Lecture 2 (9/11/2006)

Crystal Chemistry

Part 1:

Atoms, Elements, and Ions
Mineralogy Website
www.d.umn.edu/~mille066/Teaching/Mineralogy06.htm
What is Crystal Chemistry?
study of the atomic structure, physical properties,
and chemical composition of crystalline material
basically inorganic chemistry of solids
the structure and chemical properties of the atom
and elements are at the core of crystal chemistry
there are only a handful of elements that make
up most of the rock-forming minerals of the earth
Fe 86%
S 10%
Ni 4%
Chemical Layers of the Earth
SiO2 45%
MgO 37%
FeO 8%
Al2O3 4%
CaO 3%
others 3%
Composition of the Earths Crust
Average composition of the Earths Crust
(by weight, elements, and volume)
The Atom
The Bohr Model
The Schrodinger Model
Nucleus
- contains most of the weight (mass) of the atom
- composed of positively charge particles (protons) and neutrally
charged particles (neutrons)
Electron Shell
- insignificant mass
- occupies space around the nucleus defining atomic radius
- controls chemical bonding behavior of atoms

Elements and Isotopes
Elements are defined by the number of protons in the
nucleus (atomic number).
In a stable element (non-ionized), the number of electrons
is equal to the number of protons
Isotopes of a particular element are defined by the total
number of neutrons in addition to the number of protons
in the nucleus (isotopic number).
Various elements can have multiple (2-38) stable isotopes,
some of which are unstable (radioactive)
Isotopes of a particular element have the same chemical
properties, but different masses.
Isotopes of Titanium (Z=22)
Isotope Half-life Spin Parity Decay Mode(s) or Abundance
38Ti 0+
39Ti 26 ms (3/2+) EC=100, ECP+EC2P ~ 14
40Ti 50 ms 0+ EC+B+=100
41Ti 80 ms 3/2+ EC+B+=100, ECP ~ 100
42Ti 199 ms 0+ EC+B+=100
43Ti 509 ms 7/2- EC+B+=100
44Ti 63 y 0+ EC=100
45Ti 184.8 m 7/2- EC+B+=100
46Ti stable 0+ Abundance=8.0 1
47Ti stable 5/2- Abundance=7.3 1
48Ti stable 0+ Abundance=73.8 1
49Ti stable 7/2- Abundance=5.5 1
50Ti stable 0+ Abundance=5.4 1
51Ti 5.76 m 3/2- B-=100
52Ti 1.7 m 0+ B-=100
53Ti 32.7 s (3/2)- B-=100
54Ti 0+
55Ti 320 ms (3/2-) B-=100
56Ti 160 ms 0+ B-=100, B-N=0.06 sys
57Ti 180 ms (5/2-) B-=100, B-N=0.04 sys
58Ti 0+
59Ti (5/2-) B-=?
60Ti 0+ B-=?
61Ti (1/2-) B-=?, B-N=? Source: R.B. Firestone
UC-Berkeley
Properties of Electrons
Occur in discrete (quantized) energy levels or orbitals
around the nucleus
Behave as particles with wave-like properties
Position of an electron in space around the nucleus is a
probability function defined by 4 quantum numbers
n principle quantum number (= 1, 2, 3, 4...)
defines the energy level of the primary electron shell
l azimuthal quantum number (= n -1)
defines the type and number of electron subshells (s, p, d, f, ...)
m magnetic quantum number (= +l to -l )
defines orientation and number of orbitals in each subshell
s spin quantum number (= +1/2 or -1/2)
defines direction of spin of the electron in each orbital



Electron Shells, Subshells, and Orbitals
Filling up the
Orbitals
Controlled by the energy
of the orbitals
Structure of the Periodic Table
# of Electrons in Outermost Shell
Noble
Gases
Anions
--------------------Transition Metals------------------
Primary Shell being filled
Ions, Ionization Potential, and Valence States
Cations elements prone to give up one or more electrons
from their outer shells; typically a metal element

Anions elements prone to accept one or more electrons
to their outer shells; always a non-metal element

Ionization Potential measure of the energy necessary to
strip an element of its outermost electron

Electronegativity measure strength with which a nucleus
attracts electrons to its outer shell

Valence State (or oxidation state) the common ionic
configuration(s) of a particular element determined by
how many electrons are typically stripped or added to an
ion
1
st
Ionization Potential
Electronegativity
Elements with a single
outer s orbital electron
Anions
Cations
Valence States of Ions common to
Rock-forming Minerals
Cations generally
relates to column
in the periodic
table; most
transition metals
have a +2
valence state for
transition metals,
relates to having
two electrons in
outer
Anions relates
electrons needed
to completely fill
outer shell
Anionic Groups
tightly bound
ionic complexes
with net negative
charge

+1 +2
+3 +4 +5 +6 +7
-2 -1
-----------------Transition Metals---------------
Next Lecture
Crystal Chemistry II
Bonding
Atomic and Ionic Radii

Read p. 56-69