Crystal Chemistry

 Mineral – “…defined, but generally not

fixed, chemical composition…”
 Modern geology – Geochemistry or
Geophysics
 Geophysics – application of physical principles
to study of earth
 Geochemistry – application of chemical
principles to study of earth
 high T or low T
 Coming up… a review of basic chemistry
 Elements
 protons, neutrons, electrons
 Bond types and controls on bonds
 Nuclear Chemistry

 Atomic number (Z) – number of protons

 Specific for particular elements (periodic table)
 Neutrons – about same mass as protons,
different number of neutrons make isotopes
 Atomic weight – sum of weight of
neutrons and protons
 Isotopes - Superscript in front of element
symbol, atomic weight exact
 Elements – atomic weight is the average of
abundance of isotopes
 Stable Isotopes
 Oxygen – Z = 8; three isotopes
 Average bulk earth abundance:
 16O – 99.757%
 17O – 0.038%

 18O – 0.205%

 Materials (minerals, water, air, shells, etc)

have variable ratios of these isotopes
 d18O = ratio of 18O/16Osample to
18O/16O
standard
 Radioactive isotope
 Potassium (z=19)
 40K has 21 neutrons
 Natural abundance = 0.0117%
 Radioactive

 Decays to 40Ar, basis of one type of age dating

 Half life = 1.248 x 109 a

 39K has 20 neutrons

 Natural abundance = 93.3%
 Stable (not radioactive)

 41K has 22 neutrons

 Natural abundance = 6.7%
 Chemical Reactions

 Based on electron transfers, charge

balance
 If number of electrons = number of
protons, no electrical charge
 Orbit nucleus in systematic way
 Organized according to energy levels
 Shells filled according to energy
 Electron Quantum number

 Quantum number - reflects energy of

electron
 Unique for each electron
 No two electrons in atom can have same
quantum number
 Controls how electrons fill shells
 Controls their chemical reactivity
 Formation of ions

 Ions – excess or deficit of electrons

relative to protons
 Anions – net negative charge
 Cations – net positive charge
 Valence or Oxidation state is the value of
the charge on the ion
 Configuration of valence electrons controls
whether gain or lose electron
 Metals – typically lose one or two valence
electron: form cations
 Non-metals – typically require a few electrons
to fill valence shells: form anions
 Valence shells fill systematically – see
table 3-3 for how shells filled
 Atomic number 1-20 and 31-38 – fill s & p
subshells
 Between atomic number 20 and 31 – shells fill
from internal subshells – fill 3d shell (4s shell
filled)
 Transition metals
 Elements may have differing numbers of
shells filled
 E.g. Ferrous and Ferric iron
 Note the various oxidation
Lose electrons (cations) to
states for the transition
become noble gas core
metals

Ferric Fe (+3)

Ferrous Fe (+2)

Metallic Fe
Gain electrons
(anions)

Noble Gases, He, Ne, Ar, Kr

Fig. 3-3
 Clearly – gain or loss of electrons
important
 “Quantified” as property called
Electronegativity
 Electronegativity
 Defined by Linus Pauling
 Propensity of element to gain or lose
electron
 Based on arbitrary scale: Li = 1, C = 2.5, F =
4
 Low electronegativity - the more likely to lose
electron form cations
 High electronegativity – likely to gain electron
to form anions
 See Table 3-4 for values
 Coming up

1) Abundance of elements on earth

2) Types of electron sharing bonds – ionic,
covalent, metallic
3) How to estimate bond types from
electronegativity
Earth abundances of elements

 What elements are most abundant?

 These elements will make up common minerals
 What part of earth do they occur?
 Crust?
 Bulk earth?
 Crust - 8 common elements
 O2-, Si4+, Al3+, Fe2+,3+, Ca2+, Na+, K+ and Mg2+
 Most minerals are made of these elements
 Determination of crustal abundance –
simply collect large number of samples
and measure
 Bulk earth composition
 The same 8 elements are common in bulk, but
different ratios
 Table 3.6
90% of atoms
are Si, Al, & O

Crust

Core/
Mantle

Mantle
 Bulk Earth composition:
 Difficult to assess – impossible to directly
sample mantle or core
 Estimated by
 Mass and density based on geophysical
measurements
 Composition of mantle magmas and xenoliths
 Composition of meteorites
 Chemical bonding
 Eight common elements (plus all others)
bond to form minerals
 Bonding controls spatial arrangement of atoms
 Two categories
 Sharing of valence electrons: ionic, covalent and
metallic
 No sharing: van der Waals and hydrogen
 These 5 types of bonds are “end members”
 Rarely just one type or the other
 However: We’ll consider most minerals to
be ionically bonded
 Ionic Bonding
 Transfer of electron(s) from one element
to another
 Results in filled valence shells of both
 The electrostatic attraction keep atoms
together
 The distance between ions depends on
attractive forces (Coulomb law) and
repulsive forces (Born repulsion)
 Attractive forces
Bonding in Halite

Repulsive forces Equilibrium distance = 2.8 Å

Face centered
cubic lattice
arrangement of
halite

Fig. 3-4 Fig. 2-10

 Ionic bonding
 Ions bond so that positive = negative
charges
 Minerals must be electrically neutral
 NaCl (Halite),
Na(Mg,Fe,Li,Al)3Al6[Si6O18](BO3)3(O,OH,F)4
(tourmaline – not all ionic bonds here)
 Characteristics:
 Ions act like spheres
 Alternating cations and anions
 One of the strongest bonds
 Brittle because like ions repel
 Cleavage is common
 Covalent Bonds
 Electrons shared when orbitals of two
different elements overlap
 Shared by only two atoms
 Differs from metallic (later – all atoms share
electrons)
 Electrons move around nucleus of both atoms
 Examples – Diamond and Graphite
 Diamond
 Stable Ne configuration by either gain or loss
of 4 electrons
 Ionic bonding not possible because all
electrons exactly the same electronegativity
 One carbon won’t “steal” electron from
another
 Instead share electrons – very strong bonding
 Covalent bonding
in diamond

• 4 orbitals shown as
bonds, call s bonds
• s bonds distorted

Each bold line

represents another
similar bond

Fig. 3-5
Graphite

Additional Sharing
electrons, p
bonds.

Similar s bonds,
but only in
layers

Fig. 3-6
 Metallic bonds

 A type of covalent bond

 Electrons shared without systematic
change in orbitals
 Free to move throughout crystal structure
 Formed with low electronegativity –
weakly held valence electrons
 Relation between valence-
dependent bonds
 Most bonds not purely ionic, covalent or
metallic
 Amount of bond type depends on
electronegativity (tendency to give up
electrons)
 Greater difference in electronegativity
between ions means more ionic
characteristic
 Only 1 anion (of 8 common elements)
 Oxygen
 Electronegativity of O = 3.5
 Electronegativity of other common elements
range from 0.8 (K) to 1.8 (Si)
 Qualitative difference in electronegativity:
 O-K = 3.5 – 0.8 = 2.7, more ionic
characteristics
 O-Si = 3.5 – 1.8 = 1.7, less ionic
characteristics
 Possible to quantify % ionic bonding:
 O-element bonding of 8 common elements
ranges from 50% ionic (Si-O) to 80% ionic
(K-O)
 O-K ~80 % ionic

O-Si ~50 %
ionic

2 X=
% ionic character = 1 – e -0.25(Xa – Xc)
electronegativity
of a, anion and c,
Note negative cation
sign, typo in 1st
Eq. 3.4
edition
Fig. 3-10
 Native elements
 Examples: S, Fe, Au…
 No differences in electronegativity
 Bonding intermediate between covalent
and metallic
 Low electronegativity values (Cu, Ag, Au)
favor metallic bonding
 High electronegativity values (non-metals,
C, S) favor covalent bonding
Range of possible mixtures of electron-sharing
valence bond types

100% covalent,
metallic or ionic
Percentages
Not 50 % covalent & 50%
Allowed metallic
Part covalent, part
metallic, and part
ionic

Continuous variations
Fig. 3-9
 Physical Properties caused by
Valence bonds
 Electrical conductance
 Ionic and covalent have little conductance
 Metallic highly conductive
 Solubility
 Ionic highly soluble (think halite)
 Brittleness
 Ionic highly brittle – cleavage common
 Halite – perfect {001} cubic cleavage
 Hardness
 Covalent – strongest bonding, so hardest.
Think diamond
 Malleable
 Metallic easily worked
 Non-valence bonds

 Result of asymmetric charge distribution

 Create electrostatic forces
 Two types
 Van der Waals and Hydrogen
 Hydrogen Bonding
 Ice example
 H2O is polar molecule
 2 H atoms at angle to O atom (not straight line)
 O is more electronegative than H

 O = 3.5, H = 2.1

 O “claims” more of the electron

 Net negative charge on O side of molecule

 The asymmetric charges allow solidifying

liquid when T < 0º C @ 1 atm P
 Ice – viewed
Asymmetrical down c axis
charge - polar

Hexagonal
symmetry
Hydrogen
bond

Fig. 3-11 & 18-2

 Van der Walls
 Carbon example
 Graphite – carbon bonded in sheets
 Bonding within sheets is covalent – s bonds
 Over time electrons evenly distributed

 At given time, excess electrons on one side of

sheet
 Creates weak electrostatic attraction

 Physical properties
 Typically soft
 Graphite good lubricant
 Covalent bonds within
the sheets

Van der Waal forces

between the sheets,
Caused by p bonds on
top of sheets

Other examples:
talc
serpentine/smectite
Fig. 3-12
 Atoms and ion size

 Assume that atoms are spheres

 Clear simplification – electron distributions are
not spherical
 Assumption works well for arrangement in
solids
 Atoms pack together in regular
arrangement
 If we assume the ions are spheres
 Can assume an effective radius
 Measure distance between adjacent atoms in the solid
 Measured with X-ray diffraction, d spacing
 Effective radius a measure of size of the atoms
 Very important – one control of how atoms pack
together
 Bond length – sum of effective radius of two
adjacent atoms
 Metallic bonds: all same effective radius
 ½ distance between nuclei
 Ionic bonds: effective radius different between two
atoms
 Not ½ distance between nuclei
Metallic bonding Covalent and ionic bonding
Bond length = d spacing Bond length = d spacing
Ionic radius = ½*d spacing d spacing = Ra + Rc

Fig. 3-13
 Clearly – what types of ions present
control ionic radius
 Primary variables controlling ionic radius:
 Oxidation state – i.e. charge on ion
 Coordination number – i.e. number of ions
surrounding central ions
 Oxidation state
 Inversely related
 More oxidized (less negative, more positive)
means smaller effective radius
 e.g., Fe3+ or Fe2+
 Cations smaller than anions, O2- very large
 Positive charge holds electron closer to
nucleus
 Coordination
Ionic radius (Å)

numbers

Charge
Fig. 3-15
(higher oxidation state)
 Coordination

 Positive correlation – high coordination

number, smaller ions
 Think of solids as large anions surrounding
small spaces filled by cations
 Size of space determined by effective radius
of anions
 Cation effective radius changes to fill space
 Note – increase in
ionic radius
independent of
Ionic radius

charge on ion

Coordination number Fig. 3-16