CRYSTAL CHEMISTRY

Unit cell
Bonding in minerals
Covalent and ionic radii
Packing structures
Radius ratio
Electronegativity

Unit Cell
The smallest repeatable unit of a crystal.
Contains all of the symmetry elements of the crystal.
The numbers of atoms define the chemical formula of a mineral.

Unit cell of NaCl

One atom of Na in the centre
Twelve -atom of Na on edges
Na : 1 + 12 = 1 + 3 = 4
Six -atom of Cl on faces
Eight -atom in corners
Cl : 6 + 8 = 3 + 1 = 4

Unit cells in cubic lattice system

Diamond

CsCl

ZnS

CaF2

Cu2O

ReO3

Bravais
14 possible units

Tetragonal

Rutile, TiO2

Monoclinic

Baddelyite, ZrO2

Triclinic

Kyanite, Al2SiO5

Orthorhombic

Trigonal

Hexagonal

Perovskite Sr2FeMoO6

KIO3

Wurtzite, ZnS

The structure of minerals depends on :

the type of bonds between atoms and/or ions
the size of constituent atoms and/or ions
the way of packing

Bonds in minerals
Atoms/ions within crystal lattices are held together by 4 types of chemical bonding:

Ionic (electron transfer)

Covalent (electron sharing, atomic & molecular orbitals)
Metallic (delocalization of electrons)
Van der Waals (weak bonds resulting from electrostatic forces between dipoles)

Ionic bonding

Electrostatic attraction of oppositely charged ions

Coulomb attraction FA

At one certain distance

(2.8 for NaCl)
FA + F R = 0

Born repulsion FR

Covalent bonding

Covalent bonds are formed by sharing of electrons by two atoms.

Covalent bonding occurs when the orbitals of two atoms overlap.
Carbon example sp3 hybridization -- diamond

Ground state

Promoted state

Hybridized

Covalent -bond

Cubic structure

Carbon example sp2 hybridization -- graphite

Relation between bonding & structure

Metallic bonding
Type of covalent bonding with valence electrons delocalized & free to move
Ideal case
positively charged cores packed into the structure
+ valence electrons as a mobile glue to hold it all together
Factors favouring metallic bonding
Valence electrons are held weakly (low electronegativity)
Large number of electrons to complete the noble gas configuration
Vacant energy levels into which electrons can migrate
Mechanism:
Single atom electrons are on
discreet energy levels
Multiple atoms in proximity
energy levels create almost
continuous bands

Van der Waals bonding

Due to the weak electrostatic interactions between asymmetric charge distribution
Does not involve valence electrons

Dipole moment

Minerals with vdW bonds

are soft, with greasy feel

Relation among bonding types

Ionic, covalent, metallic involves valence electrons
Many bonds are intermediates
Ionic
Ionic Character

100
80
60
40

20
0

Covalent

Metallic

1
2
3
Difference in Electronegativity

Average Electronegativity

Difference between ionic & covalent statistical, where the electron is located
Ionic
Around anion

Covalent
Around two atoms

Metallic
Around several atoms

Bonding

Properties

Ionic

Fairly strong bond

Crystals tend to be brittle, under stress fracture along cleavages
Often soluble

Covalent

Strong bond.
Highly directional bonds spatial geometry of hybridized orbitals)
Bonds can be polarized gives rise to dipole interactions
Limited (or none) solubility

Metallic

Moderately strong nondirectional bond -- malleability.

Easy to substitute one metal atom for another alloys.
Superior electric conductivity (cloud or sea of free electrons)

Van der Waals

Weak bond
Crystals tend to be soft, with greasy feel

Size of atoms and ions

Size probabilistic, particles are not spherical, boundaries not defined strictly
Approximation to spheres gives effective radius, based on distances between
centres within the structure (i.e., bond length)
Bond type affects the effective size metallic, covalent & ionic radii

Simplest case metals, closely packed spheres of same size

However, metallic radius depends on coordination (packing)
Effective radius can be measured by XRD method
Higher coordination (CN=12) gives higher atomic radius
CN=4
x=0.88
CN=6
x=0.96
CN=8
x=0.97
CN=12 x=1

Trends in periodic table

Atomic radius
About 10 000x the radius
of its nucleus

More protons in nucleus stronger attraction

Sudden shift new electron shell

Ionic radius
May differ substantially from atomic/covalent radius

Same ions/atoms have differing radii

(HS = high spin, LS = low spin, M = metallic

CN

spin

Fe

12

1.26

Fe2+

0.71

HS

Fe2+

0.69

LS

Fe2+

0.86

HS

Fe3+

0.57

HS

Fe3+

0.63

LS

Fe3+

0.73

HS

Ionic Crystals
Radius ratio = Rcation /Ranion

LiI : 90/206=0.44

RbF : 166/119=1.39

Coordination
Affects the effective ionic radii

Radius ratio
<0.155

0.255-0.414
0.155-0.225

0.732-1.0
0.414-0.732

1.0

Close packing

Close packing
Spheres of equal size can be
close-packed in two ways
Hexagonal (HCP)
two repeating layers

ABABABABABAB

Cubic (CCP or FCP as face-centered packing)

three repeating layers
ABCABCABCABC
Both ways give the same packing density 74.05%
but the symmetry is different

All native metals have one of these structures

Bi HCP

Au FCP

Electronegativity

Dimensionless property characterizing the propensity of an atom to attract an electron

Determined as an average of first ionization potential and electron affinity
First ionization potential energy required to remove an electron from the outer shell
Electron affinity energy released when electron is added to the outer shell

High electronegativity anion easily formed (F-, O2-, )

Low electronegativity cation easily formed (K+, Cs+, )

High difference between electronegativities ionic bond (CaF2)

Low difference between electronegativities covalent bond (ZnS)

Electronegativity periodic trends

Bonding in ore minerals

Metals mostly covalent (metallic) bonding with close packing
Oxides mostly ionic due to large differences in electronegativities
Sulphides mostly covalent due to small differences in electronegativities