CHEMICAL COMPOSITION OF

THE EARTH
Nisa Nurul Ilmi, S.Si., M.Sc.
Fakultas Teknik Geologi
Universitas Padjadjaran
2015
INTRO

BASIC CHEMISTRY REVIEW

The Electronic Structure of Atoms
Electrons and Orbits

The electronic structure of

an atom largely determines
the chemical properties of
the element.
Elements within the same
group of the Periodic Table
have the similar outer
electronic configuration and
behave chemically similar.

Each electron shell

corresponds to a period or
row in the Periodic Table.
The periodic nature of
chemical properties reflects
the filling of successive
shells with additional
electrons.
 Electron Donor vs. Acceptor
qualitatively
Electron donors Electron acceptors
(cations – metals) (anions – non-metals)
 Electron Donor vs. Electron Acceptor
quantitatively

• Defined by:
- First ionization potential
the energy required to remove one electron from a positively charged
particle.
indicates how strongly the nucleus of a neutral atom attracts an
electron in a partially filled orbital.
- Electronegativity
the ability of an atom in a molecule to attract electrons to itself.
measures the ionic character of covalent bonds, indicating the extent
to which two atoms share their valence electron equally.
elements with low electronegativity are electron donors/ metals
 First ionization potential
Ionization potential

The First Ionization

Potential is the energy
required to remove the
least tightly bound
electron from the atom.

Example: H --> H+ + e-

The second, third, …

ionization potentials are
defined
correspondingly.

Valence is the number

of electrons given up or
accepted. Transition
metals often have more
than one valence.
Example: Fe(II) and
Fe(III)
First ionization potential
First ionisation potential >>>

First ionisation potential <<<

 First ionization potential
• The increase coincides
with the progressive
filling of the electron
orbitals
• Reflects the reluctant of
atoms to give up
electrons from orbitals
that are nearly full

Atomic number

Character of elements in each periods changes from metallic (low ionisation potential,
electron donor) to nonmetallic (high ionisation potential, electron acceptor).
 First ionization potential

First potential
ionisation of Be
and N is higher
due to filling of s-
orbital, and the
half-filling of p-
orbital

The systematic variation of the first ionization potentials

confirms that the metallic character of the elements in each
period decreases with the increasing atomic number
 Electronegativity
Electron Affinity
Electron Affinity is a measure of the desire or ability of an atom to gain electrons. It is an
energy concept. The formal definition states that Electron Affinity is the amount of energy
released when an electron as added to an atom. Most atoms tend to lose energy when they
gain electrons. Some atoms do not. The elements located in the upper right corner of the
Periodic Chart have the high E.A. values (usually found as anions ) while those in the lower
left corner have the low E.A. value (usually found as cations ). A generic equation of the EA
process would be as follows.

X + e- --> X-1 + EA. Often this is measured in electronvolts.

Electronegativity
The concept of Electronegativity refers to the ability of a bonded atom to pull electrons
towards itself.
It is defined as the relative ability of an atom in a molecule to attract electrons towards itself.
As atoms bond, electrons are shared or transferred. The atom with the higher
electronegativity will dominate the electrons.

In order to be able to determine electronegativity values it is important to observe the

behavior of atoms in a bonded situation. Consequently, the Noble Gases do not usually
appear with listed electronegativity values.
 Electronegativity
Electronegativity>>>
Electronegativity<<<
 Electronegativity
Halogens have high electronegativity

Noble gases have zero electronegativity

• Electronegativity increases as the available orbitals become filled with electron

• The electronegativities of the noble gases are shown as ‘zero’ (these elements
do not attract electrons to themselves).
• Electronegativities of group A elements (demonstrated by Alkali metal and
halogens) decrease with increasing atomic number in one group.
• Differences in electronegativity of elements related to the ionic character of
the bond formed by their atoms.
 Electronegativity and first potential
ionisation

The binding energy of valence electrons

decreases.
i.e. the larger the atom, the more loosely it
holds its valence electrons

Both parameters decrease within a group

 Covalent Character
Covalent character >>>
Covalent character <
 Covalent Character

The covalent character of bonding

between elements increases with
increasing atomic number in a
period but is little changed within a
group

• The alkali metal-oxygen bonds are highly ionic

• The halogen-oxygen bonds are highly covalent
• All other elements in the periodic table form bonds with oxygen whose
character is intermediate between these extremes
 C – O in CO32-
N – O in NO3-
Covalent vs. Ionic S – O in SO42-
Si – O in SiO44-

Na – Cl
K – Cl
Cs – F
 Bonding in Molecules

What difference does it make in

geochemistry whether chemical bonds are
covalent or ionic?

The physical and chemical properties of all compounds depend on the

character of the bonds that hold them together
 Chemical Bonding
Ionic Bond: total transfer of electrons from one atom to another

Covalent Bond: the outer electrons of

the bound atoms are in hybrid orbits that
encompass both atoms.
Due to different electronegativity, covalent
bonds are often polar --> dipole
interactions (Van der Waals interactions)
 Chemical Bonding

Metallic Bond: valence electrons are not

associated with any single atom, but are
mobile (“electron sea”).

This bond type is less important in

geochemistry than the other bonds.
 Example in geochemistry
In calcite mineral (CaCO3) when dissolved in water:

CaCO3 → Ca2+ + CO32

Ionic interaction
(bond)
Covalent bond between C – O
(this bond would not affected
by water)
 Ionic Radius
Ionic radius
Cations have smaller radii than anions. Ionic radius decreases with increasing charge.
Ionic radius is important for geochemical reactions such as substitution in crystal lattices,
solubility, and diffusion rates.

Comparison of some atomic and respective ionic

radii (in nanometers)
 Ionic Radii
Ionic Radii <<<
Ionic Radii >>
Ionic Radii vs. Atomic number
Ionic Radii vs. Atomic number
 Ionic radii in geochemistry
The radius ratio of a cation with respect to the surrounding anions
determines its coordination number and hence affects the three-
dimensional patterns the ions form in ionic crystal
Chemical Composition of The Earth
• Major objectives:
In general: Study the
chemical
composition of the
continental crust
In spesific: Study the
different types of
rocks composing the
crust
 The Continental Crust
Why is it important?

The crust of the Earth

consist of all of the
natural resources that
sustain us

Source:
http://elearning.stkc.go.th/lms/ht
ml/earth_science/LOcanada1/102/
4_en.htm
 CONTINENTAL VS. OCEANIC CRUST
The crust is the outer shell of the Earth,
which lies above the mantle

Continental Crust vs. Oceanic crust

Continental crust Oceanic Crust

• 30-50 km thick • 5-8 km thick

• Primarily • Primarily
composed of composed of
igneous and basalt, diabase,
metamorphic and gabbro
rocks rocks
Source:
http://elearning.stkc.go.th/lms/html/ea
rth_science/LOcanada1/102/3_en.htm
 The Continental Crust
• Mainly igneous and metamorphic rock
• Metamorphic rock mostly in orogenic belts
• The difference between igneous and
metamorphic rocks are unclear
• Sedimentary and volcanic rocks form at the
surface of the Earth, underlying the
metamorphic and igneous rocks
Estimating chemical composition if the
continental crust
1. Averaging large numbers of chemical analysis
2. Combining chemical analysis of different rock
types weighted in terms of their abundance
3. Anaylsing sediment derived from the
continent
4. Combining composition of acidic and mafic
rocks in varying proportions
5. By modelling
Earth Crust Composition:
MAJOR ELEMENT
Estimates of The Average Chemical Composition
of The Continental Crust in Weight Percent
 Chemical Composition estimation by
Clarke & Washington (1924)
• Averaging a large number
of chemical analysis of Oxide from rocks
Clarke and Washington (1924)
a b
igneous rocks from SiO2 59.12 59.07
continent and ocean basins TiO2
Al2O3
1.05
15.34
1.03
15.22
• Combining the average Fe2O3
FeO
3.08
3.80
3.01
3.71
chemical composition of MnO 0.12 0.11

igneous rocks with MgO

CaO
3.49
5.08
3.45
5.1
chemical composition of Na2O 3.84 3.71

shale, sandstone, and K2O

P2O5
3.13
0.30
3.11
0.3
limestone (related to their CO2
H2O 1.15
0.35
1.3
abundance) Sum 99.50 99.56

• Based on ≥ 5000 rock

samples
Chemical Composition estimation by V.
M. Goldsmith (1954)
• Analysing 77 glacial clay from southern Norway
• The reason: Oxide from rocks Goldsmith (1954)
– glacial sediment of Pleistocene age was produced by SiO2 59.19
mechanical erosion of bedrock in Scandinavia with TiO2 0.79
little chemical weathering Al2O3 15.84
– Transport at the base of the ice sheet and subsequent Fe2O3 3.41
deposition by melt water caused the glacial clay to be FeO 3.58
well mixed MnO 0.11
• The rock sample in the ice sheet is suitable to MgO 3.3
represent the cause CaO 3.07
• Concentration of CaO and Na2O lower than Clarke & Na2O 2.05
Washington (1924) presumably because of the loss K2O 3.93

of the compound in the clay by leaching P2O5 0.22

• Glacial clay has lower TiO2 content as the regional CO2 0.54
H2O 3.02
characteristic of the rocks of Scandinavia. Sum 99.03
 Chemical Composition estimation by
Daly (1914)
• Estimates the composition by
Oxide from rocks Daly 1914
SiO2 60.06
TiO2 0.90
combining analysis of granite Al2O3 15.52
Fe2O3 3.55
and basalt in equal proportion FeO 4.06
MnO 0.21

• The reason: MgO

CaO
3.56
5.62

The rock types were thought to Na2O

K2O
3.28
2.88
originate from fundamental P2O5 0.36
CO2 -
magmas of granitic and basaltic H2O -

composition Sum 100.00

 Chemical Composition estimation by
Poldevaart (1955)
• Constructed a detail model by dividing Oxide from rocks
the crust into the continental shield, SiO2
Poldevaart (1955)
59.4
young folded belts, the suboceanic TiO2 0.7

regian, and the deep oceanic regian Al2O3

Fe2O3
15.0
2.4

• Each region were assigned by their FeO

MnO
5.6
0.1
certain lithologic composition MgO 4.2

• The lithologic composition were

CaO 6.6
Na2O 3.1

combined with the chemical K2O

P2O5
2.3
0.2
composition of the different rock CO2 -

types according to their abundance H2O

Sum
-
100.0
• The data shown here contains his
estimation as the whole crust
 Chemical Composition estimation by
Poldevaart (1955)
• Poldevaart also distinguish the chemical composition estimation as 4 different
crust division based on their structural unit
• This illustrating the difference in chemical composition between continental (
continental shield + young folded belts) and oceanic crust (deep oceanic
region)
• Compare with the continental crust, the oceanic crust has:
– higher average concentration of: Fe2O3 + FeO, MgO, CaO, MnO, P2O5, and
TiO2
– Lower concentration of: SiO2, Al2O3, Na2O, and K2O
• The reason:
– Continental is composed primarily of granitic rocks
– Oceanic crust consist largely of olivine basalt
• However, Moores (1982) found that oceanic crust is actually composed of
mafic and ultramafic rocks. The composition of these rocks in average might
be the same as basalt, although trace elements concentrations have been
altered by interaction with heated seawater.
 Chemical Composition estimation by
Ronov & Yaroshevsky (1976)
• Modeled the chemical Oxide from rocks Ronov & Yaroshevsky (1976)
SiO2 59.3
composition based on two TiO2
Al2O3
0.7
15.0

distinct crust, continental Fe2O3

FeO
2.4
5.6

crust and oceanic crust MnO

MgO
0.1
4.9

• The composition is similar

CaO 7.2
Na2O 2.5
K2O 2.1
to those proposed by P2O5 0.2
CO2 -
Poldevaart (1955) H2O
Sum
-
100.0
 Chemical Composition estimation by
Taylor & McLennan (1985)
• The method was by estimating the chemical
composition of the continental crust by:
demonstrating that the average concentrations of rare
earth elements (REEs) in sedimentary rocks can be
duplicated by combining chemical analyses of mafic and
felsic igneous rocks in the proportion 1:5
• The results is similar to diorite or andesite. The
crustal model called the andesite model
• Continental crust consist of 75% average
Archean rocks and 25% andesite crust
 Chemical Composition estimation by
Taylor & McLennan (1985)
• The result is different that Oxide from rocks Taylor & McLennan (1985)

any other estimation SiO2

TiO2
57.3
0.9
before Al2O3 15.9
Fe2O3 -

• The concentration of SiO2, FeO 9.1

MnO -
TiO2, Na2O and K2O are MgO 5.3

lower CaO
Na2O
7.4
3.1

• The concentration of
K2O 1.1
P2O5 -

Al2O3, Fe as FeO, MgO, and CO2

H2O
-
-

CaO are higher Sum 100.1

 Technique to determine elements
concentration
1. Wet chemistry: gravimetric/ volumetric
2. Modern Spectroscopy techniques
 Trace Elements
Trace elements are those elements that are not
stoichiometric constituents of phases in the system
of Interest.
Example for most silicate rocks:
• O, Si, Al, Na, Mg, Ca, and Fe are major elements
• H, C, S, K, P, Ti, Cr, and Mn are sometimes major
elements as they could be stoichiometric
constituents of phases, but also referred as minor
elements
• The rest of this called Trace Elements
 Trace Elements
• The existence of trace elements does not
affect the chemical and physical properties of
the system as a whole to a significant extent.
• For dilute concentration of trace elements A
and major component B, the interaction
between A-A is not significant compared to A-
B
Major vs. Trace Elements
 Behavior of the Elements
• Geochemical characteristic of the elements by
Goldsmith. Goldsmith’s Classification
– Atmophile
– Lithophile
– Siderophile
– Chalcophile
 Atmophile
• Elements that are generally extremely volatile
• They form gasses or liquids at the surface of
the Earth
• The elements are concentrated in the
atmosphere and hydrosphere
 Lithophile
• Refer to the tendency of the elements to
partition into a silicate liquid
• Showing affinity for silicate phases
• Concentrated in silicate portion of the Earth
(crust and mantle)
 Siderophile
• Refer to the tendency of the elements to
partition into a metal liquid
• Have an affinity for a metallic liquid phase
• They are depleted in the silicate portion of the
earth
• Presumably concentrated in the core
 Chalcophile
• Refer to the tendency of the elements to
partition into a sulfide liquid
• Have an affinity for a sulfide liquid phase
• Depleted in the silicate earth and maybe
concentrated in the core
• Most elements that are chalcophile are
usually siderophile and visa versa.
 Geochemical Affinity

Gas Phase Atmophile H, He, N, Noble gases

Alkalis, Alkaline Earths,

Silicate Liquid Lithophile Halogens, B, O, Al, Si, Sc, Ti,
V, Cr, Mn, Y, Zr, Nb,
Lanthanides, Hf, Ta, Th, U
Sulfide Liquid
Chalcophile Cu, Zn, Ga, Ag, Cd, In, Hg, Tl,
As, S, Sb, Se, Pb, Bi, Te
Metallic Liquid
Siderophile Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt,
Mo, Re, Au, C, P, Ge, Sn
Goldsmith’s Classification of The
Elements
 Basis for Goldsmith’s Classification in
The Chemistry of Elements
• Siderophile elements are mainly group 8, 9 & 10
elements (and their neighbors)
• Calcophile elements are mainly group 11, 12, and
the heavier group 13-16 elements
• Atmophile are mainly noble gases
• The distribution of electropositive elements
among metal, sulfide, and silicate phases is
controlled by the free energies of formation with
those of ferrous sulfides, and ferrous sillicates
 The Geochemical Periodic Table
• Goldsmith’s classification is relevant mainly
to:
– Distribution of elements in meteorites;
– How elements distribute themselves between the
Earth’s major geochemical reservoir
• The classification is based on how the
elements behave in the silica portion of the
earth (the mantle and crust)