCl).
- Ductile - bends easily and does not return to its original shape
- Flexible: Bends somewhat but does not resume to its original position upon release of pressure.
- Elastic: on being bent, resumes to its original position upon release of pressure e.g. micas.
Brittle minerals usually exhibit ionic bonding while malleable, sectile and ductile minerals show metallic
bonding.

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7. Specific gravity (G)

A number that expresses the ratio between the weight of a substance and the weight of an equal volume of water
at 4ºC . It’s dependant on the kind of atoms present and manner in which they are packed.
Please read about the methods used in the accurate determination of specific gravity of minerals (e.g. using a
jolly balance, torsion balance, pycnometer, heavy liquids, e.t.c.).
For practical purposes, we shall just estimate specific gravity by hand (where it’s termed as heft), through
experience in handling objects of different weight. Heft can thus be light, moderate/medium or heavy.
A similar sense can also be developed for minerals. Hence minerals with
S.G.<2.5 = Light,
2.5-5.0 = Medium &
>5.0 = Heavy
Density refers to the mass per unit volume. Most silicates of light elements have densities in the range 2.6 to 3.5.
Sulfides are typically 5 to 6. Iron metal about 8, lead about 13, gold about 19, and osmium, the densest substance,
and a native element mineral, is 22.
Specific Gravity is the relative density, (weight of substance divided by the weight of an equal volume of water).
The units of density are grams per cm 3, and since water has a density of 1 g/cm 3, specific gravity would have the
same numerical value as density, but no units (as units would cancel). Thus, Specific gravity is very similar to
density, but is a dimensionless quantity and is measured in a slightly different way.
Specific gravity is measured by determining the weight in air (Wa) and the weight in water (Ww) and computing
specific gravity from SG = Wa / (Wa-Ww). In practice this is done using a Jolly balance.
Specific gravity is often a very diagnostic property for those minerals that have high specific gravities. In
general, if a mineral has higher atomic weight of the cation, then it has a higher specific gravity. For example, in
the orthorhombic carbonate minerals, the following is observed:
Atomic weight of Specific
Mineral Composition
Cation Gravity
Aragonite CaCO3 40.08 2.94
Strontianite SrCO3 87.82 3.78
Witherite BaCO3 137.34 4.31
Cerussite PbCO3 207.19 6.58
Specific gravity can usually be qualitatively measured by the heft of a mineral, in other words those with high
specific gravities usually feel heavier.  Most common silicate minerals have a specific gravity between about 2.5
and 3.0.  These would feel light compared to minerals with high specific gravities.
Generally, specific gravity is given either as a mean or as a range because few minerals have fixed compositions
and many contain inclusions of other minerals.

Relationship between density, crystal structure & chemical composition of minerals:

-The higher the specific gravity, the denser the mineral. Many minerals have the same range of density . Hence
specific gravity was adopted as a standard measure of density depending on the internal structure and
composition of the minerals.
* The internal structure is controlled by the tightness of the packing hence closely packed structures have high
density while open structures have low density.
* The composition depends on the atomic weight of the constituent elements and thus low –density minerals are
those with light weights.
* High –pressure implies high density in the mineral e.g. diamond (3.50) while low pressure implies lower
density in the mineral e.g. graphite (2.23).
*Temperature affects density in such away that higher temps permit open and expanded structures and thus
leading to low density (e.g. cristobalite: 2.32) while lower temperatures imply higher density (e.g. quartz: 2.65)

Optical properties:
1. Streak:
Is the colour of a finely powered mineral. It’s tested using an unglazed porcelain plate (Streak plate). Determined
by rubbing the mineral on a piece of an unglazed porcelain. Thus Streak can also be defined as the color

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produced by a fine powder of the mineral when scratched on a streak plate. It’s often different from the color of
the mineral in non-powdered form but more diagnostic than colour.
The presence of transition metals with unfilled electron shells (e.g. V, Cr, Mn, Fe, Co, Ni, and Cu) in oxide and
silicate minerals causes them to be opaque or strongly colored so that the streak will also be strongly colored.
Warning:
- The streak plate has a hardness of about 7 hence cannot be used with minerals of greater hardness.
- Minerals that are transparent do not leave a streak on the porcelain hence its most important for minerals have a
variety of colours.

2. Lustre:
Refers to the general appearance of a mineral surface in reflected light or the amount and quality of reflection of
light from the mineral surface.
Its influenced by:
- nature of atomic bonding in the crystal,
- reflective and absorptive indices,
- dispersive power &
- degree of roughness of the reflecting surface .
The lustre of minerals can be divide into two main types:
- metallic luster and
- non metallic lustre
Those lying in between are said to be sub-metallic .
Minerals with metallic luster have the shiny appearance of metals and are usually opaque & hence give black or
very dark streaks.
Non-metallic luster is common in minerals without metallic appearance that are generally light coloured and
transmit light through their edges hence their streaks are colorless or very light in color.
Terms used to describe the lustre of non-metallic minerals:
- Vitreous: Reflecting light like glass e.g. quartz, tourmaline and other silicates.
- Resinous: Having the appearance of a resin e.g. sphalerite and sulphur
- Pearly: Having the irridescent appearance of pearls .e.g talc and apophyllite & chlorite.
- Greasy: looking as if covered with a thin layer of oil. e.g. graphite, nepheline.
- Silky (silk-like): Is the result of a fine fibrous aggregate e.g. gypsum, malachite, serpentine.
- Adamantine: Having a brilliant lustre like that of diamond & cerussite. It’s typical of the minerals with high
indices of refraction.
Note that lustre is rarely used as a diagnostic property because weathering may alter lustre and because fine-
grained aggregates may have a different lustre from a clean crystal surface.

3. Transparency (diaphaneity):
Is the transmission of light through a mineral. The following terms are used to express varying degrees of this
property ;
Transparent: If the out line of an object viewed thru it is perfectly clear or distinct.
Translucent: Objects cannot be seen thru it.
Opaque: transmits no light.

4. Color:
The recognition of color is a response of the eye to small portion of the electromagnetic spectrum.
It’s dependant on the optical properties of each mineral and the impurities in a given mineral.
Color is sometimes an extremely diagnostic property of a mineral, for example olivine and epidote are almost
always green in color.  But, for some minerals it is not at all diagnostic because minerals can take on a variety of
colors.  These minerals are said to be allochromatic.  For example quartz can be clear, white, black, pink, blue, or
purple.    

Some minerals are invariably of the same color (hence termed idiochromatic) e.g. carbonates, sulphides, and
sulphosalts but most of them occur in a variety of colors (thus termed allochromatic).
The different colors may be a result of:

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- Small inclusions of other minerals e.g. rutile [TiO 2] inclusions are responsible for the effects of asterism &
chatoyancy. Air & water inclusions are common in gypsum & quartz.
At times inclusions can be diagnostic and even assist in the identification of the mineral’s locality e.g. emeralds
(green variety of beryl) mined in Russia are known to have tiny inclusions of actinolite, unlike other emeralds.
- Chemical impurities in the structure
- Defects in the structure

Color may help in interpreting the history of the mineral’s formation and hence
- It should always be noted on a freshly broken surface
- Staining/corrosion can help in identifying sulphides and sulpho-salts.

- Idiochromatic (self colored) minerals are those in which a specific coloring element (called a chromphore) is a
major constituent.
Examples:
 Cr- uvarovite (a green chromium-rich garnet)
 Cu- azurite (blue), malachite (green), cuprite (red)
 Fe- Lazulite (blue), olivine (green), almandine (red garnet), goethite (yellow)
 Mn- rhodonite (pink), spessatine (orange coloured Mn-rich garnet).
- Allochromatic minerals are those in which an impurity element (a trace element) is the coloring agent.
Examples:
 Cr- emerald (deep green beryl) , Cr-tourmaline (green ) ruby, spinel, topaz (red)
 Fe- aquamarine (greenish-blue beryl) , tourmaline (black, called schorl) ,citrine (yellow quartz),
orthoclase (yellow), jade (green-yellow-brown)
 Mn- tourmaline (pink, called rubellite), andalusite (green-yellow)
However few minerals have characteristic colors e.g. sulphur,(yellow), galena (grey), malachite (green), cinnabar
(red), azurite(blue).

5. Play of colors:
A mineral is said to show a play of colors if on turning it, several spectral colors are seen in rapid succession e.g.
diamond, opal.
Interference of light reflected from the surface or from within a mineral may cause the color of the mineral to
change as the angle of incident light changes.  This sometimes gives the mineral an iridescent quality.  Minerals
that show this include: bornite (Cu5FeS4) , hematite (Fe2O3), sphalerite (ZnS), and some specimens of labradorite
(plagioclase).

6. Luminescence:
Minerals have the ability to luminesce (emit light) during exposure to exciting radiation (e.g. UV light, X-rays,
cathode rays).

→ If the luminescence disappears immediately after the exciting radiation is cut off the mineral is said to be
fluorescent e.g. fluorite(hence the name). Such minerals light-up when exposed to ultraviolet light, x-rays, or
cathode rays. Some specimens of the same mineral show fluorescence while others don't. For example some
crystals of fluorite (CaF2) show fluorescence and others do not.  Other minerals show fluorescence frequently, but
not always.  These include - scheelite (CaWO4), willemite (Zn2SiO4), calcite (CaCO3), scapolite (3NaAlSi3O8.
(NaCl - CaCO3), and diamond (C).

→ If the luminescence continues after the exciting rays are cut-off, the mineral is said to be phosphorescent.

→ Triboluminescence:
The ability of some minerals to become luminous on being crushed, scratched, or rubbed. Most minerals showing
this property are non–metallic and possess good cleavage e.g. fluorite, lepidolite.

→ Thermoluminescence:

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Ability of some minerals to emit visible light when heated to a temperature below that of red heat. It’s best
shown by non –metallic minerals which contain impurity irons as activators e.g. calcite, apatite, feldspar.

*Other optical properties of minerals:

1. Chatoyancy: Cat’s eye effect caused by the reflection of light from parallel fibres, crystals or channels within
a mineral e.g. chrysoberyl (cymophane). Such minerals have a lustre resembling the changing lustre of the eye of
a cat.
2. Asterism: Star-like effect seen either in reflected or transmitted light and found in some minerals like ruby
(red variety of corundum) and sapphire (blue variety of corundum) caused by parallel fibres or channels in 3 sets
intersecting each other at 60 degrees or from inclusions arranged at right angles to these directions e.g. garnet,
diopside , rosy quartz. Such minerals (especially those in the hexagonal system) show star–like rays of light when
viewed in the direction of the C-axis.
3. Opalescence: A milky or pearly reflection from the interior of a mineral shown by opal, caused by reflection
of light from thin layers in the internal structure of the mineral.
4. Adularescence (Schiller effect): A bluish sheen in moonstone caused by thin plates (formed by laminar
twinning) within a mineral that interfere with reflected light with some components of white light being cancelled
and others reinforced.
5. Iridescence: Display of a series of spectral colours in the interior or the surface of a mineral e.g. chalcopyrite,
fluorite.
6. Pleochroism: Ability of minerals to display various colours when viewed in different directions in transmitted
light. It’s due to the selective absorption of light in the different crystallographic directions with a given mineral.
It’s only observed under an optical microscope. For minerals showing two such absorption directions, the
property is called dichroism. This property must be distinguished from other properties like play of colors or
iridescence, which refers to reflected light.
7. Double refraction: This is when a ray of light entering a non-opaque mineral (except those in the isometric
system) is broken-up into two rays, each of which travels through the minerals with a characteristic velocity and
has it’s own refractive index. Generally all crystalline minerals, except those belonging to the cubic system show
double refraction when viewed under an optical microscope.

Electrical properties:
- Piezoelectricity:
If pressure is exerted at the ends of a polar axis ( present in only those crystals that lack a centre of symmetry), a
flow of electrons towards one end, produces a negative electrical charge while a positive is induced at the
opposite end – This is piezoelectricity e.g quartz (SiO 2) has 3 polar axes and is therefore used to control radial
frequency.
If a mineral develops an electric charge on it’s surface as a result of pressure exerted at the ends of it’s axis it’s
said to show piezoelectricity.

- Pyroelectricity:
It’s the simultaneous development of positive and negative charges of electricity at opposite end s of a polar axis
under proper conditions of temperature change e.g tourmaline(develops an electrical charge at opposite end
under an applied thermal gradient).

- Electrical conductivity is an important physical property but requires an impedance bridge to measure. In
general native metals are good conductors, sulfides of transition metals are semi-conductors, whereas most
oxygen-bearing minerals (i.e., silicates, carbonates, oxides, etc.) are insulators.

Magnetic properties:
Magnetic minerals result from properties that are specific to a number of elements.
Minerals that do not have these elements, and thus have no magnetism are called diamagnetic. Diamagnetism is
the property of an object which causes it to create a magnetic field in opposition to an externally applied
magnetic field, thus causing a repulsive effect. Specifically, an external magnetic field alters the orbital velocity
of electrons around their nuclei, thus changing the magnetic dipole moment.  
Diamagnetic minerals have a small negative value of magnetic susceptibility and are slightly repelled by the
field.
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In general, diamagnetic minerals are those that are usually considered to be non-magnetic. Examples of
diamagnetic minerals are quartz, plagioclase, calcite, apatite, copper, gold, graphite, diamond, silver, lead and
bismuth. 

Elements like Ti, Cr, V, Mn, Fe, Co, Ni, and Cu can sometimes result in magnetism.   Minerals that contain these
elements may be weakly magnetic and can be separated from each other by their various degrees of magnetic
susceptibility. These are called paramagnetic minerals.  *Differences in magnetic susceptibility are used to
separate pure concentrations of minerals from crushed rocks or ores by use of a high intensity magnetic field .
Electro-magnetic separators are used for this work in laboratories and industries.
Paramagnetic minerals only show magnetic properties when subjected to an external magnetic field.  When the
magnetic field is removed, the minerals have no magnetism.
Paramagnetic minerals have a small positive value of magnetic susceptibility and are weakly attracted by the
field. Paramagnetic materials include magnesium, molybdenum, lithium, and tantalum.

Ferromagnetic minerals possess a magnetic moment even in the absence of an applied field.
Therefore, Ferromagnetic minerals have permanent magnetism if the temperature is below the Curie
Temperature.  These materials will become magnetized when placed in a magnetic field, and will remain
magnetic after the external field is removed.  Examples of such minerals are magnetite, hematite-ilmenite solid
solutions (Fe2O3 - FeTiO3), and pyrrhotite (Fe1-xS).
The Curie temperature (Tc), or Curie point, is the temperature at which a ferromagnetic material becomes
paramagnetic on heating. The effect is reversible. A magnet will lose its magnetism if heated above the Curie
temperature. Below the Curie temperature neighboring magnetic spins are aligned parallel within in
ferromagnetic materials. As the temperature is increased towards the Curie point, the alignment (magnetization)
within each domain decreases. Above the Curie temperature, the material is paramagnetic so that magnetic
moments are in a completely disordered state.
For practical purposes, we shall only differentiate between magnetic and non- magnetic substances.
Magnetite (Fe3O4), ilmenite (FeTiO3), and pyrolusite (MnO2) are all dense, black, opaque minerals which can
easily be distinguished by testing the magnetism with a magnet. Magnetite is strongly magnetic and can be
permanently magnetized to form a lodestone; ilmenite is weakly magnetic; and pyrolusite is not magnetic at all.

Other properties:
- Melting Point: It’s the temp at which a solid state mineral changes to the liquid state. Since different minerals
have different melting points , then it can be used to identify different minerals or groups of minerals.

- Radioactivity:
Occurs in minerals that contain uranium , thorium, or any other unstable isotopes.
These decay by emitting alpha (α) or beta (β) particles or gamma [γ] rays.
Examples of geologically important unstable nuclei are the following isotopes: 40K ,87Rb, 232Th, 238U, 204Pb, 235U ,
e.t.c.
Radioactivity is specially useful in:
-Medicine for treatment of cancer & location of bone structures
- Age dating of rocks(where half life of isotopes is used:
t1/2 = λt
e.g. t1/2 for 12C = 5570 years)
Minerals containing the elements U or Th are radioactive (although generally not dangerously so), and this
radioactivity can be easily detected with a Geiger counter. Examples of radioactive minerals are uraninite (UO 2),
thorite (ThSiO4), and carnotite (K2(UO2)(VO4)2.xH2O).

- Reaction to acids:
Dilute hydrochloric acid or dilute acetic acid (vinegar) is used (as they’re relatively mild) to test for carbonate
minerals or a few minerals that contain significant amounts of carbonate ions. The key to this property is not the
fact that the mineral reacts (although that’s diagnostic) but how well it reacts e.g. calcite & aragonite react easily
with cold dilute acid with a fizzing noise but dolomite and other carbonates react less vigorously and may only
produce a small reaction when the mineral is powdred or the acid is heated. In some cases the reaction is so slow

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that it’s only seen by the eventual dissolution of the mineral. Therefore, dilute acids are only used to identify
carbonates.
Minerals do dissolve e.g. gold can be dissolved in ‘aqua regia’ (mixture of one part nitric acid and 3-
4parts hydrochloric acid). Some minerals are soluble in water e.g. nitrates, borates, some carbonates, some
sulphates & some phosphates. Solubility can therefore be a diagnostic property for minerals that dissolve
rapidly. However, identification of minerals using the solubility test destroys the specimen (if soluble) hence a
small fragment could be used for such tests.

- Senses:
Our senses can also help in identifying few minerals, for example:
Some minerals like halite/rock salt (NaCl) have characteristic taste but one has to be cautious because
some minerals are poisonous. Usually, minerals with a taste ‘look wet’. Halite (NaCl) (common table salt) and
sylvite (KCl) are very similar in most of their physical properties, but have a distinctly different taste on the
tongue, with sylvite having a more bitter taste. Whereas it is not recommended that students routinely taste
mineral specimens (since some are toxic), taste can be used to distinguish between these two common minerals.
Hands-on experience is the only way to learn the characteristic ‘feels’ of different minerals.
Some minerals on being touched remind you of something e.g. talc has a greasy/oily cold feel
(resembling that of soap) as well as graphite and molybdenum. Minerals that have a distinctive feel are generally
low in hardness (but not always). Several metallic minerals such as copper have a jagged feel due to minute
sharp protrusions.
Some minerals have characteristic smell (scent), which may aid in their identification e.g. sulphides (like
marcasite) and sulphur (S) have a smell of sulphur. Arsenic minerals have a garlic scent e.g. arsenopyrite gives
off a garlic smell when struck or crushed. Occasionally, a mineral may have a rather distinct and therefore
diagnostic odor but it’s a fairly uncommon property and not reliable in general.

CLASSIFICATION OF MINERALS:
One of the goals of mineralogy, as in any science, is the classification of the objects to be studied. Only by
grouping minerals into definite categories is it possible to study, describe and discuss them in a systematic and
intelligent manner. Here, minerals sharing a large number of characteristics are grouped together.

Minerals may be grouped according to:

- Crystallographic characteristics
- Internal structure of minerals and kinds of chemical bonds between their atoms
- Chemical composition

The commonest method of classifying minerals is by chemical composition.

The simplest minerals are very few and contain one element or a solid solution of 2 or more elements. These are
simply classified as native metals, native non-metals and native semi-metals.

The majority of minerals are compounds that are made-up essentially of two parts:
a metal or semi-metal and,
ii) a non-metal or a metal-nonmetal combination, called a radical.

Minerals may thus be classified according to the chief metal present but the classification according to the
radicals present is the most widely accepted system e.g. Barite (BaSO 4), celesite (SrSO4), and anglesite PbSO4)
are classified as sulphates because they all contain the sulphate radical (SO 42-). They are all very similar in
appearance, behave similarly when treated chemically and occur under similar geologic conditions even though
they contain different metals- Ba, Sr, Pb. The Pb & Sr commonly substitute for Ba in barite leadind to a mixed
crystal (solid solution).

Based on their chemistry i.e. the presence of a major chemical component that could be an anion or anionic
complex, minerals are classified into 11groups as listed below:

Native elements
Sulphides and sulphor-salts
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Halides
Oxides and Hydroxides
Carbonates
Nitrates
Tungstates and Molybdates
Phosphates, Arsenates and Vanadates
Sulphates and Chromates
Borates &
Silicates

N.B: Write down the diagnostic properties of each of the common minerals in each group and grasp them.

For the above chemical classes, the anionic part of their chemical formula is used for classification. This
classification has been successful because minerals rarely contain more than one anion whereas they typically
contain several different cations.
Therefore, mineral classification is based on the dominant anion or anionic group because such minerals tend to
strongly and remarkably resemble, to occur together in the same geologic environment and it’s also the current
practice used in naming and classifying inorganic compounds. X-rays are used to determine the internal
structure of minerals.
Chemical composition and structure are therefore the basis upon which mineral classification is done and
determine the physical properties of a mineral but represent the real essence of a mineral. The above-mentioned
broad classes of minerals are discussed below:

1. NATIVE ELEMENTS:
- These are sufficiently inert to occur freely in nature i.e. in an uncombined form. Only about 20 elements have
been found occurring in the native state, excluding the free gases of the atmosphere. These elements are divided
into 3 groups:
o Metals,
o Semimetals and
o Nonmetals.
- Native metals display simple structures, have metallic lustre, they’re malleable and constitute 3 sub-groups:
i) Gold group: consists of Au, Ag & Cu. Related metals are Hg & Pb. They are all isostructural.
ii) Platinum group: consists of ruthenium (Ru), rhodium (Rh), palladium (Pd), Osmium (Os), Iridium (Ir), &
Platinum (Pt). They are among the rarest and most useful of all metals, non-reactive, good conductors, dense,
have high melting points. Only Pt & Pd occur in pure form. Others are found as natural alloys. All are
isostructural
iii) Iron group: consists of pure iron (Fe) and Nickle–iron in form of two minerals (Kamacite and taenite) where
the latter is the Ni-rich variety.
Native semimetals: Consist of Antimony (Sb), Arsenic (As) and Bismuth (Bi).
Nonmetals: Comprise of Sulfur & carbon. They are brittle and poor conductors. Divided into 2 groups:
o Carbon group: Diamond © & graphite ©
o Sulfur group: Has Sulfur (S) ± tellurium (Te) & selenium (Se).

Native metals:
Gold group:
- Belong to the same group in the periodic table
- Have similar chemical properties
- Sufficiently inert hence of elemental state in nature. In elemental state, form crystal structures with weak
metallic bonds.
-Have same structure i.e. isostructural (face-centred cubic lattice) with atoms in 12 coordination system hence
possess similar properties.
- The may be complete solid solution between Ag & Au but limited solid solution between Cu & Ag/Au

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- All are rather soft, malleable, ductile, sectile, excellent conductors of heat and electricity have metallic lustre,
hackly fracture, and low melting points due to metallic bonding.
Have high densities due to cubic closest packing of their structures.
- Difference in properties is due to properties of the atoms of individual elements e.g. yellow Au, red Cu, white
Ag.

Platinum group:
- Harder than those of the gold group.
- Rare but very useful metals
- Non-reactive, good conductors, dense, have high M.P.
- Only Pt and Pd occur in pure form, others found as natural alloys e.g. platiniridum, iridosmine.
- Have cubic or hexagonal close-packed structure

Iron group:
- Are isometric
- Pure iron is rare on the earth’s surface but Kamacite and Taenite are common in meteorites. Fe-Ni alloys of this
type constitute a large part of the earth’s core.
- Fe & Ni substitute @ other since they have identical atomic radic and show cubic close-packing.

Native semi-metals:
- As, Sb, Bi are isostructrural
- Rather uncommon
- Brittle and poor conductors of heat and electricity.
- Bond type is intermediate between metallic and covalent
- Complex structure since @ atom is somewhat closer to 3 of its neighbors than to other surrounding atoms
resulting into a layered structure, with weak bonding between them which gives rise to good cleavage. See their
structures on pg. 342; fig. 10.6.

Native non-metals:
S, diamond and graphite are the commonest members with variable structures.
- Sulphur naturally occurs as orthorhombic crystals that are stable at atmospheric pressure below 95.5ºC yet its
two monoclinic polymorphs are rare and stable between 95.5 oC-119oC but can be synthesized. The unit cell of S
contains 28 Sulphur atoms. S atoms are arranged in form of rings of 8Sulphur atoms hence forming closely
bonded S8 molecules. The rings are bonded together by Van-der-waals forces. Substitution with Se may occur.
See figure10.7; page 343.
- In diamond, each carbon atom is bound by strong covalent bonds to 4 carbon neighbors at the apices of a
regular tetrahedron, resulting into widely spaced sheets of carbon atoms, which accounts for the octahedral
cleavage and electrical insulation in diamond.
- Structure of graphite consists of six-membered rings in which @ C atom has 3 neighbours arranged at apices of
an equilateral triangle, with covalent bonds in plane of the sheet yet the fourth is left to wander over the surface
of the sheet, creating electrical charge which is responsible for its high electrical conductivity. Sheets are widely
separated with weak van-der waals forces in between them which gives rise to perfect basal cleavage and gliding
parallel to sheets. Diamond and graphite are polymorhs of carbon. See page 344 Fig 10.8 for their structures.

2. SULPHIDES AND SUIPHO-SALTS:

- This group comprises compounds in which the large atoms S, Se, Te, As, Sb and Bi are combined with Fe, Co,
Ni, Cu, Zn, Mo, Ag, Cd, Sn, Pt, Au, Hg, Tl, Pb and Bi.
- Very important class since it includes majority of ore minerals. Contain many metals necessary for civilization
but are complex in chemistry and origin
- Also included in this class are sulfarsenides, arsenides and tellurides.
- Most are opaque with distinct colours and colored streaks yet the non-opaque ones like orpiment, cinnabar,
realgar transmit light only on thin edges. Have extremely high refractive indices, heavy, relatively soft with
metallic or submetallic lustre and relatively high thermal and electrical conductivity, dark coloured.
- Generall formular is XmZn where X = metallic/semimetallic elements yet Z = non metallic element(s).

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- Sulfides are divided into different groups of similar structures but it’s difficult to make generalisations of their
structures. Please read about each type of structure.
- May display ionic, covalent or metallic bonding.
- Simple sulphides have regular octahedral or tetrahedral coordination about sulphur yet complex sulphides show
distorted polyhedra. Refer to the other properties in Battey (1981), page 177.
Assignment: How are sulphide minerals formed?

Sulfide minerals include:

- Realgar (AsS)
- Orpiment (AS2S3)
- Greenockite (CdS)
- Cinnabar (HgS)
The above mentioned minerals contain many metals necessary for civilization but are complex in chemistry &
origin.
- Stibnite group: Stibnite (Sb2S3) and Bismuthinite (Bi2S3).
- Molybdenite group: Molybdenite(MoS2), Tungstenite(WS2).
- Galena group: galena (PbS) & others like Altaite(PbTe) ,Albandite (MnS).
- Argentite group: Argentite (Ag2S) & others like Hessite (Ag2Te) , naumannite (Ag2Se).
- Chalcocite group: Chalcocite(Cu2S) & others like acanthite/argentite(Ag 2S) , stromeyerite (AgCuS), Digenite
(Cu2-xS).
- Sphalerite group:
i) Sphalerite (ZnS) ± metacinnabar (HgS) ± tiemannite (HgSe) .
ii) Chalcopyrite (CuFeS2)/
iii) Stannite (CuFeSnS4) / Related mineral is bornite (Cu5FeS4)
- Niccolite group: i) Niccolite (NiAs), pyrrhotite ( Fe 1-xS) , Pentlandite (Fe,Ni)9S8
ii) Covellite (CuS), Millerite (NiS)
- Pyrite group: pyrite (FeS 2) ± hauerite (MnS2), Penroseite ( Ni,Cu,Pb)Se2, Marcasite ( FeS2) , Loellingite
(FeAs2) , safflorite (Co, Fe) As 2, Arsenopyrite (FeAsS).
- Cobaltite group: Cobaltite (Co,Fe)AsS, gersdorffite (Ni,Fe,Co)AsS.
- Skutterudite group: Is a complete solid solution between smaltite (Co,Ni) As 1-x and cloanthite (Ni,Co)As1-x.
Skutterudite is a town in Norway.
- Krennerite group: Krunnerite (Au2Te4) , Calaverite (Au2Te4) & Sylvanite (AgAuTe4).

Sulfosalts are special types of sulfides in which sulfur is combined with one or more metals and one or more
semimetals (As, Sb). They are chemically and crystallographicaly complex but geologically similar to sulfides.
They include the following groups of minerals:
- Ruby silver group: pyrargyrite (Ag3SbS3) & Proustite ( Ag3AsS3)
- Tetrahedrite group : Tetrahedrite (Cu,Fe) 12Sb4S13, Tennantite (Cu,Fe) 12As4S13), jamesonite, boulangerite,
Zinkenite & Stephanite.
- Enargite group: Enargite ( Cu3AsS4) & Famatinite
- Bournonite group: Bournonite ( PbCuSbS3) , Seligmannite (PbCuAsS3).

3. HALIDES:
Halides: These are salts consisting of one (or more) halogen(s) and one (or more) metal(s).
All are soluble in water & are formed at low temps. Bonds are ionic or covalent. Such minerals include:
- Colomel (HgCl)
- Marshite ( Cul)
- Nantokite ( CuCl)
- Miersite ( Agl)
- Halite group: Halite ( NaCl), Sylvite (KCl) , Villiaumite ( NaF), Cerargyrite (AgCl), Sal-Ammoniac ( NH 4Cl)
- Flourite group: Flourite (CaF2) , Yttrofluorite ( Ca,Y,)F2, Cryolite (NaAlF6), carnalite (KMgCl3.6H2O),
atacamite Cu2 (OH) 3Cl.
They have diverse structural types and diverse geological origins.

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- Bonds predominantly ionic but where halogen ions are combined with smaller and more strongly polarizing
cations than those of the alkali metals, the bond has more covalent properties.
- In the Halite group, each cation and @ anion is surrounded by 6 closest neighbors in octahedral coordination
hence forming the NaCl structure. The resulting structure is cubic with identical atoms at the corners of a cube
and at centres of all the 6 faces. Halides of K + & Na+ are very ionics but those of Ag+ are more covalent.
- In the fluorite group, each cation is coordinated to 8 anions, which surround it at the corners and face centres
of a cube, yet each anion is surrounded by 4 cations hence forming fluorite type structure.
- Most halides have ionic bonding, low hardness, moderate to high M.P’s, poor conductors of heat and electricity.

4. OXIDES AND HYDROXIDES:

- Oxides are a group of minerals formed when one or more metals or semi-metals combine with oxygen.
- Oxides fall into 2 groups i.e. some are relatively hard, dense, refractory minerals that generally occur as
accessory minerals in igneous and metamorphic rocks and also as resistant detrital grains in sediments. Others
are secondary alteration products of sulphide ores that are softer and may be earthy.
- Oxide structures have strong ionic bonding.
- Hydroxide structures are characterized by presence of hydroxyl (OH -) group or water molecule hence bonds
weaker than in oxides. Hydroxides, however, have lower density & hardness and are found in secondary
alteration/weathering products, and less well-crystallised and more difficult to characterize than oxides. On
heating, Hydroxides dissociate (break apart into ions).
- Oxides may be classified into the following groups:
*A2O e.g. cuprite(Cu2O),
*AO e.g. periclase group that includes minerals like Periclase (MgO), Bunsenite (NiO), Manganosite (MnO) &
zincite group with minerals such as Zincite (ZnO), Bromellite (BeO), *A 2O3 e.g. hematite group with hematite
(Fe2O3), & corundum group with Corundum (Al2O3),
*ABO3 e.g. Ilmenite (FeTiO3), AB2O4 like the spinel group (mixed oxides) which are the most complex group of
oxides with minerals such as Spinel (MgAl 2O4), gahnite (ZnAl2O4), hercynite (FeAl2O4), Magnetite ( Fe3O4 or
FeFe2O4), Chromite (FeCr2O4, Franklinite (ZnFe2O4), Chrysoberyl (BeAl2O4)
*AO2 e.g. rutile group with minerals like Rutile (TiO 2), anatase (TiO2), brookite (TiO2), Pyrolusite (MnO2),
Cassiterite (SnO2) -+ plattnerite (PbO2); Uraninite group: Uraninite (UO 2), Thorianite (ThO2). This excludes
SiO2 & AmBnO2(m+n) of Ni, Ta, Ti and rare earths.
*Diaspore group: Diaspore AlO(OH) [loses water on heating and converts to corundum], goethite FeO(OH),
manganite MnO(OH), bauxite (mixture of diaspore , gibbsite, boehmite and other materials). Read about the
characteristic structure and features of each individual group.

5. CARBONATES:
These are minerals where triangular CO32- anionic groups are linked together by intermediate cations. All
effervesce in dilute cold/warm acids like HCl. Carbonate structures consist of triangular
(CO3)2- ions held together by metal ions.
- The calcite group has a structure similar to that of halite hence each Ca 2+ ion is surrounded by six oxygen
atoms of the CO32-groups. Like NaCl, carbonates in the calcite group have perfect cleavage but not at right
angles. There’s also extensive solid solution among members of the calcite group.
- The Aragonite group differs in structure from the calcite group in that the metal ions are shielded by 9 (rather
than 6) oxygen ions. Additional shielding is required by the larger ions of Barium, Strontium and Lead which is
why the carbonates of these ions are found only with aragonite structure, yet calcite (CaCO 3) with its smaller Ca 2+
ion may crystallize in either groups as calcite (or aragonite). Crystals are commonly psendohexagonal since
arrangement of Ca2+ and CO32- ions is nearly hexagonal.
- Dolomite CaMg(CO3)2 is structurally similar to calcite but with Mg 2+ and Ca2+ ions in alternating positions. For
this reason, it’s sometimes put in a separate group.
- The miscellaneous carbonates have OH - groups or water molecules within their structure, in addition to the
principle metal cations & CO32- anions.
Examples of carbonate minerals in each group are given below:
Calcite group:
Calcite CaCO3
Siderite FeCO3
Dolomite CaMg(CO3)2
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Magnesite MgCO3
Ankerite Ca(Mg,Fe,Mn)(CO3) 2
Smithsonite ZnCO3
Aragonite group:
Aragonite CaCO3
Witherite BaCO3
Strontianite SrCO3
Cerussite PbCO3
Miscellaneous:
Azurite Cu3(CO3) 2(OH)2
Malachite Cu2CO3(OH)2
Natron Na2CO3.10H2O
Trona Na3H(CO3) 2.2H2O

6. NITRATES:
The nitrate ion (NO3-1) is structurally the same as the carbonate ion (CO 32-), with one less charge. The nitrate ion
is a complex triangular ion that joins with monovalent alkaline earth ions to form minerals with either calcite
structure (e.g. Soda niter-NaNO3) or aragonite structure (e.g. niter – KNO3 = saltpeter).
- Nitrates are very soluble in water hence not widespread geologically but are important in the manufacture of
explosives and fertilizers. There are only 10 species of naturally occurring nitrates but only niter and soda niter
are found in significant amounts. The offers are not important mineralogically.

7. TUNGSTATES AND MOLYBDATES:

- The chemistry of tungstate ion, (WO 4)2- and molybdate ion, (MoO4)2- is so similar that they are always
associated with extensive solid solution as in the Wulfenite group. The anions are distorted tetrahedra, with the
tungsten atom (W) or Molybdenum (Mo) atom bonded to four oxygen atoms by covalent bonds.
- Tungstates are important to industry in that: since Tungsten metal oxides readily burn at high temperature in air,
it’s used almost exclusively for making filaments of light bulbs, vacuum tubes and X-ray tubes hence such tubes
and bulbs must be evaccuated.
- W is also alloyed with Fe to produce very strong corrosion-resistant steel.
- With development of nuclear reactors for generating electricity, W, Mo & Ta are all important refractory
metals. Also suitable as cladding for fuel rods containing mixtures of uranium and plutonium oxides because
they’re non-reactive, have high melting, points and are good conductors of heat. Wolframite & scheelite are the
most important members of this class. The subgroups are indicated below:
Wolframite group:
Wolframite (Fe,Mn)2WO4
Scheelite group:
Scheelite Ca(WO4,MoO4)
Wulfenite group:
Wulfenite Pb(MoO4,WO4)

8. PHOSPHATES, ARSENATES AND VANADATES:

The basic building blocks of these minerals are the phosphate ion (PO 4)3-, the arsenate ion (AsO4)3- and the
Vanadate ion (VO4)3-, all having a tetrahedral shape like the sulphate ion, where the 3 negative charges on each
ion that are evenly distributed over the 4 oxygen atoms are neutralized by metal ions hence forming relatively
dense crystals. There are over 240 recognized mineral species but most of them are rare. The phosphates are
abundant minerals and are important as fertilizers. Arsenates and vanadates are considerably less common but
are important source of rare earth elements (REE) especially uranium (U). Examples of these minerals are given
below:
Turquoise CuAl6(PO4)4(OH)8.4H2O
Lazulite (Mg,Fe)Al2(PO4)2(OH)2
Apatite Ca5(PO4)3(OH,F,Cl)
Monazite (Ce,La,Th)PO4
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Erythrite (Co,Ni)3(AsO4)2.8H2O
Vivianite Fe3(PO4)2.8H2O
Variscite( Al,Fe)PO4.2H2O
Carnotite (K2(UO2) 2 (VO4)2.nH2O
Tyuyamunite Ca(UO2) 2(VO4) 2.n H2O
Amblygonite (Li,Na)Al(PO4)(F,OH)
Triphylite LiFePO4
Pyromorphite Pb5(PO4,AsO4)3Cl
Vanadinite Pb5(VO4)3Cl
TorberniteCu(UO2)2(PO4)2.nH2O
Autunite Ca(UO2) 2(PO4) 2.nH2O

9. SULPHATES
Sulphates are compounds of oxygen (O) and sulphur (S) with one or more metals. The oxygen and sulphur form
the sulphate ion; SO42- in which a sulphur atom is surrounded by 4 oxygen atoms located at the corners of a
tetrahedron, with the 2 excess negative charges distributed evenly over the O atoms. Sulphates are complex
minerals because of the numerous number of ways in which cations can be accommodated among SO 42- ions in a
crystal structure. Over 150 have been named and many are hydrated but the common sulphate minerals include:
Gypsum CaSO4.2H2O
Anhydrite CaSO4
Epsomite MgSO4.7H2O
Barite group:
Barite BaSO4
Celestite SrSO4
Anglesite PbSO4
Bronchantite Cu4SO4(OH)6
Alum group: Have general formular M +1M+3(SO4)2.12H2O (where M+1 is a large ion e.g. K +, NH4+, Rb+, Cs+ and
M+3 is a small ion e.g. Al3+, or Fe3+
.

10. CHROMATES: Like other transition metals, chromium combines chemically with O in several oxidation
states but crocoite PbCrO4 and tarapacaite K2CrO4 are the commonest chromates with Cr in the +6 oxidation states
yet in the less common Lopezite K2Cr2O7, Cr is in the +5 oxidation state. Chromates have the ionic group (CrO4)2-
- Chromates are usually treated together with sulphates because they have similar structure. The chromate ion
CrO42- is a tetrahedron like the sulphate ion. The net negative charges on chromate ions are balanced by metal
ions packed among the tetrahedra and holding the structure together.
- The size of these ions and the way they can be packed with the tetrahedra determine the structure. They are
sources of Cr used in eletroplating steel for automobiles bumpers and alloyed with Fe to form stainless steel.

11. BORATES:
Are a complex class of about 45 minerals, all containing boron and oxygen in chemical combination with metals.
About 4/5 of them contain water, and some contain hydroxyl ions (OH -) or halogen ions like chlorine- yet others
are compound borate-phosphates, borate-sulphates or borate-arsenates.
- The basic building block of most borates is a boron ion surrounded by three oxygen ions in the same plane –
BO3. This boron triangle, like the silica tetrahedron, can form infinite rings and chains. Boron fibres are
important in some newly developed materials.
- Borax is the commonest member of this class and has a structure in which the boron ion is surrounded by 3
oxygen ions and one hydroxyl ion. Other combinations are: (BO 3) 3-, (B2O5) 4-, (B2O4) 2-, (B4O8) 4-, BO2)n-n.
Examples include Borax [Na2B4O5(OH)4.8H2O] ± colemanite (Ca2B6O11.5H2O), boracite (Mg3B7O13Cl), Ulexite
NaCaB5O9.8H2O).

12. SILICATES:
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- This class of minerals is of greater importance than any other because 25% of the known minerals and nearly
40% of the common ones are silicates. Almost all rock-forming minerals are silicates and constitute well over
90% of the Earth’s crust.
When the average weight percentages of the 8 most common elements in the Earth’s crust are recalculated on the
basis of atomic percent, out of 100 atoms, 62.5 are O, 21.2 are Si, & 6.5 are Al, Fe, Mg, Ca, Na & K. Therefore,
the dominant minerals of the Earth’s crust are thus shown to be silicates, oxides and other oxygen compounds
like carbonates.
The silicates are classified [not so much on chemical as] on structural basis and more specifically on the way in
which the basic unit (SiO4)4- is linked with the neighboring ions.

- In all silicate structures, the basic unit is the Silica-oxygen tetrahedral group: (SiO4)4- where silicon lies
between four oxygens found at the corners of a tetrahedron.

The different silicate types arise from the various ways in which these silicon-oxygen tetrahedra are related to
each other as illustrated below:

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Therefore, differentiation of the subclasses depends on the way in which the tetrahedra are joined together. We
thus have the following subclasses:

a) Nesosilicates (Independent tetrahedral silicates): Here isolated Si-O tetrahedral groups are present as separate
entities, interconnected by cations & the resulting composition is SiO 4 e.g. forsiterite (Mg2SiO4). Members of
this subclass have a compact habit and a high degree of hardness, a high specific gravity and a high refractive
index. Note that the independent tetrahedral silicates have only one silicon-oxygen tetrahedron e.g.
- Zircon group: Zircon (ZrSiO4), Thorite ( ThSiO4)
- Epidote group: Epidote Ca2(Fe,Al)2O(OH)(Si2O7)SiO4, Zoisite & clinozoisite CaAl(Al3)O(OH)(Si2O4)SiO4
- Garnet Group: Includes the following garnet minerals that are mostly differentiated by their colours plus other
physical characteristics.
* Almandite Fe3Al2(SiO4) 3
* Andradite Ca3Fe2(SiO4) 3
* Grossularite Ca3Al2(SiO4) 3
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* Pyrope Mg3Al2(SiO4) 3
* Spessartite Mn3Al3(SiO4) 3
* Uvarovite Ca3Cr2(SiO4) 3
- Olivive group: Minerals of this group are silicates of bivalent metals and crystallize in the orthorhombic
system. There are a number of species:
* Forsiterite Mg2SiO4
* Fayalite Fe2SiO4
* Olivine (Fe,Mg)2SiO4
* Tephroite Mn2SiO4
* Monticellite CaMgSiO4, e.t.c.

- Subsaturates group:
Kyanite Al2OSiO4
Andalusite Al2OSiO4
Sillimanite Al2OSiO4
straurolite (Fe,Mg)2 (Al,Fe)9O6 l(SiO4)O(OH)2
Topaz Al2 (SiO4)(OH,F)2
b) Sorosilicates (Double tetrahedral silicates/ Couplet silicates): Two Si-O tetrahedra are linked by sharing one
oxygen between them. Thiss produces a double silicon tetrahedral unit. The remaining 6 oxygens are balanced
by cations, which come in to balance the structure. For two such tetrahedra linked, the resulting composition is
Si2O7 e.g. epidote [Ca2(Al,Fe)3(SiO4)(Si2O7)O(OH), akermanite (Ca2MgSi2O7), gehlenite (CaAl(AlSiO7),
allanite/orthite, lawsonite, hemimorphite & Mellilite which is intermediate in composition between gehlenite and
akermanite and hence forms a complete solid solution of minerals.

c) Cyclosilicates (ring silicates): Here 3, 4 or 6 tetrahedra are linked by sharing one oxygen hence closed units of
a ring-like structure are formed giving compositions of Si nO3n, with rings containing up to 6 silicon-oxygen
tetrahedra e.g benitoite (BaTiSi 3O9) with 3 linked tetrahedra & beryl (Be 3Al2Si6O18) with 6. Other members
include tourmaline [(Na,Ca)(Mg,Fe2+,Fe3+,Mn,Li,Al)3Al6(BO3)3(Si6O18)(OH,F)4] & cordierite (Mg2Al4Si5O18).
They are characterized by prismatic, trigonal, tetragonal and hexagonal habits.

d) Inosilicates (chain silicates): Tetrahedra may be joined together to produce chains of indefinite extent,
(elongated in the c-direction of the crystal and bonded to each other by metallic elements) in two ways:

i) single open chains in which the Si:O ratio is 1:3 e.g. pyroxenes; ii) double
closed chains in which alternate tetrahedra in two parallel single chains are cross-linked and the Si:O ratio is 4:11
e.g. amphiboles. Acicular or fibrous habits are predominant
and there is also a characteristic easy cleavage parallel to the elongation. Members crystallize either in the
orthorhombic or monoclinic system.

Single Chain Silicates:

- Pyroxene group: The main members of this group are given in the triangular diagrams while the others are
listed below. The pyroxene group includes both orthorhombic and monoclinic minerals. Thus, the pyroxenes fall
naturally into two divisions, those of orthorhombic symmetry and those of monoclinic symmetry. The
orthorhombic subgroup consists essentially of the compositional series MgSiO 3-FeSiO3 while monoclinic
subgroup includes members having a wide range of chemical composition.
The chemical composition of the pyroxenes can be expressed by the general formular (W) (X,Y) 1+pZ2)6 in wh ich
the symbols W,X,Y &Z indicate elements having similar ionic radii and capable of replacing each other in the
structure. In the pyroxenes, these elements may be
W: Na, Ca
X: Mg, Fe2+,Li, Mn
Y: Al, Fe3+, Ti
Z: Si, Al (in minor amount)
On the basis of chemical composition and crystal symmetry, the following distinct species are recognized:
Orthorhombic pyroxenes:
Enstatite MgSiO3
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Ferrosilite FeSiO3
Hypersthene (Mg,Fe)SiO3
Monoclinic pyroxenes:
Clinoenstatite MgSiO3
Clinohypersthene (Mg,Fe)SiO3
Diopside CaMgSi2O6
Hedenbergite (CaFe2+Si2O6
Augite (Ca,Mg,Fe,Ti,Al)2(Si,Al)2O6 - intermediate between diopside & hedenbergite with some Al
Pigeonite (Mg,Fe2+,Ca)(Mg, Fe2+)Si2O6 – intermediate between augite & clinoenstatite-clinohypersthene
Aegirine (acmite) NaFe3+Si2O6
Aegirine-augite (Na,Ca)(Fe3+,Fe2+,Mg)Si2O6
Jadeite NaAlSi2O6
Spodumene LiAlSi2O6
Johannsenite Ca,(Fe,Mn)Si2O6
Triclinic pyroxenes:
Rhodonite MnSiO3
Wollastonite CaSiO3
Pectolite Ca2NaHSi2O6
Bustamite (Mn,Ca,Fe)SiO3
Pyroxmangite (Mn,Fe)SiO3

…………………………………………………………………………………….

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Double Chain Silicates:

- Amphibole group:
A general formula for all members of the amphibole group can be written as
(WXY)7-8(Z4O11)2(O,OH,F)2 in which the symbols W,X,Y,Z indicate elements having similar ionic radii and
capable of replacing each other in the structure:
W stands for the large metallic cations Ca and Na (K is sometimes present in small amounts);
X stands for the smaller metallic cations Mg and Fe 2+ (sometimes Mn);
Y for Ti, Al, and Fe3+; and
Z for Si and Al.
In the general formula the degree of atomic substitution is as follows:
- Al may replace Si in the Si 4O11 chains to the extent of AlSi 3O11 (the amount of replacement is a function of the
conditions of formation; high-temperature amphiboles can be more aluminous than low-temperature amphiboles).
- Fe2+ and Mg are completely interchangeable.
- The total (Ca, Na, K) may be zero or near zero or may vary from 2 to 3; however, total Ca never exceeds 2, and
K is present only in minor amounts.
- OH and F are completely interchangeable. The maximum is 2, but it may be less, presumably by O replacing
OH or F. Thus, contain water in form of OH- in their structure, which may be replaced by F-.
With these possibilities it is clear that the composition of the amphiboles may be very complex because solid
solution is very common. There are about 30 members but the minerals listed below are common.
However, on the basis of chemical composition and crystal structure five distinct series are recognized:
Orthorhombic amphiboles:
Anthophyllite series (Mg,Fe)7(Si4O11)(OH)2
- Mg predominant over Fe.
- Corresponds to the orthorhombic enstatite-hypersthene series in the pyroxene group.
- Gedrite is another member of this series.

Monoclinic amphiboles:
Cummingtonite series (Fe,Mg)7(Si4O11)2(OH)2
- Fe predominant over Mg.
- Grunerite is another member of this series.
Tremolite series Ca2(Mg,Fe)5(Si4O11)2(OH)2. Actinolite is another member of this series.
Hornblende series CaNa0-1(Mg,Fe,Al)5[(Al,Si)4O11]2(OH)2.
- Pargasite & Hastingsite are some of the other members of this series.
Alkali amhibole series (Na>Ca) e.g.
Glaucophane Na2Mg3Al2(Si4O11)2(OH)2
Riebeckite Na2Fe32+Fe23+(Si4O11)2(OH)2
Arfvedsonite Na3Fe42+Fe3+(Si4O11)(OH)2
Richterite, katophorite, eckermannite, aenigmatite are some of the other members.

d) Phyllosilicates (sheet silicates): Here, 3 oxygens of each tetrahedron are shared with adjacent tetrahedra to
form extended flat sheets. This forms a double chain inosilicate structure extended indefinitely in two directions
instead of just one, giving a Si:O ratio of 2:5, as the fundamental unit in all mica and clay structures. Hence form
a hexagonal planar network responsible for such characteristics as pronounced pseudohexagonal habit and perfect
basal cleavage parallel to the plane of the sheet, low specific gravity and hardness e.g. muscovite.

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They show a wide range of solid solution because positive ions come in to neutralize the negative charges on the
apex of the tetrahedron and hence their complexity. Can be divided into:
1). Two-layer sheet silicates e.g. serpentine Mg 3Si2O5, Kaolinite Al2Si2)5(OH)4
2). Three-layer sheet silicates:
i) K+ between the layers: Muscovite KAl2Si3AlO10(OH)2, sericite, illite, biotite (Mg:Fe<2:1), phlogopite
(Mg:Fe>2:1), glauconite (has complex formular similar to biotite), lepidolite K(Li,Al) 3(Si,Al)4O10(OH)2
ii) Ca2+ & Na+ between layers: Paragonite NaAl2(Si3Al)O10(OH)2, prehnite Ca2(Si3Al)O10(OH)2.
iii) No ions between layers: Talc Mg3Si4O10(OH)2, pyrophyllite Al2Si4O10(OH)2
- Montmorillonite (Ca, Na)(Al, Mg, Fe)4(Si,Al)8O2(OH)4.nH2O
- Vermicullite (Mg,Ca)(Mg, Fe, Al)6(Al,Si)8O20(OH)4.8H2O
- Chlorite (Mg,Al,Fe)(Si,Al)4O10(OH)8
There are generally 2 main groups of sheet silicates i.e.
- the mica group and
- the clay mineral group.
The Mica group: The members of the mica group are readily recognizable because of their characteristic perfect
basal cleavage. The composition of individual specimens may be very complex, but a general formula of the type
W(X, Y)2-3Z4O10(OH,F)2 can be written for the group as a whole. In this formula W is generally potassium (Na in
paragonite); X and Y represent Al, Li, Mg, Fe 2+ , and Fe3+; Z represents Si and Al, the Si: Al ratio being
generally about 3: 1. The different species form a typical isomorphous group. Two members of the group
frequently crystallize together in parallel position e.g. Biotite crystallizes in this way with muscovite, muscovite
with lepidolite, and so forth. In the following list the formulas have been simplified to an ideal type conforming
to the structure established by X-fay investigation.
Muscovite KAl2(AlSi3O10)(OH)2
Paragonite NaAl2(AlSi3O10)(OH)2
Phlogopite KMg3(AlSi3O10)(OH)2
Biotite K(Mg,Fe)3(AlSi3O10)(OH)2
Lepidolite KLi2Al(Si4O10)(OH)2

The clay mineral group: Clay minerals are hydrous aluminosilicates with sheet structure. They consist of sheets
of silicon-oxygen tetrahedra and aluminium or magnesium octahedra linked together by oxygen atoms common
to both.
Structurally, two basic groups of clay minerals exist and these are the Kandite group and Smectite group.
Kandite group members have a two-layered structure consisting of a silica tetrahedral sheet linked to an alumina
octahedral (gibbsite) sheet by common O/OH ions (see figure below). Replacement of Al and Si does not occur so
that the structural formular is (OH) 4 Al2Si2O5. Members of the kandite group are kaolinite, by far the most
important, the rare dickite and nacrite which have different lattice structures, and halloysite which consists of
kaolinite layers separated by sheets of water. Kaolinite has a basal spacing i.e. distance between one silica layer
and the next of 7Å
Smectite group members have a three-layered structure in which an alumina octahedral layer is sandwiched
between two layers of silica tetrahedral (see figure below). The typical basal spacing is 14Å but smectites have
the ability to adsorb water molecules and this changes the basal spacing, which may vary from 9.6 Å (with no
adsorbed water) to 21.4 Å. This feature of smectites, as a result of which they are often called “expandable
clays”, is utilized in thier x-ray identification. Smectite basic formula is 2Al 2O3 8SiO2 2H2O.nH2O
Mont morillonite Al4 (Si4O10)2 (0H)4 nH2O is the common smectite but substitution of the Al 3+ by Fe2+ and Mg2+ by
Zn2+ can take place. A net negative charge resulting from such substitutions is balanced by other cations,
especially Ca2+ and Na+, which are contained in interlayer positions.
Vermiculite has a structure similar to smectite although it is less expandable, with all the octahedral positions
occupied by Mg2+ and Fe2+ and much substitution of Si4+ by Al3+.
Illite, the most common of the clay minerals in sediments, is related to muscovite. It has a three layered structure,
like the smectite but Al3+substitution for Si4+ in the tetrahedral layer results in a deficit of charge which is
balanced by potassium ions in interlayer positions. Some hydroxyl OH -, Fe2+ and Mg2+ ion also occur in illite.
The basal spacing is about 10 Å.
Other clay minerals are chlorite, glauconite and palygorskite. chlorite like smectites and illite has a three–
layered structure, but with a brucite (Mg-OH) layer between (Fig 3.5). Substitute by Fe 2+ occurs in chlorite
imparting the green color and the basal spacing is 14 Å.
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Glauconite is related to illite and the micas but contains Fe 3+ substituting for Al3+. Palygorskite is a magnesium-
rich alumino-silicate.
In addition to the four common clays: illite, kaolinite, montmorillonite and chlorite, there are mixed layers of
these minerals such as illite-montmorillonite or chlorite– montmorillonite.

e) Tectosilicates (Framework silicates): Here, every SiO 4 tetrahedron shares all its 4 oxygens at the corners with
other tetrahedra, giving rise to an open three-dimensional (3D) structural network in which the Si:O ratio is 1:2
e.g. silica (quartz, tridymite, cristobalite, e.t.c.), feldspars, feldspathoids and zeolites. Si 4+ is balanced by two
bivalent oxygen atoms. Si may partly be replaced by Al so that the composition is (Si,Al)O 2. The presence of Al
in the place of Si at the centre of certain tetrahedral makes it possible for stably bonded cations to be present in
the in the framework structures as in the feldspars. Members of this subclass are characterized by low density,
compact habit with few exceptions.

Tecto/framework silicates include:

- Silica group comprises of silica minerals i.e. Quartz, Tridymite, Cristobalite, Opal, coesite, chalcedony (onyx,
agate), e.t.c.
- Feldspar group consists of 2 main series:
* Alkali feldspar series &
* Plagioclase feldspar series
i) Alkali (K-Na) feldspar series; Form 50wt% of igneous rocks and include: sanidine, Orthoclase, microcline,
adularia (habit modification of orthoclase), anorthoclase.
Potassium feldspars have the formular KAlSi 3O8 and include microcline, sanidine, orthoclase, and adularia.
Albite is a sodium feldspar.
ii) Plagioclase (Ca-Na) series; Form 60wt% of igneous rocks and includes: albite, oligoclase, andesine,
labradorite, bytownite, anorthite. Within the plagioclase feldspars, albite and anorthite are the end members
hence albite NaAlSi3 O8 (Ab) occurs in solid solution with anorthite CaAl 2Si2O8 (An) to form other members of
the group. Thus, albite has 0-10%An & 90-100%Ab, oligoclase has 10-30%An & 70-90%Ab, andesine has 30-
50%An & 5o-70%Ab, labradorite has 50-70%An & 30-50%Ab, Bytownite has 70-90%An & 10-30%Ab,
anorthite has 90-100Ab & 0-10%Ab (see figure below).

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Orthoclase
Microcline

No feldspars

Mixed feldspars include: Perthite (KAlSi3O8 & NaAlSi3O8) and anorthoclase (Na,K)AlSi3O8
Miscellaneous feldspars include: Celsian feldspar (BaAl 2Si2O8), strontium feldspar (SrAl2Si2O8-synthetic!), lead
feldspar (PbAl2Si2O8- synthetic)
- Feldspathoid group: The feldspathoids are silica deficient anhydrous silicates richer in interstitial cations than
feldspars. They are a group of alkali-aluminum silicates that appear in place of the feldspars when an alkali-rich
magma is deficient in silica. They are never associated with primary quartz. The following minerals are the more
important members of this group:
Leucite KAlSi2O6 – the commonest potassium feldspathoid abundant in volcanics
Nepheline NaAlSiO4
Sodalite Na8Al6Si6O24Cl2
Cancrinite Na8Al6Si6O24(HCO3)2, nosean, kalsilite, kaliophilite, e.t.c.
*N.B: Analcime, NaAlSi2O6.xH2O, is sometimes included among the feldspathoids; it appears occasionally as a
primary mineral of igneous rocks deficient in silica.
The feldspathoids are not a homogeneous series like the feldspars or the pyroxenes. They are grouped together
more on petrographical than mineralogical similarities. Structurally, the feldspathoids belong to the tectosilicates,
with the SiO4 and AlO4 tetrahedra being linked as in the feldspars, whereas the metal ions (and the chloride,
sulfate, and carbonate ions, when present) fit into cavities in this framework. The feldspathoids are readily
attacked by acids. This characteristic is evidently due to the comparaltvely high Al: Si ratio; the aluminum is
removed in solution and the lattice then collapses, often with the formation of gelatinous silica.
- Zeolite group: These are alumino-silicates containing H2O, Na+, Ca2+ and include analcime, chabazite, e.t.c.
- Scapolite series: This group is less important but the commonest member is cancrinite.

All silicate minerals can be placed in one of the types listed above but few have more than one type of linkage in
the structure. Other constituents of silicate structure e.g. O 2 atoms, OH-, H2O and cations are arranged with the
silicate groups to produce a mechanically stable and electrically neutral structure. The rigid structure of silicates
is caused by the great strength of the Si-O bond but the easy substitutability of the other cations produces
complex solid solution with two or more extreme limits of the different groups of minerals e.g. olivine group,
pyroxene group, amphibole group, feldspar group, e.t.c. as illustrated above.
The above-mentioned minerals are the common members of each class and some of these will be tackled in the
practicals.

Assignment:
Illustrate:
a) How the physical properties of given minerals can give us information on their internal structure.
b) The relevance of mineralogy to solving environmental problems.
END
60 | P a g e By: Mrs. Peggy K. Kalegga