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Schedule

Date 9/26 9/28 10/3

Topic Introduction to Earth Materials Elements, minerals and cosmochemistry Atoms and crystals ionic radii and Paulings rules

Reading Ch. 1 [WB]; Ch. 1-3 [M] Ch. 2 pp. 12-22; [WB]

Ch. 2; pp. 23-31 [WB]

10/5

Atoms and crystals symmetry and crystal structure Ch. 3 pp. 32-44 [WB] Ch. 5 [WB]

10/10 10/12

Crystal growth and habit

Physical and mechanical properties of crystals Ch. 8,11,13 [WB skim]

10/17 10/19 10/24 10/26 10/31 11/6 11/7

Identifying minerals (classification) MIDTERM I Minerals in hand specimen Mineral genesis Introduction to igneous systems Igneous rocks and minerals Introduction to sedimentary minerals

Ch. 14 [WB]; Ch. 7 [M]

Ch. 15 [WB] Ch. 16 [WB] Ch. 18 [WB] Ch. 19;35 [WB] Ch. 21-23 [WB]

11/9 11/14 11/16 11/21

MIDTERM II Sulfides and related minerals Metamorphic environments Ch. 24 [WB] Ch. 26 [WB]

Practical mineralogy soil minerals & cement Ch. 27, 32 [W] skim

11/23 11/28

THANKSGIVING Practical mineralogy gemstones Ch. 30-31 [WB]; Ch. 9-10 [M]

11/30

MIDTERM III

12/9

PAPER DUE BY THE END OF EXAM WEEK

NOTE: Initials in brackets refer to the text book: WB is Wenk and Bulakh

Mineralogy and
M is Murray Evidence from the Earth

Lecture 1 Earth Materials - Minerals and Rocks Overview Details

Minerals:

basic compounds of the solid earth.

~ 3000 known; these 3000 contain all of the

chemical elements of which the earth is made. Rocks: physical mixtures of minerals. Most of the rocks that make up the earth are composed of only ~ 50 of the known minerals Why study? Minerals occur in nearly all inorganic materials of everyday life, and are thus important economically, aesthetically and scientific terms.

Definition of a mineral: A mineral is a naturally occurring, inorganic, homogeneous solid with a definite chemical composition and an ordered atomic arrangement

The crystalline state of matter is the most fundamental property of minerals

Aspects of Earth Materials that we will cover this term: - crystal chemistry - the chemical nature of minerals - crystallography - the study of symmetry and the internal order of crystals - mineral physics - the physical properties of minerals - petrology the study of rocks and the minerals that form them

Lecture 1

Earth Materials - Minerals and Rocks

Minerals:

basic compounds of the solid earth.

~ 3000 known; these 3000 contain all of the

chemical elements of which the earth is made. Rocks: physical mixtures of minerals. Most of the rocks that make up the earth are composed of only ~ 50 of the known minerals Why study? Minerals occur in nearly all inorganic materials of everyday life, and are thus important economically, aesthetically and scientific terms.

ECONOMIC Many minerals have economic value - early on were used for pigments, gemstones for ornamentation, clay for bricks, iron for utensils. Not until the 19th century, however, were metals mined and extracted. ore minerals - minerals from which valuable metallic elements can be extracted industrial minerals - nonmetallic materials used manufacturing (EX: insulators, ceramics, glass, cement, fertilizers, etc.) gangue minerals - those minerals not considered useful but which must be mined anyway Some minerals are now considered "strategic" - [ex. Al and Cr in WWII] Synthetic minerals are now important in materials science (Ex. high-T superconductors)

AESTHETIC Gemstones have been important throughout the history of most cultures, and precious metals, prized for their aesthetic values, form the basis of most economies.

SCIENTIFIC Minerals are the building blocks of all solid parts of the universe, and are therefore fundamental to all aspects of the geological sciences. Some examples: - petrologists use individual minerals that form under restricted conditions of pressure and temperature to map physical conditions within the Earth - geophysicists studying the Earth's interior need to understand how minerals behave under pressure, and how they transmit seismic waves - geochemists use changes in water chemistry to understand processes of weathering and contamination by interaction with mineral surfaces Minerals are also important to a number of related scientific disciplines, including - agricultural sciences (soils) - hydrology (important for understanding development of aquifers and aquitards) - materials science (development of synthetic minerals with specific properties) - medical science (e.g., asbestos) - biological sciences (may have been important as templates for the origin of life)

Definition of a mineral: A mineral is a naturally occurring, inorganic, homogeneous solid with a definite chemical composition and an ordered atomic arrangement

- naturally occuring - this modifier in the definition is considered superfluous by some, but is an important distinction to others (especially gemologists) - homogeneous solid- a single, solid substance (phase) that cannot be physically separated into distinct compounds; this distinguishes minerals from rocks that can be disaggregated into individual mineral constituents

- definite chemical composition -al'>ineral is a chemical element or compound whose composition can be represented by a chemical formula (e.g., SiO 2). The compositions of minerals are either fixed, or vary within specified limits (EX: the mineral olivine may vary in composition from Mg2SiO4 to Fe2SiO4). The composition dictates the mineral structure, which in turn controls the physical properties of the mineral - ordered atomic arrangement - nearly all minerals are crystalline. It means that the internal structure is characterized by periodic or predictable arrays of atoms, ions, or molecules ... this ordered arrangement of atoms is often expressed in the symmetry of the external form. It also means that different minerals may have the same composition but different structures (EX: graphite and diamond).

The crystalline state of matter is the most fundamental property of minerals

In fact, the word 'crystal' is an anglicized version of the Greek word for ice, and was generally employed through the Middle Ages for describing quartz - 'rock crystal' - as quartz was considered to be permanently solidified water. The word has persisted for any quartz clear

enough for ornaments (e.g., New Age uses) or glass.

Aspects of Earth Materials that we will cover this term: - crystal chemistry - the chemical nature of minerals - crystallography - the study of symmetry and the internal order of crystals - mineral physics - the physical properties of minerals - petrology -al'> study of rocks and the minerals that form them

A bit of history Very early man recognized natural pigments and used them in cave paintings. Stone Age man knew something about the hardness of minerals, and about mineral cleavage (how they break) - jadeite commonly used as tools. The mining and smelting of minerals for iron, copper, bronze, lead, silver probably dates back to > 4000 yrs. However, there is no written record of any of this.

300 BC

Theophrastus (pupil of Aristotle) wrote On Stones

23-79 AD

Pliny the Elder recorded a great deal of natural history, and described a number of

minerals mined as gemstones, ores, and pigments. His are the earliest comments on crystal form and the quality of crystal faces. Books 33-37 of his volume on Natural History cover such topics as precious metals (not only mining and uses but also man's greed and exploitation of mineral resources); use of minerals for pigments and painting; mining and metallurgy; marble and other materials used in sculpture; and precious stones.

1556 AD

Georgius Agricola (Georg Bauer; German physician) published De Re Metallica, in

which "I have omitted all those things which I have not myself seen, or have not read or heard of from persons upon whom I can rely." He is considered the founder of geology as a discipline, and his work contributed to the fields of mining geology, metallurgy, mineralogy, structural geology and paleontology. This book became a handbook of mining practices for the next two centuries, and laid the framework of stratigraphic principles. In other books he developed a classification systems for minerals based on their physical properties, gave them standardized names and recorded where they could be found.

1611 AD

Kepler speculated on the planar arrangement of spheres as an explanation for the

symmetry of snowflakes.

1669

Nicolaus Steno recognized that the interfacial angles of quartz crystals were the

same regardless of the size or shape of the crystal. This led to his hypothesis of the constancy of interfacial angles, with the basis that there is an underlying pattern of symmetry to crystal forms. He concluded that processes of crystal growth may allow different faces to dominate under different growth conditions - this results in crystals of the same composition having very different external forms. SIGNIFICANCE OF CRYSTAL FORM

1768 AD

Carolus Linnaeus developed a mineral classification based primarily on external

form. Throughout 18th century, studies of chemistry and mineralogy closely linked, as chemists worked with minerals as their raw materials. Saw the discovery of many new minerals and, with that, identification of many new elements (cobalt, nickel, manganese, tungsten, molybdenum, uranium ...)

1784 AD

The French mineralogist Rene Hauy recognized that the perfection of external

form, the symmetry possessed by crystals, and the existence of perfect cleavage must be manifestations of the internal structure of minerals (involving planes of atoms). In his study of calcite crystals Hauy defined axes of reference for a few crystals, and recognized that all faces on a crystal cut those axes at simple multiples - this led to his conception of crystal structures made up of identical "integral molecules" ... turns out that this concept is similar to the modern concept of a space lattice. RELATIONSHIP BETWEEN CRYSTALLOGRAPHY AND MINERALOGY

1830 AD

Johan Hessel proved that geometric constraints limit the number of crystal classes

to 32, and that only 2-, 3-, 4-, and 6-fold axes of rotational symmetry are possible in minerals.

1837 AD

James D Dana (Yale) completed the 1st edition of A System of Mineralogy, a book

which, in the 4th edition, introduced the chemically based classification system that we still use.

1848

Auguste Bravais proposed the existence of 32 crystal classes He also proposed that there

were only 14 space lattices (that is, he demonstrated that only 14 regular patterns in space can result form the periodic arrangement of points) - his work was the forerunner of space group theory. He also perceived that the 14 space lattices consisted of 7 different lattice symmetries, which correspond to 7 crystal systems.

1870 AD

Petrographic (polarizing) microscope invented in mid-1800s ... brought to this

country by G. Huntington Williams (Johns Hopkins). This allowed determination of the optical properties of minerals, and also made possible the study of fine-grained rocks...

1862-1870 AD Periodic table developed first by a geologist and mineralogist Alexandre Beguyer de Chancourtois (1862), who published a list of all of the known elements in order of their atomic weights. He also recognized that some elements had the same physical properties, thus introducing the idea of periodicity. In 1868 Dmitri Mendeleev expanded on the idea that there was a periodic repetition of elements with similar physical and chemical properties. Ex. atoms numbered 3,11,19,37,55 (Li, Na, K, Rb, Cs) all soft, silvery white metals. All these elements are reactive, and form perfect cubes when combined with chlorine. The resulting compounds (LiCl, NaCl, KCl, RbCl and CsCl) are all colorless and display perfect cubic cleavage. In fact, the symmetry of his table was so compelling that he recognized absence of elements where not yet discovered ...

1895 AD

Wilhelm Roentgen discovered xrays; he showed that xrays were able to pass

through materials that are opaque to light, invisible to the human eye, and could be recorded on photographic paper. For this work Roentgen was awarded the first Nobel Prize in physics in 1901.

1912 AD

The physicist Max von Laue first demonstrated that xrays were diffracted by a

crystal structure (in his case, copper sulphate). The implications of this observation were that the wavelengths of xrays were comparable with the spacing between atoms in crystals. This was the start of an entire field devoted to the determination of crystal structure.

1913 AD

The father-son team W. Lawrence and W. Henry Bragg used diffraction to analyze

the first crystal structure, that is, the precise position of atoms in the structure was ascertained, along with the distances and angles between atoms. This work allowed inferences about atomic size and bond strengths, and thus won the Braggs the Nobel Prize in 1915.

The twentieth century has seen a dramatic increase in the 'tools' available for studying minerals XRD, XRF, electron microprobe, electron microscope, spectroscopic techniques, and, most recently, computer-assisted tomography, TEM and atomic force microscopy, where individual atoms can be imaged...

We now realize that the internal structure of any mineral can be described as a 3-D array of positive (cations) and negative (anions) ions built up by a regular repetition of the unit cell. Symmetry and form of a crystal are determined by the shape of that unit cell. The chemical formula of a mineral expresses the relative proportions of its constitutive elements.

Lecture 2 - Atoms and Elements

1862-1870

Periodic table developed first by a geologist and

mineralogist Alexandre Beguyer de Chancourtois (1862), who published a list of all of the known elements in order of their atomic weights. He also recognized that some elements had the same physical properties, thus introducing the idea of periodicity. In 1868 Dmitri Mendeleev expanded on the idea that there was a periodic repetition of elements with similar physical and chemical properties. Ex. atoms numbered 3,11,19,37,55 (Li, Na, K, Rb, Cs) all soft, silvery white metals. All these elements are reactive, and form perfect cubes when combined with

chlorine. The resulting compounds (LiCl, NaCl, KCl, RbCl and CsCl) are all colorless and display perfect cubic cleavage. In fact, the symmetry of his table was so compelling that he recognized absence of elements where not yet discovered ...

1897 J.J. Thompson discovered electrons; soon after Rutherford recognized that atoms had a small nucleus composed of protons and neutrons (to explain charge and mass).

Bohr model of the atom: Bohr introduced the concept of energy levels, known as quantum numbers. He believed that these levels were arranged as spherical shells, a geometry now known to be too restrictive

SUMMARY OF QUANTUM NUMBERS 1. The principle quantum number (n) determines the major energy level. n = 1-7, with each level also designated by a le to Q, with K (n=1) being the lowest energy level and Q (n=7) the highest.: K is equivalent to (n=1). When an electron moves from a higher energy level to a lower one, energy is released as electromagnetic radiation (usually x-rays); this forms the basis for many of our analytical techniques. The maximum number of electrons allowed at any one level is 2n2.

2. The angular momentum quantum number (l) represents 'subshells' or orbitals, within each energy level. l varies from 0 to n-1, with higher values of l corresponding to higher angular momentum. The corresponding orbitals are s, p, d, and f for l = 0-3; these may hold up to 2,6,10 and 14 electrons, respectively. Electrons fill orbitals from lowest to highest energy. The outermost electrons are called the alence

electrons

3. The magnetic quantum number (m) relates to the magnetic field generated by an electron with angular momentum and may be 1, 1 4. The spin quantum number relates to the intrinsic magnetism of the electron itself, and may be either -1/2 or +1/2

Modern periodic table 1. Periods are rows; the number of the period indicates the orbitals occupied by electrons. EX: elements in 1st period contain electrons in 1s orbital; elements in 2nd period have electrons in 2s and 2p orbitals; elements in 3rd period have electrons in 3s and 3p 4th

to 7th periods have 10 extra elements with electrons in d-orbitals. 6th and 7th periods have additional 14 elements with electrons in f-orbitals [listed separately at the bottom of the table includes rare earth elements and actinide series] 2. Groups -orbitals that are readily given up to produce cations. Elements near the right hand side of the table have nearly full orbitals and thus easily acquire additional electrons; these elements become nions. Properties of elements in the middle of the table (the transition elements) are less predictable. Important groups are the alkalis (I), the alkali earths (II), the halogens (VII), and the transition elements (partially filled d- and f-orbitals, and therefore may have unpredictable behavior).

IONS

Atoms are most stable if electrons completely fill energy levels and sublevels. For this reason, many atoms will either give up or accept extra electrons in order to stabilize their configuration, thereby creating ions. The number of electrons gained or lost is referred to as the valence, or valence state. The process of losing an electron is called oxidation, while gaining an electron is reduction. When one or more electrons are lost from the electron configuration of the atom, a cation is formed. When electrons are added, an anion is formed. Energy required to removed the most weakly held electron is known as the first ionization potential. Note that the noble (inert) elements have the highest ionization energy, while the alkalis (row 1 of the periodic table) have the lowest. However, a more common measure is that

of the ability of an atom in a crystal structure or molecule to attract electrons to its outer shell calculated from known bonds strengths, and known as electronegativity (concept developed by Pauling). Atoms with different electronegativity form ionic bonds with one another, and elements of periodic table can be divided into two groups, electron donors (the metals, in the left-hand side of the periodic table) and electron acceptors (the nonmetals, on the righthand side of the periodic table). Elements with similar electronegativities form covalent bonds (C). Additionally, several elements are found in more than one valence state. EX: Fe can occur in a divalent state Fe2+ (ferrous iron) or Fe3+ (ferric iron). Sizes of ions Anions are formed when atoms gain 1 or more electrons Cations are formed when atoms lose 1 or more electrons Anions are thus generally larger than cations, and crystal structures can be envisaged as large spheres packed around small spheres in such a way that the space between spheres is minimized, and positive and negative charges are balanced. Thus the chemical classification system that we use is based primarily on the anion or anion group.

Atomic number and mass Atomic number is the number of protons in an element's nucleus (Z) and, in a neutral atom, is also equal to the number of electrons. It is also close to the number of electrons in most ions. Most important in controlling elemental properties. Atomic mass (A) is the number of protons (Z) + number of neutrons (N). Most elements have several different isotopes (same Z different N). Although chemists don't worry much about isotopes, very important in geology as climate tracers and for radioactive dating of geologic materials. A mole of an element is defined as the amount of that element that has its weight in grams equal to its atomic weight. Given by Avogadro's number (N): one mole of an element or compound always has 6.022 x 1023 atoms.

EX: Box 1.2

What is a mole of quartz?

SiO2 = 28.0855 + 2(15.994) = 60.0843 grams

Bonding in minerals A chemical bond exists when the forces acting between two elements are sufficient to form a new aggregate or molecule. There are four primary types of chemical bonds: Covalent bonds involve shared electrons in outer shell; this means that an electron pair occupies two different orbitals simultaneously; such bonds are directional because of this orbital control. Covalent bonds are strong (diamond) and molecules with these bonds tend to be electrical insulators. Ionic Metallic bonds are al'>acteristic of native metals, which are elements that easily lose their outer electrons. In a metal there are more bond sites (empty orbitals) than there are electron pairs to fill them. Detached electrons mover freely through the structure, thus metals are good electrical conductors. Van der Waals; not important in most minerals (except graphite).

Type of bonding in minerals determines both the symmetry and the physical properties of minerals; the most important bond in many minerals that we will examine is the Si-O bond, which is partly ionic and partly covalent (called polar covalent); directionality of covalent part of bond is preserved.

Effects of size valence state is the As important as relative size of the two ions

(ionic radius), which dictates their separation. Note that the attractive force increases as the atoms approach each other, with a maximum when they are just touching. As soon as their electron clouds overlap, repulsive forces become strong (counteracts attractive energy). The minimum energy configuration occurs where the distance between centers of ions is equal to the sum of their ionic radii (closest packing).

Lecture 2 - Atoms and Elements


Overview Details

A. Bohr model of the atom B. Quantum numbers 1. The principle quantum number (n) determines the major energy level. n = 1-7, with each level also designated by a letter: K - Q, with K (n=1) being the lowest energy level and Q (n=7) the highest. 2. The angular momentum quantum number (l) represents 'subshells' or orbitals, within each energy level. l varies from 0 to n-1, with higher values of l

corresponding to higher angular momentum. The corresponding orbitals are s, p, d, and f for l = 0-3; these may hold up to 2,6,10 and 14 electrons, respectively. Electrons fill orbitals from lowest to highest ene

3. The magnetic quantum number (m) relates to the magnetic field generated by an electron with angular momentum; may be 1, 1 4. The spin quantum number relates to the intrinsic magnetism of the electron itself, and may be either -1/2 or +1/2

C. Modern periodic table 1. Periods - rows; the number of the period indicates the orbitals occupied by electrons 2. Groups - columns; have valence electrons in similar orbitals, and hence they have similar chemical properties. D. Ions Anions are formed when atoms gain 1 or more electrons Cations are formed when atoms lose 1 or more electrons Anions are thus generally larger than cations, and crystal structures can be envisaged as large spheres packed around small spheres in such a way that the space between spheres is minimized, and positive and negative charges are balanced.

E. Atomic number and mass Atomic number is the number of protons in an element's nucleus (Z) - most important in controlling elemental properties. Atomic mass (A) is the number of protons (Z) + number of neutrons (N). A mole of an element is defined as the amount of that element that has its weight in grams equal to its atomic weight. Given by Avogadro's number (N): one mole of an element or compound always has 6.022 x 1023 atoms.

F. Bonding in minerals Covalent - shared electrons in outer shell

Ionic -bond between a cation and an anion where complete electron transfer has occurred Metallic - detached electrons move freely through the structure Van der Waals

Effects of size - The minimum energy configuration occurs where the distance between centers of ions is equal to the sum of their ionic radii (closest packing).

Cosmochemistry

1. Origin of the elements and Earth

Big Bang First determined by E Hubble, who measured the speed at which some galaxies were moving away from the Earth. He then recognized that the universe seemed to be expanding, and that he could use the measured velocities of expansion to figure out the time of origin.

Radiometric dating of meteorites indicates that the solar system began to form about 4.56 Ga BP as the solar nebula, consisting mostly of molecular H2 plus He and minor Be and Li (the only products of the Big Bang). About 2% estimated to be heavier dust created by nuclear synthesis reactions in early stars and supernovae. The first 100,000 years: The nebular cloud began to collapse because of gravitational interactions. Also flattened into a disk because of rotation (centrifugal forces), with 1-10% of mass constituting the central disk. Most of the mass gradually lost angular momentum and collapsed into the center to form the sun. Planetesimals (kilometer-size bodies) began to form by accretion, and gravitational collapse provided heat that eventually permitted nuclear synthesis (fusion) of hydrogen to helium. The next 10 million years: known as the T-Tauri stage; during this stage the solar wind began to emanate radially outward from the and the nebula lost about 1/2 of its initial mass during this stage. Of the remaining material, 99.9% of the mass collapsed to form the

sun; the other 0.1% remained in the disk. The disk material had sufficient mass to contract to the median plane, where it aggregated into the planets. Planet formation

took place under conditions of strong gradients in T and P generated by the early sun. As a result, the more volatile elements evaporated in the inner, hotter portion, were stripped off by the solar winds, and condensed to solids further outward where the temperatures were sufficiently low. The actual condensation temperatures depended on the elements/compounds involved. Only the most refractory elements condensed in the innermost zone; with the more volatile elements condensed in the outermost zone. As a result, the nebula experienced chemical differentiation, with refractory oxides (Al2O3, CaO, TiO2) concentrated in the innermost portions of the solar system, and FeNi alloys, Fe-Mg-Ni silicates, alkali metals and silicates, sulfides, hydrous silicates, H2O, and solids of ammonia & methane concentrated progressively outward.
Condensed solids then began to accrete as planetesimals. The terrestrial (Earth-like) planets (Mercury, Venus, Earth, Mars) formed from the more refractory materials, as well as the parent bodies that produced asteroids and meterorites. In the outer portions, the large gaseous planets formed (Saturn, Jupiter, Uranus, Neptune). [Pluto is anomalous in orbit and probably composition; may actually be an escaped moon]

IF YOU'D LIKE TO KNOW MORE ABOUT THE SOLAR SYSTEM...

THUS the Earth's composition is a product of its accretion history. However, as the process of chemical differentiation was not perfectly efficient, the Earth contains some of every stable element (not just those elements that were condensable at our distance from the sun). That said, only 7 elements comprise 97% of Earth: O (50.7%), Mg (15.3%), Fe (15.2%), Si (14.4%), S (3.0%), Al (1.4%), Ca (1.0%), consistent with solar abundances and condensates anticipated for Earth's position.

2. Differentiation of the Earth Differentiation may have started during accretion; continued afterward because of intense heating by gravitational collapse, impacts, and radioactive heat. Eventually part of the Earth melted, which increased mobility such that dense melts moved inward and light melts moved to the surface. Gravitational energy released by this process may have melted the entire Earth (magma ocean), with the possible exception of the outermost surface. The result was a layered Earth structure.

Goldschmidt (1937) proposed that Earth's elements separate into different phases; this concept gave rise to the terms: lithophile (stone-loving) elements form the light silicate phases chalcophile (copper-loving) elements form an intermediate sulfur phase

siderophile (iron-loving) elements form a dense metallic phase

However, although we still use this classification it has limited applicability. For example, Fe, a siderophile element, is found in all three phases. This is partly dictated by the availability of the anions (particularly S).

These three layers do not correspond to the three layers of the Earth. The core is siderophile, but chalcophile component likely dissolved in siderophile core and was never a separate phase. Mantle is the lithophile phase; Earth's crust had not yet formed.

O is the most common element, and the dominant anion. It combined with silica to form the outer lithophile layer, with neutrality provided by the addition of other cations. Thus the abundance of O determined the thickness of the upper layer. Most common lithophile elements of early Earth:

olivine orthopyroxene clinopyroxene

(Mg,Fe)2SiO4 (Mg, Fe)SiO3 Ca(Mg,Fe)Si2O6

The inner siderophile layer comprised the excess of siderophile cations (mostly Fe) that were left over after all the O, S depleted. All other elements (remaining 3% of Earth's mass) went into one of these layers in accordance with the atom's affinity. Again, differentiation not perfect, thus we find gold (siderophile) and copper (chalcophile) etc. at the Earth's surface.

3. How do we know this? Best interpretations of available data; scenario presented is consistent with physical laws of celestial mechanics, gravity, nuclear synthesis, etc., as well as with the seismic probes and samples (mantle xenoliths) we have of the Earth's interior.

What evidence do we have?

gravitational constant - use to calculate Earth's mass (average density), which is 5.52 g/cm3. Density of surface rocks rarely > 3, therefore the Earth must contain a large proportion of very dense material. nebular composition e material the comprises the solar system can be measured using various types of spectroscopy (emission of characteristic light spectra). H by far the most abundant, as it made up most of original nebula. All other elements except He, the next most abundant, were synthesized from H in the sun and other stars. Together H & He comprise > 99% of all atoms in solar system. Decrease in abundance with increasing Z reflects increasing synthesis difficulty. Also evident is (1) relatively low abundance of some elements such as Li, Be, B, Sc is a consequence of their formation only by spallation by cosmic rays, supernova explosions and because of their consumption in subsequent fusion processes; (2) sawtooth pattern "Oddo-Harkins rule", which says that atoms with even numbers are more stable because their nuclei are more tightly bound. (3) Fe is particularly stable because its nucleus is tightly bound Note abundance of Fe (plus Mg, Ni) in solar system relative to Earth's crust; used to infer that these components must constitute much of the Earth's core. Fe is also dense enough to satisfy density requirement. seismic studies locities of P and S waves in various materials can be measured and compared with known seismic velocities. Reflection and refraction of seismic waves at discontinuities provides direct evidence for layered structure, while absence of shear wave transmission indicates the liquid nature of the outer core. mantle rocks ophiolites, xenoliths

3. Meteorites Solid extraterrestrial objects that strike the Earth; many are likely fragments derived from collisions of larger bodies (particularly asteroid belt between Mars and Jupiter). Believed to represent early stages in development of the solar nebula, and thus provide information about state of early solar system. Classification:

irons -composed of Fe-Ni alloy stones - composed of silicates (can be difficult to tell from terrestrial rocks, but comprise about 94% of meteorites) chondrites contain chondrules (spherical silicate inclusions that appear to have formed as droplets of glass); considered to be "undifferentiated" meteorites most primitive

achondrites do not contain chondrules stony-irons - contain subequal amounts of each

TO SEE PICTURES OF METEORITES...

Chondrite Earth Model (CEM) - average composition assumed to represent original composition of the Earth. However, Earth is denser, and has a higher Fe/Si ratio, than provided by

CEM.

Cosmochemistry Details

1. Origin of the elements and Earth

Big Bang (~15 Ga)

Solar system (~ 4.56 Ga) The first 100,000 years The next 10 million years

BOTTOM LINE: the Earth's composition is a product of its accretion history. However, as the process of chemical differentiation was not perfectly efficient, the Earth contains some of every stable element (not just those elements that were condensable at our distance from the sun). That said, only 7 elements comprise 97% of Earth: O (50.7%), Mg (15.3%), Fe (15.2%), Si (14.4%), S (3.0%), Al (1.4%), Ca (1.0%), consistent with solar abundances and condensates anticipated for Earth's position.

2. Differentiation of the Earth Goldschmidt (1937) proposed that Earth's elements separate into different phases this concept gave rise to the terms: lithophile ("stone-loving") elements form the light silicate phases chalcophile ("copper-loving") elements form an intermediate sulfur phase siderophile ("iron-loving") elements form a dense metallic phase

These three layers do not correspond to the three layers of the Earth. The core is siderophile, but chalcophile component likely dissolved in siderophile core and was never a separate phase. Mantle is the lithophile phase; Earth's crust had not yet formed.

Most common lithophile components of early Earth (and mantle): olivine orthopyroxene clinopyroxene (Mg,Fe)2SiO4 (Mg, Fe)SiO3 Ca(Mg,Fe)Si2O6

3. How do we know this? gravitational - use to calculate Earth's mass (average density), which is 5.52 g/cm3. Density of surface rocks rarely > 3, therefore the Earth must contain a large proportion of very dense material. nebular composition -Together H & He comprise > 99% of all atoms in solar system. Decrease in abundance with increasing Z reflects increasing synthesis difficulty. Also evident is (1) relatively low abundance of some elements - Li, Be, B, Sc consequence of formation only by spallation by cosmic rays, supernova explosions and because of their consumption in subsequent fusion processes, and (2) "sawtooth" pattern "Oddo-Harkins rule", which says that atoms with even numbers are more stable because their nuclei are more tightly bound. (3) Fe is particularly stable because its nucleus is tightly bound

Note abundance of Fe (plus Mg, Ni) in solar system relative to Earth's crust; used to infer that these components must constitute much of the Earth's core. Fe is also dense enough to satisfy density requirement. seismic studies -velocities of P and S waves in various materials can be measured and compared with known seismic velocities. Reflection and refraction of seismic waves at discontinuities provides direct evidence for layered structure, while absence of shear wave transmission indicates the liquid nature of the outer core. mantle rocks -ophiolites, xenoliths

3. Meteorites Solid extraterrestrial objects that strike the Earth; many are likely fragments derived from collisions of larger bodies (particularly asteroid belt between Mars and Jupiter). Believed to represent early stages in development of the solar nebula, and thus provide information about state of early solar system.

Classification: irons -composed primarily of Fe-Ni alloy (probably fragments of the core of some terrestrial planet; contain both siderophile - Fe-Ni alloy and chalcophile FeS troilite phases) stones -composed of silicates (can be difficult to tell from terrestrial rocks, but comprise about 94% of meteorites) chondrites - contain chondrules (spherical silicate inclusions that appear to have formed as droplets of glass); considered to be "undifferentiated" meteorites most primitive achondrites -do not contain chondrules stony-irons - contain subequal amounts of each

Chondrite Earth Model (C - average composition assumed to represent original composition of the Earth.EM) However, Earth is denser, and has a higher Fe/Si ratio,

than provided by CEM.

Lecture 7 Classification

First, to continue where we left off last time

Last week we discussed physical properties of minerals, particularly those related to the interaction of light with the mineral surface or interior. Now Id like to briefly discuss some other physical properties that youve had a chance to use in lab.

4. Density (specific gravity)

Ratio of the weight of a substance and the weight of an equal volume of water. Determined as

Specific gravity (the ratio) can be measured by a Jolly balance; density requires a pycnometer.

The density can also be calculated from the mineral formula if you know the dimensions of the unit cell and the number of formula units per unit cell.

5. Magnetism

Magnetite and pyrrhotite are the only common minerals with a magnetic signature.

ANISOTROPY AND PHYSICAL PROPERTIES

Many physical properties are anisotropic, such that their magnitude depends on the direction in the crystal. An easy way to picture this is by a mechanical analogue with springs of different stiffness in different directions net displacement is the result of the vector sum of the components, thus the direction of displacement is not necessarily the same as the direction of the applied force.

DIRECTIONAL PROPERTIES

thermal conductivity relateds heat flow to temperature gradient

electrical conductivity relates electrical current density to electric field

diffusivity relates atomic flux to concentration gradient

elastic properties relate strain (extent of deformation) to applied stress

seismic properties relate to velocity of seismic wave propagation (related to density, rigidity, bulk modulus)

optical properties relate to refractive index variations Examples: calcite shows double refraction ulexite is a natural fiber optic

Each of these properties is controlled by the crystal structure, such that the directional variation in the value of a physical property must be consistent with the point group symmetry of the crystal since physical properties can always be broken into three mutually perpendicular components, the symmetry of physical properties may be greater than the symmetry of the crystal itself

Physical properties may be isotropic uniform in all directions (isometric crystals) uniaxial similar in two directions and different in the third (hexagonal and tetragonal crystals) biaxial different in all three directions (orthorhombic, monoclinic, trigonal crystals)

Classification of Minerals

While there are many different ways that one could classify minerals (color, shape, association, etc.), you can already guess that mineralogic classification systems are based primarily on composition and structure. We use a classification system that is little changed from that originally proposed by Dana, and assign minerals to classes based on either their anions or anion complexes. Thus the mineral class is related to the mineral formula. It also means that minerals within the same class tend to have similar structures, and thus similar physical properties. Finally, minerals in a single class are often found in association with one another.

Common mineral classes and example minerals are listed in Table 2.5 of your text. Of these, the silicates are the most abundant, and are subdivided on the basis of the structure of the silica tetrahedral (see below). Other common mineral classes (and ones that you have seen or will be seeing in lab) include halides oxides hydroxides [with anions Cl-, F-, Br-, I-] [with anion O2-] [with anion complex OH-]

carbonates

[with anion complex CO32-]

native elements sulfides [with anion S2-]

Classification of silicates

In most silicates, Si4+ exists in 4-fold coordination with O2-. The subclasses are classified according to how the tetrahedral are linked (see Table 2.6 in your text); because the linkage determines the number of Si per O, each subclass has its own distinctive Si:O ratio. The most common subclasses of silicates are:

Framework silicates (including quartz and feldspar, the most abundant elements in the Earths crust); Si:O ratio is 2:1, although in many framework silicates Si is replaced to some extent by Al (as in the feldspars). Framework silicates are subdivided by groups shown in Table 2.7

Sheet silicates this group includes serpentines, clays and micas. Sheet silicates consist of sheets of SiO4- tetrahedral (arranged as joined 6-fold rings) separated by octahedral layers that contain cations (commonly either Al3+ or Mg2+). The Si:O ratio in these minerals is 2:5 (which often appears in the mineral formula as 4:10). The tetrahedral and octahedral layers can then be stacked in different ways for example, serpentine and kaolinite have alternating T and O layers, while pyrophyllite and talc have TOT sequences that are loosely joined to each other by van der Waals bonds (hence the softness of talc)

Single chain silicates the single chain silicate group contains all of the pyroxenes, with structures based on chains of SiO4- tetrahedral linked by shared (often called bridging) oxygens. The Si:O ratio is 1:3 (often written as 2:6). The most common pyroxenes involve solid solutions between Mg, Fe and Ca, but other forms may include Na (jadeite) and Li (spodumene). In the image below diopside is the pale blue mineral more commonly, however, it is green. Chrome diopside is a beautiful dark green gemstone.

e) is also called jade tends to be a darker color).

Jadeite is one mineral known as jade, although nephrite (an amphibol (and green in

Double chain silicates these structures are intermediate between the pyroxenes and the sheet silicates in having linked chains of tetrahedral, separated by octahedral layers. The characteristic Si:O ratio is 4:11 (8:22). This group includes all of the amphiboles and the pyroxenoids.

Isolated tetrahedra this group contains some important minerals, many of which you already know. First there are the olivines, with Si:O ratios of 1:4. Also in this group are the aluminosilicates (sillimanite, kyanite, and andalusite) with fairly invariant formulas of Al2SiO5.

Finally, there are some other distinctive minerals such as staurolite (whose name means cross), titanite (CaTiSiO5), topaz, and zircon (ZrSiO5).

HOMEWORK

Id like you to try to work through the process of normalizing a mineral analysis (that is, converting a chemical analysis to a mineral formula) between now and Thursdays class. I will not require you to hand your work in instead, bring it with you and I will go over it at the start of class.

Analytical instruments can be used to obtain chemical analyses. The resulting data are generally reported in weight percent of the major oxides in the mineral. Use the following chemical analysis and the instructions below to determine the specific mineral formula and the identity of the unknown mineral. Be sure to show all your work! Using a spreadsheet program like Excel makes these calculations easier, although this particular analysis can be done pretty quickly by hand as well. A similar set of instructions appears in Box 1.5 (p. 22) of your text.

Analysis

SiO2
FeO 20.38%

38.05%

MgO

41.57%

Total

100 %

(Assume the known total number of oxygen atoms per formula unit is 4)

Mineral formula_______________________________________

What mineral is this?________________________________

Steps for determining a specific mineral formula:

1) Convert oxide wt.% into molecular proportion of each oxide. This is done by dividing the wt. % of each oxide by the molecular weight of the oxide. This gives the molecular proportion of each oxide. (The molecular weight for each is calculated from their atomic weights.)

2) Multiply the molecular proportion for each oxide by the # of oxygen atoms present in each oxide. This gives the O atomic proportion.

3) Sum the O atomic proportion column.

4) Divide the known total # of Oxygen atoms per unit cell in the mineral by the sum of the O atomic proportion. (e.g. Olivine is know to have 4 oxygen atoms in its mineral formula, Feldspars have 8). This operation gives you a normalization factor.

5) Next, normalize the O atomic proportions from each oxide by multiplying each entry by this normalization factor. This gives the number of anions based on the known number in the mineral formula.

6) Determine the number of cations associated with the oxygens by dividing the number of anions determined in step 5 by the number of oxygens in the reported oxide. (e.g. SiO2 has 2 O per 1 Si, Al2O3 has 1.5 O per 1 Al).

7) The number you obtain after doing step six is the number of cations that are in the final mineral formula.

EXAMPLE:

Olivine:

step 1
Element Oxide wt. % Molec. Wt. Molec. Prop. of oxides 0.530179 0.816247 0.011982 0.210675

step 2

step 4

step 5 step 6 step 7


Oxygen Cations per cation 2 1 1 1

# O atomic Normaliza. # of Oxygen Anions proportion factor 2 1 1 1 1.060368 0.816247 0.011982 0.210675 1.90543 1.90543 1.90543 1.09543 2.02043 1.5553 0.02283 0.04142

SiO2 FeO MnO MgO

31.85 58.64 0.85 8.49

60.074 71.841 70.937 40.299

1.0102 1.5553 0.02283 0.40142

(step 3) Total
Normalization factor=

2.09926 4Oxygens/2.09926

Formula: (Fe 1.555 Mg 0.401 Mn 0.023) Si 1.01 O 4


Lecture 5 Classification of Minerals; Crystal growth

Review from last time - Paulings Rules:

1. The Coordination (radius ratio) Principle a coordination polyhedron of anions surrounds each cation. The cation-anion distance is determined by the sum of the cation and anion radii and the number of anions coordinating with the cation is determined by the relative size of the cation and anion.

2. Electrostatic Valency Principle in a stable ionic structure, the total strength of the valency bonds that reach an anion from all neighboring cations is equal to the charge of the anion.

3. Sharing of Polyhedral Elements I the existence of edges (and particularly faces) common to coordination polyhedra decreases the stability of ionic structures

4. Sharing of Polyhedral Elements II in a crystal containing different cations, those with large valence and small coordination number tend not to share polyhedral elements with each other.

5. Principle of Parsimony the number of essentially different kinds of constituents in a crystal tends to be small.

Chemical Variation in Minerals

Paulings rules can be used to explain not only crystal structure, but also allowed variations in mineral compositions.

Only a few minerals have a fixed composition even quartz, which comes about as close as possible to being purely SiO2, has trace amounts of other elements, yielding varieties of quartz like amethyst rose quartz Fe3+ Ti4+

smoky quartz structural defects

This raises an issue of terminology: major elements are fundamental to the mineral, control its structure and gross physical properties

minor elements are present in small amounts (up to a few %), usually as substitutes for major elements trace elements are present in extremely small amounts but are often responsible for mineral color.

We also need to introduce the idea of mineral formulas, which is how we describe mineral compositions. Conventions: Cations are listed before anions and anion complexes Subscripts outside of parentheses refer to everything inside cations in same structural site are grouped together elements separated by a comma inside parentheses are substitution pairs Charges must balance Largest cations are listed first (listed in order of decreasing coordination number) Loosely bonded interstitial compounds are on the right; when water occupies an interstitial site it is often separated from the main formula by a dot.

EX:

olivine natrolite montmorillonite

(Mg, Fe)2SiO4 Na2Al2Si3O10.2H2O (Na, Ca)(Al,Mg)2(Si4O10)(OH)2.nH2O

We can also write a single formula in different ways to convey different information. Lets look at an oxide mineral that is a type of spinel.

Idealized formula

Fe2ZnO4

The cations are Fe3+ and Zn2+, and they coordinate with O2-, which is the only anion. Based on knowledge of cation size, we can anticipate that Zn will be in 4-fold (tetrahedral) coordination and Fe in 6-fold (octahedral) coordination, consistent with the order in which they are written.

Structural formula

VI

Fe2IVZnO4

Often, a structural site may be interchangeably occupied by different cations as part of a solid solution series. In this case, the interchangeable cations are grouped within parentheses. The spinel formula shown above can be modified to show that the octahedral sites can hold either Fe3+ or Mn3+ ions and the tetrahedral sites can hold either Zn2+ or Fe2+ ions.

General formula

(Fe, Mn)2(Zn,Fe)O4

Note that in this formula, the cations in parentheses are conventionally assumed to be listed in order of decreasing abundance that is, Fe is more likely than Mn to occupy the octahedral site, while Zn is more likely than Fe to occupy the tetrahedral site.

Using certain analytical techniques, it is possible to determine the proportion or relative abundance of each type of cation occupying a substitution site in a given sample. This information yields the samples specific mineral formula, which could look something like this: Specific formula (Fe1.4 Mn0.6)(Zn0.8 Fe0.2)O4

In this example, Fe3+ ions proportionally across the structure occupy 1.4 of every two filled octahedral sites, while Mn3+ ions occupy the remaining 0.6 of every two filled octahedral sites. Similarly, Zn2+ ions proportionally occupy 0.8 of every filled tetrahedral site, while Fe2+ ions occupy 0.2 of every filled tetrahedral site.

HOMEWORK

Solid Solutions The discussion above leads directly to a discussionof substitutions of one element for another within the stable mineral structure called isostructural substitutions. This process is known as solid solution, defined in a mineral structure as specific atomic sites that are occupied in variable proportions by two or more different chemical elements.

Three main factors determine whether or not solid solution is possible:

1. Comparative size of ions (atoms, molecules) that are substituting for one another This results directly from Paulings first rule of radius ratios, in that ions that substitute must be able to occupy the same interstitial site. Generally, for this to happen the radius ratios must be within 15%; substitution is unlikely when the radii differ by > 30%. 2. The valence state (charge) of the ions involved in the substitution. This stipulation relates to Paulings second rule, which involves electrical neutrality. If the substituting elements have the same charge (Fe2+ and Mg2+; Na+ and K+), then neutrality will be maintained. If the charges are different (Al3+ and Si4+; Na+ and Ca2+), then another ionic substitution must take place to maintain neutrality this is called a coupled substitution, for example Ca2+Al3+ for Na+Si4+ 3. The temperature at which the substitution takes place. Substitution of ions of different size is favored by elevated temperatures, where the structure is expanded and there is greater tolerance for size variation.

Types of substitution

Simple cationic/anionic: Ions of similar size and charge substitute for each other. Examples:

K = Na

KCl NaCl (sylvite - halite); KAlSi3O8-NaAlSi3O8 (orthoclase albite) Mg2SiO4 Fe2SiO4 Mn2SiO4 (forsterite fayalite - tephroite; olivine) MgSiO3 FeSiO3 (enstatite ferrosilite; pyroxene) KCl - KBr (Zn, Fe)S (sphalerite)

Mg = Fe (= Mn)

Cl - Br Fe = Zn

Depending on the relative sizes of the ions involved, the solid solution may be either partial (K = Na; ionic radii 1.46:1.08 in 6-fold coordination) or complete (Mg = Fe; ionic radii 0.77:0.80 in 6fold coordination).

Coupled substitution: For electrical neutrality to be maintained, substitution of two elements requires an additional substitution. Examples:

Fe2+ + Ti4+ = 2Al3+ Ca2+Al3+ = Na+Si4+ Mg2+ + 2Al3+ = 2Fe2+ + Ti4+

(Al, Ti)2O3 (corundum, var. sapphire) CaAl2Si2O8-NaAlSi3O8 (plagioclase) (Mg, Fe)(Al, Ti)2O4 (spinel group)

Interstitial substitution: Between some ions or ionic groups there may exist structural voids. Particularly where these have the form of channels (as in beryl and some zeolites), they may be partially filled. Example:

BERYL Be3Al2Si6O18 may contain substantial amounts of Li, Na, K, Rb through coupled substitutions involving Si4+ and Al3+

Vacancy solid solution: remember that close packing of anions often creates more cation sites than can be filled. Partial filling of these sites forms another type of substitution. A common example is the mineral amphibole, which has the end member

TREMOLITE

[] Ca3Mg5Si8O22(OH)2

where [] represents a vacant site that may be filled using the coupled substitution

[] + Si4+ = Na+Al3+ Omission solid solution: this is the opposite of filling a vacancy, that is, creating one. An example is the substitution of the large Pb2+ cation for the equally large K+ cation as

K+ + K+ = Pb2+ + []

The result of these substitutions is a wide variety of mineral and mineral formulas!!!

Crystallization and polymorphs

So how, and why, do crystals form?

Crystals typically form from a supersaturated solution, as we experimented with in lab. That solution may be an aqueous phase, a magma, or a gas. During metamorphism we also see examples of solid state crystallization (that is, one crystal growing from another solid).

We may create a supersaturated solution by changing the temperature, changing the pressure, or changing the composition (by either adding or subtracting components). We usually show mineral stability fields using phase diagrams, as shown below for the system SiO2.

The figure shows graphically the ranges of pressure-temperature conditions under which each of the different polymorphs are stable. At low temperatures and pressures like those at the Earth's surface, low quartz is the thermodynamically stable polymorph, accounting for its great abundance. As P and/or T change however, the low quartz structure becomes unstable, and the SiO4 tetrahedra rearrange themselves to form new structures each of which has different symmetry:

Polymorph low quartz high quartz tridymite cristobalite coesite stishovite

Symmetry trigonal hexagonal orthorhombic tetragonal monoclinic tetragonal

You will note from the figure that the reaction boundaries separating adjacent stability fields are either quite P-dependent (roughly parallel to the T-axis, e.g., coesite = stishovite), quite Tdependent (roughly parallel to the P-axis, e.g., high quartz = liquid), or dependent on both P and T. As a rule, if a reaction is very pressure dependent, this means that the polymorph on the high-P side of the boundary has a lower molar volume that that on the low-P side of the boundary. This is illustrated by the transition from coesite (density = 2.93 g/cc) to stishovite (density = 4.30 g/cc), which is accompanied by a nearly 50% increase in density or a nearly 50% decrease in molar volume.

The phase transitions between the various polymorphs are of two types with that between low quartz and high quartz being of a type referred to as displacive and all others being of a type known as reconstructive. The reconstructive transitions are most familiar and consist of actual breaking of bonds and formation of new bonds in a different configuration. Transitions of this type require considerable energy (enthalpy of reaction) to break the bonds and, as a consequence, these reactions are often sluggish leading to the common preservation of high-T or high-P forms at conditions way outside of their stability fields. By contrast, the displacive transitions do not require any breakage of bonds but instead, bonds and polyhedra rotate to new positions with different symmetry. Transitions of this type are extremely rapid and consequently, only the low-T, low-P forms are preserved at the Earth's surface for us to collect.

Lecture 5 - OVERVIEW Classification of Minerals; Crystal growth

Details

Review from last time - Paulings Rules:

1. The Coordination (radius ratio) Principle a coordination polyhedron of anions surrounds each cation. The cation-anion distance is determined by the sum of the cation and anion radii and the number of anions coordinating with the cation is determined by the relative size of the cation and anion.

2. Electrostatic Valency Principle in a stable ionic structure, the total strength of the valency bonds that reach an anion from all neighboring cations is equal to the charge of the anion.

3. Sharing of Polyhedral Elements I the existence of edges (and particularly faces) common to coordination polyhedra decreases the stability of ionic structures

4. Sharing of Polyhedral Elements II in a crystal containing different cations, those with large valence and small coordination number tend not to share polyhedral elements with each other.

5. Principle of Parsimony the number of essentially different kinds of constituents in a crystal tends to be small.

Chemical Variation in Minerals

This raises an issue of terminology: major elements are fundamental to the mineral, control its structure and gross physical properties minor elements are present in small amounts (up to a few %), usually as substitutes for major elements trace elements are present in extremely small amounts but are often responsible for mineral color.

We also need to introduce the idea of mineral formulas, which is how we describe mineral compositions.

Idealized formula

Fe2ZnO4

Structural formula

VI

Fe2IVZnO4

General formula

(Fe, Mn)2(Zn,Fe)O4

Specific formula

(Fe1.4 Mn0.6)(Zn0.8 Fe0.2)O4

Solid Solutions The discussion above leads directly to a discussion of substitutions of one element for another within the stable mineral structure called isostructural substitutions. This process is known as solid solution, defined in a mineral structure as specific atomic sites that are occupied in variable proportions by two or more different chemical elements.

Three main factors determine whether or not solid solution is possible: 1. Comparative size of ions (atoms, molecules) that are substituting for one another 2. The valence state (charge) of the ions involved in the substitution. 3. The temperature at which the substitution takes place

Types of substitution

Simple cationic/anionic: Ions of similar size and charge substitute for each other. Examples:

K = Na

KCl NaCl (sylvite - halite); KAlSi3O8-NaAlSi3O8 (orthoclase albite) Mg2SiO4 Fe2SiO4 Mn2SiO4 (forsterite fayalite - tephroite; olivine) MgSiO3 FeSiO3 (enstatite ferrosilite; pyroxene) KCl - KBr (Zn, Fe)S (sphalerite)

Mg = Fe (= Mn)

Cl - Br Fe = Zn

Coupled substitution: For electrical neutrality to be maintained, substitution of two elements requires an additional substitution. Examples:

Fe2+ + Ti4+ = 2Al3+ Ca2+Al3+ = Na+Si4+ Mg2+ + 2Al3+ = 2Fe2+ + Ti4+

(Al, Ti)2O3 (corundum, var. sapphire) CaAl2Si2O8-NaAlSi3O8 (plagioclase) (Mg, Fe)(Al, Ti)2O4 (spinel group)

Interstitial substitution: Between some ions or ionic groups there may exist structural voids.

Vacancy solid solution: remember that close packing of anions often creates more cation sites than can be filled.

Omission solid solution: this is the opposite of filling a vacancy, that is, creating one.

The result of these substitutions is a wide variety of mineral and mineral formulas!!!

Crystallization and polymorphs

Lecture 6 Crystal growth, Physical properties of minerals

Crystallization
Crystallization involves nucleation of a seed crystal and subsequent growth of that crystal. Nucleation involves competition between the supersaturation driving crystallization and the surface energy created by formation of a new phase. For this reason, high supersaturations (a large driving force) promotes nucleation. In contrast, once nuclei exist, they may grow at smaller supersaturations.

The figure below illustrates the different supersaturation regimes anticipated for different locations of magma cooling. Slow cooling (low supersaturation) of rocks within the Earths crust is often invoked to explain the lower number density, but larger size, of crystals in

plutonic rocks relative to volcanic rocks that cool on the Earths surface.

Differences in nucleation and growth behavior can also explain the difference between the salt and alum crystals that you grew in lab.

Crystal growth
Processes of crystal growth arent perfect for example, crystals that grow rapidly may develop skeletal or dendritic forms. Such a crystal is shown in the photo on the right. This is a scanning electron microscope image where backscattered electrons are collected to yield an image that tells us about composition. You can see many different features in this image. First, the crystal appears to have a hole in the middle this is the texture that we call skeletal. Second, note that the structures at the corners of the crystals are decorated with the onset of dendritic overgrowths. Finally, note that the crystal is zoned in gray scale, which represents compositional zoning (discussed below).

And most crystals have some sort of imperfection (many of which are diagnostic of that crystal). Which leads to a discussion of:

Crystal imperfections - defects Defects important in that they increase crystal reactivity ... Point defects All crystals above absolute zero contain some defects ... increases energy of system, thus more at high temperatures

1. Impurity defect results from the presence of a foreign atom, either replacing one normally in the structure or filling a vacancy.

2. Paired vacancies Anion vacancies are regions where there is more positive charge may trap nearby electron ... transitions between energy levels may be invisible range - color center For this reason, can induce colors using radiation (Pleichroic halos around zircon inclusions) Vacancies are important for process of diffusion, that is, moving ions through the crystal structure.

3. Line defects - happen when rock is stressed. Most easily understood with reference to simple cubic lattice. dislocations - extra plane of atoms.

edge dislocation occur when a plane of atoms in a structure terminates at a line in the crystals interior screw dislocation - caused by displacement of part of crystal structure one translation unit relative to another such that the displacement terminates along a line perpendicular to growing face.

4. Stacking faults may separate layers that are out of order

Crystal imperfections zoning Compositional zoning occurs when different parts of a mineral have different compositions (through various substitution mechanisms). This is illustrated nicely in the olivine picture above, where the dark gray part of the crystal is enriched in Mg, and the bright part of the crystal is rich in Fe. Compositional zoning is particularly common (and diagnostic) in plagioclase. The crystal shown on the left shows several different types of zoning, including normal zoning (the general outward trend from brighter, Ca-rich plagioclase to darker, Na-rich plagioclase) oscillatory zoning (the fine scale structure that oscillates between slightly darker and slightly lighter shades of gray) sector zoning (which is illustrated by the faint diagonal bands that open outward from the crystals interior

Crystal imperfections - twinning Twins result when different domains of a crystal structure have different orientations. They share atoms along a surface typically a composition plane. You can think of these as mistakes in where the next plane of atoms is placed (think of stacking the clear plastic spheres

Descriptions of types of twinning:

simple twins if composed of only two parts, that is, if the twins can reflect across a single plane multiple twins refers to twins of multiple orientations penetration twins describes the growth condition when two or more parts of a crystal appear to penetrate each other.

Most common (and distinctive) are the twinning habits of feldspars. Plagioclase feldspar is triclinic, thus there are no planes of symmetry to control twin planes. Twinning in plagioclase consists of numerous repeated twins, called polysynthetic twins. Most spectacular when viewed in thin section.

Physical properties of minerals

Well look at two different aspects of physical properties those that are important for diagnostic identification of minerals (mostly scalar), and those that dictate the physical behavior of minerals (those that often show directionality, that is they are vector properties).

HAND SPECIMEN PROPERTIES

As these properties are best learned in lab, I will just present an overview in class.

1. Appearance LUSTER general appearance or sheen examples include metallic, vitreous, adamantine (diamond-like). Metallic luster is the result of near-complete reflection of light by the mineral surface. The adamantine luster of diamond is a consequence of its high index of refraction

DIAPHENITY refers to a minerals ability to transmit light (transparent, translucent, opaque). Most opaque minerals have metallic luster.

COLOR often useful for quick ID (particularly when color is distinctive), but can be very misleading. Color is controlled by chromophores and is a consequence of the interaction of light with electrons in the crystal.

Allochromatic minerals have color caused by elements that are present in trace amounts, like the Cr that causes the green color of beryl to the right (emerald), or the Ti that gives corundum the blue that we call sapphire.

In contrast, idiochromatic minerals have color as an intrinsic property, sometimes on that changes with solid solution composition, and thus may be diagnostic not only of mineral type but also end member composition (as in garnet). Examples of idiochromatic minerals include Cu-bearing minerals (which are typically blue or green) and Mn-bearing minerals, which are typically pink. Color can also be created by electron vacancies to form color centers (particularly common in fluorite).

STREAK the color of finely powdered mineral; useful for distinguishing oxides and sulfides

LUMINESCENCE any emission of light that is not the direct result of incandescence; includes properties such as fluorescence and phosphorescence. Luminescence of minerals is another property that may be controlled by trace amounts of an element. COLOR PLAY refers to properties of light scattering, as seen in the star sapphire in the picture. In this case the star of light is created by light scattering from small inclusions that are arranged along the three principle crystallographic directions. Other examples of color play include the iridescence that is characteristic of labradorite; here the scattering is the result of very fine-scale exsolution. Opalescence opalescence is the bodies that are able to is probably one of the best examples of color play result of silica precipitation as tiny spherical scatter light.

2. Crystal shape Called crystal habit the appearance of minerals, either as single crystals or as aggregates; includes terms such as the fibrous growth of cerussite (Pb carbonate) crystals to the left, or the botryoidal habit of smithsonite (Zn carbonate) to the right.

3. Strength related primarily to bonding

TENACITY cohesiveness, or resistance to breaking. Terms to describe tenacity include brittle (ionic bonding); malleable (metallic bonding), flexible (characteristic of sheet silicates like mica)

CLEAVAGE, FRACTURE, PARTING reaction of crystal (strain) to an external force (stress). Cleavage is the tendency of minerals to break along certain planes (EX: graphite). When minerals break along planes of weaknes they have parting; weakness may be twinning, pressure solution. When minerals do not have a dominant plane of weakness they fracture in patterns that may be described as conchoidal, fibrous, hackly.

HARDNESS resistance of a smooth surface to scratching. Hardness is probably a consequence of weakest bond in structure.

4. Density (specific gravity)

Ratio of the weight of a substance and the weight of an equal volume of water. Determined as

Specific gravity (the ratio) can be measured by a Jolly balance; density requires a pycnometer. The density can be calculated from the mineral formula if you know the dimensions of the unit cell and the number of formula units per unit cell.

5. Magnetism

Magnetite and pyrrhotite are the only common minerals with a magnetic signature. ANISOTROPY AND PHYSICAL PROPERTIES

Many physical properties are anisotropic, such that their magnitude depends on the direction in the crystal. An easy way to picture this is by a mechanical analogue with springs of different stiffness in different directions net displacement is the result of the vector sum of the components, thus the direction of displacement is not necessarily the same as the direction of the applied force.

DIRECTIONAL PROPERTIES

thermal conductivity relateds heat flow to temperature gradient

electrical conductivity relates electrical current density to electric field

diffusivity relates atomic flux to concentration gradient

elastic properties relate strain (extent of deformation) to applied stress

seismic properties relate to velocity of seismic wave propagation (related to density, rigidity, bulk modulus)

optical properties relate to refractive index variations Examples: calcite shows double refraction ulexite is a natural fiber optic

Each of these properties is controlled by the crystal structure, such that the directional variation in the value of a physical property must be consistent with the point group symmetry of the crystal since physical properties can always be broken into three mutually perpendicular components, the symmetry of physical properties may be greater than the symmetry of the crystal itself

Physical properties may be isotropic uniform in all directions (isometric crystals) uniaxial similar in two directions and different in the third (hexagonal and tetragonal crystals) biaxial different in all three directions (orthorhombic, monoclinic, trigonal crystals) Lecture 6 OVERVIEW

Details
Crystal growth, Physical properties of minerals

Crystallization

Crystal nucleation

Crystal growth

Crystal imperfections Defects Point defects Impurity defects Paired vacancies Line defects edge dislocation screw dislocation Stacking faults

Zoning

Twinning simple twins multiple twins contact twins penetration twins

Physical properties of minerals

HAND SPECIMEN PROPERTIES

1. Appearance LUSTER DIAPHENITY COLOR Allochromatic minerals Idiochromatic minerals STREAK LUMINESCENCE COLOR PLAY

2. Crystal shape

3. Strength related primarily to bonding

TENACITY CLEAVAGE, FRACTURE, PARTING HARDNESS

4. Density (specific gravity)

5. Magnetism

ANISOTROPY AND PHYSICAL PROPERTIES

DIRECTIONAL PROPERTIES

thermal conductivity relates heat flow to temperature gradient

electrical conductivity relates electrical current density to electric field

diffusivity relates atomic flux to concentration gradient

elastic properties relate strain (extent of deformation) to applied stress

seismic properties relate to velocity of seismic wave propagation (related to density, rigidity, bulk modulus)

optical properties relate to refractive index variations

Physical properties may be isotropic uniform in all directions (isometric crystals) uniaxial similar in two directions and different in the third (hexagonal and tetragonal crystals) biaxial different in all three directions (orthorhombic, monoclinic, trigonal crystals)

Lecture 4 Radius ratios and Pauling's Rules

As we have discussed, the outward symmetry of crystals is an expression of internal ordering of atoms and ions in the crystal structure. This in turn reflects the intrinsic symmetry of the packing of atoms, and their interaction with neighboring atoms...

The ultimate reason for a particular arrangement of atoms in a mineral structure lies in the nature of the cohesive forces that hold atoms together. In theory, we should be able to predict a mineral structure from the chemical composition, but in reality the problem rapidly becomes too complex to solve.

We'll be discussing the subject of crystal chemistry for the next few weeks - defined as the elucidation of the relationship between chemical composition, internal structure and physical properties of crystalline material.

A reminder: the chemical composition of the Earth's crust - 8 elements make up ~99 wt% of the crust ("major elements") ... O and Si are most abundant, thus most common minerals are silicates and oxides.

Ionic radii

Size of atoms difficult to define, let alone measure. Determined be maximum charge density, which itself is a function of the type and number of nearest neighbor atoms. Therefore it is possible to assign each ion a radius such that the sum of the radii of two adjacent ions is each to the interatomic (separation) distance. Thus we can determine effective radii by measuring bond lengths in crystals.

Within a given period (say, the alkalis), the radius increases with atomic number. (Table 13.1) Radii also vary systematically across a row, being smaller at the center (cation charge increases) and largest to the right (the anions; Table 13.2).

Ionic radii depend strongly upon the valence state of the ion, with larger sizes for negative ions and smaller sizes for positive ions (Table 13.3, 13.4). EX: S+6: S: S-2 radius = 0.6 A radius = 1.04 A radius = 1.7A

Finally, the size of an ion is dependent on its coordination number.

Coordination number

Many simple mineral structures can be viewed as close packing of large anions, with smaller cations in interstitial sites. The anions are packed in a regular structure, while the cations fit in between. The number of anions to which a particular cation bonds is the cations coordination number. EX: Si+4 typically bonds to 4 O atoms, and therefore has a coordination number of 4.

The size of the interstices depends how the anions are packed different in 2- and 3dimensions.

EXAMPLES

We give coordination arrangements geometrical names: 2-fold linear

3-fold

triangular

4-fold

tetrahedral

6-fold

octahedral

8-fold

cubic

12-fold

dodecahedral

Closest packing

What is the most economical way to pack spheres?

2D: If spheres of equal size are packed together as close as possible in a plane, they arrange themselves as follows:

Center of spheres are at the corners of equilateral triangles; each sphere is in contact with 6 others. Note that within this layer there are 3 close-packed directions, each at 60o. Unit cell is hexagonal, with lattice parameter

a = 2r. Packing is 90.7% efficient. Hexagonal (closest) packing

Here the center of spheres are at the corner of squares, each sphere is in contact with 4 others. There are only two close-packed directions and the unit cell is square. Packing is 78.5% efficient. Tetragonal packing

Closest packing in three dimensions Metals have structures that are typically formed by close-packing of atoms, around which electrons pass freely. This type of structure is highly ordered so as to minimize void space.

Build 3-D structure by placing these layers one on top of the other. Most economical way of doing this is such that spheres in one layer rest in hollows of layer below. Two different positions are possible, B or C. (choice equivalent to rotating 180o). By doing so, create a layered sequence of AB.

Let's add a third layer. Again, we have two choices. If third layer goes above A position: ABABABABA simplest form of close packing - hexagonal closest packing (has underlying hexagonal lattice) this is true for Na metal

If third layer goes in the C position, stacking sequence would be ABCABCABC. cubic closest packing (has underlying cubic lattice). In both of these closest packing sequences, each atom has twelve equidistant nearest neighbors, six in its own plane, and three each in the layer above and the layer below. Examples include Au (shown to the left), Ag, and Cu. This simple structure means that metal atoms of similar size can easily substitute for each other, thus allowing for alloys of metals like silver and gold. Because of the close packing, metals are dense; they are also malleable and good electrical conductors.

Other minerals that have a cubic closest packed structure are sphalerite halite

ZnS

NaCl

Most minerals are not formed by metallic bonds, and thus do not have this simple structure. For example, the covalent bonds of diamond are strongly directional, which prevents the atoms from adopting a closepacked structure. As a consequence, diamond has a lower specific gravity than a typical metal.

Ionic Bonding One of the most successful models for predicting crystal structure is to treat crystals as packing of anions and cations as different sized spheres these rules are collectively known as Paulings Rule and can be summarized as follows:

1. The Coordination (radius ratio) Principle a coordination polyhedron of anions surrounds each cation. The cation-anion distance is determined by the sum of the cation and anion radii and the number of anions coordinating with the cation is determined by the relative size of the cation and anion.

2. Electrostatic Valency Principle in a stable ionic structure, the total strength of the valency bonds that reach an anion from all neighboring cations is equal to the charge of the anion.

3. Sharing of Polyhedral Elements I the existence of edges (and particularly faces) common to coordination polyhedra decreases the stability of ionic structures

4. Sharing of Polyhedral Elements II in a crystal containing different cations, those with large valence and small coordination number tend not to share polyhedral elements with each other.

5. Principle of Parsimony the number of essentially different kinds of constituents in a crystal tends to be small.

Well look at each rule separately.

Coordination (radius ratio) Principle: This principle states that the number of anions with which a cation coordinates is determined by the ratio of their radii rc/ra.

Bottom line: most stable configuration is achieved when oppositely charged ions (e.g. Na+ and Cl-) are as close together as possible without overlapping. Inter-ionic distance determined by the balance of electrostatic attractive forces between outer electron charges, and repulsive forces between nuclei. Thus in 3 dimensions, ions with positions that follow principles of ionic bonding form highly symmetric polyhedra (coordination polyhedra) that have same inter-ionic distances - will control where certain cations fit into crystal structures. Tetrahedra and octahedra are most common structural types, but triangles, cubes, and other forms important. These coordination polyhedra link together in various ways to form the polyhedralframe structures. Include all of rock-forming silicates, as well as many borates, sulfates, phosphates, tungstates, oxides, hydroxides.

To reiterate, a coordination polyhedron of anions is formed about each cation, the cationanion distance being determined by the radius sum and the coordination number of the cation by radius ratio. Thus when bonding dominantly ionic, each cation in the structure will tend to attract, or coordinate, as many anions as will fit around it.

NaCl

Appropriate radii: Na+ Clrc/ra = 0.097nm = 0.181nm (almost twice as large) = 0.54

If we imagine these as rigid spheres, how closely can we pack them?

First lets look at 2 dimensions. If the radius of the cation is very small relative to the cation, the cation can fit into small space between three close-packed anions. As the cation becomes larger, the anions move farther apart. At some ratio of ionic radii, closest packing switches to one in which the cation is surrounded by 4 anions (this is the case for NaCl)

From trigonometry:

rc / ra = .414

Thus the radius ratio between anions and cations tells us how the spheres can be packed. For smaller ratios, all 4 anions would not touch the cations, and distances would not be minimized. For larger ratio, distance between anions > 2ra, and eventually a new configuration becomes stable.

What about the third dimension? In order to maintain rc/ra = .414 (minimum separation = closest packing), we must add two additional anions, one above and one below. Thus each cation is in 6-fold (octahedral) coordination.

In general:

Rc/Ra <0.15 0.15 0.15-0.22

Expected coordination of cation 2-fold coordination ideal triangular triangular

C.N. 2 3

0.22 0.22-0.41 0.41 0.41-0.73 0.73 0.73-1.0 1.0 > 1.0

ideal tetrahedral tetrahedral ideal octahedral octahedral ideal cubic cubic ideal dodecahedral dodecahedral

12

Lets return to our model of close-packed spheres. As you determined in lab, stacking of close-packed layers of spheres generates two kinds of interstices:

tertrahedral site between 4 close-packed atoms. Thus any small atom occupying this site will be tetrahedrally-coordinated with its neighbors. Tetrahedral sites form in two distinct orientations - apex pointing up or apex pointing down. For this reason, there are twice as many tetrahedral sites as there are close-packed ions (one above and one below).

octahedral site is larger - has 3 atoms below and 3 above.

NOTE: when one close-packed layer is placed on top of another, both types of sites are created. Specifically, there are two 4-fold sites and one 6-fold site per sphere. Let's look at elements in rock-forming minerals.

ranion = 0.13 nm

Radius ratios with oxygen: Si4+ = 0.30nm Al3+ = 0.47nm

Si fits into range for tetrahedral coordination - usually found tetrahedrally coordinated in silicate minerals. However, Al in boundary region between tetrahedral and octahedral coordination... In natural minerals it is found in either coordination.

Most other common cations in Earth's crust fall in range of octahedral coordination.

Electrostatic valency principle: we can calculate the strength of a bond (its electrostatic valence) by dividing valence by coordination number (CN). As a consequence, in a stable crystal structure the total strength of the valency bonds that reach an anion from all neighboring cations is equal to the charge of the anion. The rule is a direct consequence of ionic bonding... total bonding capacity of a cation is proportional to its charge (z): z/CN

Ti+4 is in octahedral coordination with oxygen. Each Ti-O bond has a strength Z/CN = 4/6 = 2/3. Each oxygen has three neighboring Ti+4 cations such that their collective bond strength (3 x 2/3) equals the oxygen charge of -2. For this reason, anions tend to be locally charge-balanced. Ex. rutile TiO2

SOME CONSEQUENCES: A. Geometrical and electrical stability - (Ex. fluorite, CaF2). Each Ca has 8 fluorine neighbors, while each fluorine has only four Ca neighbors. rCa = .99A rF = 1.33A rc/ra = .74

Even though relative sizes would allow closest packing, charge balance requires the 2:1 ratio, and thus determines the structure.

Fluorite and halite illustrate another consequence of rule 2, which is that when all ionic bonds have the same strength, anions pack together in a highly symmetrical arrangement, thus these minerals are highly symmetric. Minerals with uniform bond strengths include the oxides, fluorides, chlorides, etc.

In contrast, when there are nonuniform bond strengths, crystal structures have lower symmetry. This is true when structures include small cations of high charge (C4+, S6+, P5+, Si4+). Additionally, this rule means that the number and kinds of coordination polyhedra that can meet together at a point are severely limited. For example, no more than 2 Si4+ tetrahedra can share a common oxygen, even though the radius ratio considerations alone would permit three, four or more ... each Si-O bond contributes an electrostatic strength of 4/4 = 1, so that two Si-O bonds will just satisfy the -2 charge of the oxygen. Similarly, exactly three divalent cation octahedra will share a common oxygen with a Si4+ tetrahedron. Mineral groups included in this category are the carbonates, sulfates, phosphates and silicates.

3) Sharing of polyhedral elements. I. The existence of edges, and particularly of faces, common to two anion polyhedra in a coordinated structure decreases its stability. Direct outgrowth of electrostatic forces... Most stable configuration is when two polyhedra share only a corner, because then the two central cations are as far apart as possible.

The figure above shows that the more anions shared between polyhedra, the closer the positively charged cations. This reduces stability, particularly when the cations are highly charged (e.g., Si4+).

4) Sharing of polyhedral elements II. In a crystal containing different cations, those of high valency and small coordination number tend not to share polyhedral elements with each other. Corollary of rule three - emphasizes the fact that highly charged cations will be as far apart from each other as possible. Effect stronger if coordination number is low. Ex. - no silicate minerals have edge-sharing or face-sharing Si tetrahedra. However, edge-shared octahedra are common (TiO2, or, as shown in the diagram below, NaCl), and even face-shared octahedra are found (Fe2O3).

5) The principle of parsimony. Number of essentially different kinds of constituents in a crystal tends to be small because, there are only a few types of cation and anion sites. No more than two or three different types of coordination polyhedra in a mineral. The number of crystallographically different sites is thus small - fundamental reason why various cations and anions in chemical fromulas are generally in small integer ratios to each other. Relative abundance controlled by availability of sites in a structure. Thus in structures of complex compositions, a number of different ions may occupy the same structural position (site).

Summary:

It is possible to regard a crystal as being made up of AXn groups that are joined together by sharing corners, edges or faces of coordination polyhedra rather than as individual ions... we'll see a lot more of these. Coordination polyhedra commonly distorted.

1. polyhedral framework structures Most of rock-forming minerals in this category, especially silicates. All structures are direct consequence of predominantly ionic bonds between constituent ions. As result of bonding, anions tend to group around cations in highly symmetric manner to define coordination polyhedra. Ex: silica tetrahedron divalent cation octahedra (SiO4)-4 (MgO6)-10

By sharing apical oxygens, polyhedra link together to define a structural frame that possesses at least half of the total bonding energy of the mineral - resulting frame is relatively strong and has important influence on most physical and chemical properties.

2. Symmetrically packed structures Either bonds between atoms are nondirectional or bond directions are highly symmetrical. Ex. metallic bond, also many examples of covalent and ionic. Atoms form highly symmetrical structures in which atoms packed together in symmetrical ways: a) monatomic (native metals) - if atoms are in contact in and between sheets - highly efficient packing called closest packing. If atoms lose contact within sheets but retain contact between sheets - close-packed.

b) mulitatomic - both cations and anions... many oxides, sulfides, halides and most of important silicates considered as framework are in this category. Anions are in symmetrically packed sites, and cation soccupy voids between. symmetry of anion packing is basic characteristic.

3. Molecular structures Composed of atoms characterized by strongly directional and low symmetry bonds. Asymmetric bonds form strong clusters, chains and layers of atoms that behave as discrete units connnected by much weaker bonds to for 3-D networks. Ex: ice Lecture 7 OVERVIEW

Details
Classification

Classification of Minerals

halides oxides hydroxides carbonates

[with anions Cl-, F-, Br-, I-] [with anion O2-] [with anion complex OH-] [with anion complex CO32-]

native elements sulfides [with anion S2-]

Classification of silicates

Framework silicates

Sheet silicates

Single chain silicates

Double chain silicates

Isolated tetrahedra

Lecture 8 OVERVIEW

Details

Composition space

Two-component systems (linear composition space) FeO SiO2 Fe2SiO4 Mg2SiO4

Three component systems (planar triangle) FeO-MgO-SiO2 MgSiO3-FeSiO3-CaSiO3

Chemical reactions between different mineral phases. EX:

The minerals that we find together in a given rock are a function of (1) which mineral or combination of minerals is stable, and (2) the bulk composition of the rock.

One more ternary example: CaO-SiO2-Al2O3

Mineral

Moles CaO anorthite 1 grossular 3 wollastonite 1 kyanite

Moles Al2O3 1 1 1

Moles SiO2 2 3 1 1

% CaO 25 43

% Al2O3 25 14

%SiO2 50 43