04-01-2023

Geochemistry Course EES 208

Dr. Ria Mukherjee Grading Policy

Quiz + Attendance: 20
Mid Sem: 30
End Sem: 50

Grading will be relative

1
04-01-2023

2
 04-01-2023

Common magmas & rocks

Basalt Magma
Hawaii 2018

3
 04-01-2023

Granitic
rocks

What is Geochemistry?
• Utilizing principles of chemistry to
study and interpret all chemical
aspects of Earth

• Geochemistry is essential for:

 understand composition of Earth’s

inaccessible interior

 measurement of geological time

 explore for economic mineral and hydrocarbon resources

 Understand how we are altering our environment

 Understand how Earth and its neighboring planets are evolving and
chemically differentiating through time

4
 04-01-2023

Geologic Time Scale

• Developed before advent of radiometric dating
• Provides reference for past geological events
• Techniques used: principles of original horizontality
superposition (layers above younger than one below)
faunal successions (e.g., fossils)

• Boundaries between different time spans usually defined by major

mountain building activity (orogenesis) or mass extinction

• Cretacious-Tertiary boundary responsible for mass extinction of dinosaurs

& marine

• Absolute time frames for each division in the time scale was added later
after radiometric technique developed

• Precambrian Eon pre-date fossil records & depend on absolute age

Atomic Structure
• Rocks comprised of minerals are crystalline solids with atoms constituting them

Quartz: SiO2 Pyroxene: Mg2Si2O6

5

• Elements: simple, uncombined chemical
substances of which all compounds
(minerals) are made
• Atoms: atoms are the smallest subdivision
of matter that retains the characteristics of
the elements
• Rutherford (1911): atoms consist of nucleus and circular orbits
o protons - massive nuclear particles with + charge (mass = 1
unit)
o electrons - very low mass wave/particles with − charge, orbit
nucleus
o neutrons - massive nuclear particles with no charge (mass = 1
unit); discovered much later in 1932
04-01-2023
Bohr’s model for the atom
• Electrons move around nucleus in
“fixed” circular orbits or shells (n) with
particular energy levels E (Quantized)
and radius r
• n = 1, 2, 3,…7 or K, L, M…Q
• Maximum electrons accepted by
quantum number n = 2n2
• E2 − E1 = hϑ
• Worked well for hydrogen but failed for multi-electron atoms
• Arnold Sommerfeld: Electrons occur in elliptical orbits with different
geometrical shapes but similar energy levels
• Schrödinger: electrons occur in elusive orbitals (variously shaped areas
in which electrons have a high probability of being found)
• e- spin around nucleus and give atom it's size (statistical size)
• Atomic Weight (A) = Z
+N
• Z = atomic number; N =
neutron number
• Chemical properties of isotopes same as number & distribution of
electrons are same
• Atomic weight (or mass number)= Ʃ masses of naturally
occurring isotopes weighted by fractional abundance of each
isotope; expressed in atomic mass units (amu)
6
 04-01-2023

Filling up electrons in orbitals

• n = 2, three 2p orbitals
f d
have same energy; n = 3,
f d p
all 3p and 3d orbitals have s
p
Relative Energy

same energy respectively f d

p s
• 1s < 2s < 3s < 4s < 5s < 6s d s
< 7s p
2p < 3p < 4p < 5p < 6p d
s
3d < 4d < 5d < 6d p
s
4f < 5f p
s
• For Z <20:
2s < 2p s
• Filling up of shells and subshells in the following order-
3s < 3p < 3d
n= 1K 2L 3M 4N 5O 6P 7Q 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 6d (Aufbau Principle)
4s < 4p < 4d < 4f, etc.
• For Z >20: • No two e- have identical sets of 4 quantum numbers (Pauli exclusion Pr.)
4s < 3d
• Single e- fill first before pairing; unpaired electrons have parallel spins; paired
have opposite spins (Hund’s rule of max multiplicity)

The Periodic Table

• It was recognized in 1869 if elements are arranged in order of

increasing atomic weight (chemical combining weight), there is a
periodic repetition of chemical properties

• This led to arrangement of elements in rows (Periods) and

columns (Groups)

• And finally, to the modern periodic table 50 years later

• Elements are arranged in terms of increasing atomic number

7

• Periods numbered according to first quantum number of orbitals filled.
E.g., 1s= 1st Period; 2s & 2p = 2nd Period etc.
• Characteristics of an atom depend a lot on e- configuration
• The outermost shell or valence e- s that are fundamental
• Elements in Periods have variable physical & chemical properties
because of increasing atomic# (e- are added)
• Similar outermost shell configurations  Groups in the Periodic Table so
similar physical & chemical properties
– alkali metals (IA) have a lonely e- in outer shell
– halogens (VIIA) have 7 e-
– inert gases (VIIIA) have 8e- a magic #... filled s & p (He only has s
with 2 e-)
Chemical Behavior of Elements
Ionization Potential (I): Energy that must be supplied to a neutral atom (M)
in the gas phase to remove an electron to an infinite distance
Lower the Ionization Potential- easier to convert atom to a cation
Ionization Potential increases left to right in a Period and top to bottom in a
Group
First ionization potential (I1): energy required to remove the first (the least
tightly bound) e-
Second ionization potential (I2): energy required to remove the second e-
M ⇒ M+ + e− (I1)
M+ ⇒ M2+ + e− (I2)
Electron affinity: energy required for detaching an electron from a singly
charged anion
M− ⇒ M + e− (Eea)
04-01-2023
Transitional elements:
• After 20Ca 3d orbitals more stable hence filled before 4s,
• So, from 21Sc – 30Zn e- enter 3d orbitals of M-shell relative to 4p
orbitals of N shell
• 21Sc – 30Zn: 3d transition elements or first transition series
• 4d transition series (39Y through 48Cd), 5d transition series (57La
and 72Hf through 80Hg), and 6d transition series (89Ac and 104Rf
through element 112)
• All transition elements are metals
• Also have 4f transition series and 5f transition series- also metals
where 4f and 5f orbitals filled up preferentially
Classification of Elements: Based on Ionization Potential & Electron
affinity
 Electron Donor: Metals; Group IA & IIA; low I1 & Eea so readily lose one
or more valence e- to form cations
• Metallic character decreases across a Period as with higher
atomic#, I1 increases in same direction
 Electron Acceptor: Non metals; Groups VIA & VIIA; higher I1 & Eea so
readily accept e- to form anions; Eea usually increases across Periods
with increasing atomic#
 Noble Metals: Inert Gases; do not lose or accept e-; Group VIIIA; 8 e- fill
up s and p orbitals, except He where 2 e- fill up s orbital; very high I1 but
near 0 Eea
 Metalloids or Semimetals: B, Si, Ge, As, Sb, Te, Po, and At; Have properties
of both metals and non metals
• Si & Ge are semiconductors in solid-state electric circuits; unlike metals
semi-conductors are highly conductive at higher temperatures
8
 04-01-2023

Chemical Bonds
• Chemical Bonds: Net attractive forces
holding atoms (or ions) in solids together

• Involve only the valence e-

• Two important bonds in

geochemistry:

(a) Ionic/Electrovalent: Electrostatic

attraction between cation and anions
by transfer of e- E.g., NaCl (loss of e-
from 3s of Na and acceptance by 3p
of Cl)

(b) Covalent: sharing of e- between

atoms due to overlap of orbitals from
two atoms. E.g., Cl2

Ionic Bonds

• Occur among atoms that are far

apart on the periodic table

• Are weaker than covalent, but

stronger than metallic bonds

• Form minerals that are soluble in

H2O, a polar solvent

• Are non-directional - anions and

cations can be approximated as
charged spheres that pack closely
together in mineral structures

• Poor electrical conductors in solid

state

• Strength  (1/bond length) &

valence

9
 04-01-2023

Properties of minerals directly related to binding forces Atomic and Ionic Radii
 Hardness
• Can't absolutely determine: e- cloud is
 Cleavage
nebulous & based on probability of
 Fusibility
encountering an e-
 Electrical and thermal conductivity, and
 Coefficient of thermal expansion
• In crystalline solids the center-to-center
In general, the stronger the bond: distance = bond length
 the harder the crystal
 the higher its melting point • Interionic distance between centers of two
 the smaller its coefficient of thermal expansion ions measured by X-ray diffraction
techniques & radius of ions determined
Example: NaCl - halite & MgO - periclase; structural patterns are through manipulation
similar, yet periclase melts at 2800°C, whereas halite melts at 801°C

- greater amount of heat energy required to separate the atoms in • Ionic radii calculated this way is constant
periclase indicates it has a stronger electrical bond than halite across compounds and total periodic table

• CN 5, 7, 9, 10 uncommon as
Why is it important?? cannot be extended into infinite
regular 3d arrays
• Coordination Number: Number of nearest neighbor (opposite
charge) of the ions in a crystalline structure • Most common anion O2- (Ionic
radius 1.4 A0
• Some Rules of packing: • Usually cations have radii between
0.6 & 1.10 A0
(1) Electrical neutrality must be maintained in crystal structure • R usually between 0.43 & 0.79
(2) Cation-Anion distance must be close to equilibrium distance R0 • Therefore CN 6 most common for
(3) Cations should be surrounded by as many anions as possible silicate minerals
but far way from each other & vice-versa • Some cations have more than 1
coordination number e.g., Al3+
• Cations are usually smaller so number of anions that can be
• R = 0.54/1.4 A0 = 0.386 (closes to
packed around cations determines crystal structure 0.414 so between CN 4 and 6
• Al3+ occurs in tetrahedral
• Radius Ratio (R)= rc/ra coordination (subst. Si4+) at high T
and low P
• R is fixed for a specifc CN and increasing R will lead to increasing
• Al3+ occurs in octahedral
CN coordination at high P and low T

10
 04-01-2023

Important Points:
• For silicate minerals with CN = 6:
Halite
(a) Cations usually smaller than anion except Rb, Ba that are larger than F- Na
(smallest anion)
Cl
(b) For elements in same Period ionic radius decreases with increasing Z
(due to increased nuclear attraction for e- cloud)
rSi4+ (0.48) < rAl3+ (0.54) < rMg3+ (0.72) <rNa+ (1.02) Cl Cl
rF- (1.33) < rO2- (1.40)

(a) For Lanthanide series (+3 charge) ionic radii decreases with increasing
Z due to increased nuclear charge – lanthanide contraction Cl

(b) For Alkali metals or halogens ionic size increases downwards in a

Group due to addition of e- with most probable distance farthest from
John Winter web sources
nucleus
(c) For cations of same elements ionic radii decreases with ionic charge
(decrease in e-)

Example of close packing: Hexagonal Cubic Packing (CN = 12)

1
2 1

John Winter web sources

John Winter web sources

11
 04-01-2023

John Winter web sources John Winter web sources

John Winter web sources

John Winter web sources

12
 04-01-2023

John Winter web sources John Winter web sources

John Winter web sources John Winter web sources

13
 04-01-2023

Ionic Substitutions
• Deviation of chemical composition of minerals from ideal chemical formula
due to incorporation of minor foreign ions by ionic substitution that are
common
• Goldschmidt’s rule of substitution: Pure ionic Substitution required!!
(i) Ions with same charge and size will substitute each other completely
forming solid solutions- ionic radii must not differ > 15%

− If radii differs between 15 – 30% then limited/partial substitution

occurs; if > 30% solid solution non-existant
− E.g., Ta5+ (0.64 A0) for Nb5+ (0.64 A0), Hf4+ (0.71 A0) for Zr4+ (0.72 A0),
Ga3+ (0.62 A0) for Al3+ (0.54 A0), and Fe2+ (0.78 A0) for Mg2+ (0.72 A0)
in many silicate minerals

(ii) For ions having same charge but different radii, smaller ion will be
John Winter web sources preferentially incorporated as it forms a stronger bond. E.g. during magmatic
crystallization early formed olivine tends to be rich in Mg2+ (0.72 A0) relative
to Fe2+ (0.78 A0)

(iii) For ions with similar radii but different charges, ion with higher charge
will be preferentially incorporated as it forms a stronger bond

− If substituting ion has higher charge than ion in lattice then it is

“captured” by crystal structure
− If substituting ion has lower charge than ion in lattice then it is
“admitted” by crystal structure
− E.g., in K-feldspars Ba2+ is captured in replacement of K; Biotite
admits Li+ for replacement of Mg2+

(iv) Ions whose charges differ by ≈ 1 unit undergo coupled substitution

provided electrical neutrality maintained. E.g., NaAlSi3O8 CaAl2Si2O8

• Goldschmidt’s rule had limitations as pointed out by Ringwood (1955)

as substitution will be limited despite same charge and radius – because
pure ionic subst. rare for most minerals and some covalent bonding
exists

14