GEOKIMIA

(geochemistry)

Rahmat Basuki
Chemistry Division, Faculty of Science and Technology
University of Jambi
 Overview
Materi
1. Introduction and Fundamental in Geochemistry
2. Geochemistry of Solid earth Material
3. Experimental Method: Diffraction Effect (XRD, ND, e diffraction)
4. Experimental Method: XPS, Auger, XES, EXAFS, EXANES)
5. Experimental Method: Optical (UV-Vis-Near IR).
6. Vibrational Spectroscopy: IR, Raman
7. Nuclear Spectroscopy: Nuclear Quadruple resonance, NMR
8. ESR

Penilaian Persentase (%)

1. Ujian sisipan (UTS) 30
2. Uian akhir (UAS) 35
3. Tugas Kelompok 20
4. Tugas Mandiri 10
5. Partisipasi kelas (minimal kehadiran 75%) 5
 Referensi
a. Govett, G. J. S (Editor)., 2000. Handbook of exploration geochemistry Vol. 7.
Australia. Elsevier Science B.V
b. Ottonelo, G., 1997. Principle of Geochemistry. New York: Columbia University
Press
c. Rollinson, H. R. 1993. Using Geochemical Data: Evaluation, Presentation,
Interpretation. London: Pearson Education Limited
d. Schulz, H. D dan Zabel, M (Editors). 2005. Marine Geochemistry 2nd Revised,
updated and extended edition. Germany: Springer-verlag
e. Gupta. C. K. dan Krishnamurty, N. 2005. Extractive Metallurgy of Rare Earth. Boca
Raton; CRC Press
f. De Vivo, B., Belkin, H. E., dan Lima, A. (Editors). 2008. Environmental
Geochemistry: Site Characterization, Data Analysis, and Case Histories.
Amsterdan: Elsevier
g. Tossel, J. A. dan Vaughan, D.J. 1992. Theoretical Geochemistry: Application of
Quantum Mechanics in The Earth and Mineral Sciences. New York: Oxford
University Press
Chapter 1
Introduction and Fundamentals in
Geochemistry

Rahmat Basuki
Chemistry Division, Faculty of Science and Technology
University of Jambi
 Geochemistry - an Introduction

Geochemistry: Study of the chemistry of the earth.

Subject: (1) distribution of the elements (and their isotopes) in all

parts of the Earth (the atmosphere, and hydrosphere, the Earth' s
crust, and its deeper interior -mantle and core-); (2) atmosphere
and hydrosphere chemistry; (3) chemistry of extraterrestrial matter
(strictly termed cosmochemistry); (4) a recent, interdisciplinary
fields (such as biogeochemistry) and a return to attempts to view
the chemical systems of the Earth (lithosphere, hydrosphere,
biosphere, and atmosphere) as a whole.
 Sub-disciplines
Geochemistry uses the tools of chemistry to understand processes on
Earth.

The wide field of Geochemistry includes:

Trace element geochemistry

Isotope geochemistry
Petrochemistry
Soil geochemistry
Sediment geochemistry
Marine geochemistry
Atmospheric geochemistry
Planetary geochemistry and Cosmochemistry
Geochemical thermodynamics and kinetics
Aquatic chemistry
Inorganic geochemistry
Organic geochemistry
Biogeochemistry
Environmental geochemistry
etc..
 Geochemistry - an Introduction
What is Geochemistry?

The urge to make geology more quantitative has led to the widespread
inclusion of the so-called basic sciences such as physics and chemistry into
the study of geology. The term geochemistry was first used by the Swiss
chemist Schnbein in 1838. V.M. Goldschmidt, who is regarded as the
founder of modern geochemistry, characterized geochemistry in 1933 with
the following words:

The major task of geochemistry is to investigate the composition of the Earth

as a whole and of its various components and to uncover the laws that
control the distribution of the various elements. To solve these problems, the
geochemist needs a comprehensive collection of analytical data of terrestrial
material, i.e. rocks, waters and atmosphere. Furthermore, he uses analyses
of meteorites, astrophysical data about the composition of other cosmic
bodies and geophysical data about the nature of the Earths inside. Much
useful information also came from the synthesis of minerals in the lab and
from the observation of their mode of formation and stability conditions.
 Geochemistry - an Introduction

The great Norwegian geochemist V.M.

Goldschmidt formulated the tasks of
geochemistry as: (1) to establish the terrestrial
abundance relationships of the elements; (2) to
account for the terrestrial distribution of elements
in the geochemical spheres (such as the minerals
and rocks of the lithosphere); (3) to detect the
laws governing the abundance relation ships and
the distribution of the elements.
 Geology and Geochemistry
What is the difference between Geology & Geochemistry?
Geology is direct observation and interpretation of field relations to infer
history and present state (e.g. hazards and resources) of the solid Earth
and its regions
structural geology, geomorphology, stratigraphy, paleontology,
petrology, mineralogy, volcanology...
Geochemistry is the application of principles of chemistry to
understanding the Earth (solid, ocean, and atmosphere)
Fundamental principles such as radioactive decay, conservation of
elemental and isotopic mass, thermodynamics and kinetics bring rigor
and certainty to geological interpretation
The tools of nuclear, electronic, and physical chemistry are explained at
a sufficient level to understand
origin and abundances of atoms; bulk composition of the Earth and its
reservoirs; origin and evolution of these reservoirs
 The Periodic Table of Elements
Symbols and numbers Isotopes

The atoms of an element can differ in

mass from each other because they
have differing numbers of neutrons.
Those with more neutrons will weigh
more and be more massive. The
atomic mass (often referred to as
atomic weight) of an element is
calculated by adding together the
number of protons and the number of
neutrons.

Examples for isotopic couples:

Stable isotopes:
H-1, H-2 (D), H-3 (T) (or 1H, 2H, 3H)
C-12, C-13, C-14 (or 12C, 13C, 14C)
O-16, O-18
Radiogenic isotopes:
Fe-54, Fe-56
U-235, U-238
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.
 The Electronic Structure of Atoms

L shell
K shell N
L M
K

Electron shell representation of

carbon atom: The copper atom has one lone
The inner-most (first) shell is full as it electron in its outer shell, which can
can hold only two electrons. The second easily be pulled away from the atom.
shell can hold eight but has only four.

Protons, neutrons, electrons

The Electronic Configuration of the Elements
 Chemical Properties of the Elements
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)
 Chemical Properties of the Elements
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.
 Chemical Properties of the Elements
Pauling Scale
The Pauling Scale is the most commonly used scale of electronegativity values. The
calculations used to arrive at the numbers in the scale are complex. It is most common to
simply know the results of those calculations. The scale is based on Fluorine having the
largest electronegativity with a value of 4.0. The Francium atom is assigned the lowest
electronegativity value at 0.7. All other values are located between these extremes.
Examples: Li--1.0 Be--1.5 B--2.0 C--2.5 N--3.0 O--3.5 F--4.0.

(Pauling scale)
Chemical Properties of the Elements
 Chemical Properties of the Elements

R.S. Mulliken (1934) proposed an electronegativity scale in which the electronegativity,

M is related to the electron affinity EAv (a measure of the tendency of an atom to form a
negative species) and the ionization potential IEv (a measure of the tendency of an atom
to form a positive species) by the equation:

M = (IEv + EAv)/2

The subscript v denotes a specific valence state.

The Mulliken electronegativities are expressed directly in energy units, usually electron
volts.
 Chemical Properties of the Elements
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)
 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
Coordination/Dative/Semipolar Bond: Covalent bond which is the two electrons
derive from the same atom.

and Bond
 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.
 Intermolecular Force
Hydrogen Bond: Electrostatic attraction between two polar group that occur when a
hydrogen bound covalently to a highly electronegative atom (F, O,
and N).

London Dispersion Force: temporary

attractive force that result
when electron in two adjacent
atoms occupy positions that
make atom form temporary
dipoles (Sometimes called
induced dipole-induced dipole
attractions)

Dipole-dipole Force: attractive

forces between
the positive end
of the polar
molecule and
the negative
end of another
polar molecule.
Chemical Properties of the Elements - Summary
Hydrogen Hydrogen is unique as it is the simplest possible atom consisting of
just one proton and one electron
Alkali Metals These are very reactive metals that do not occur freely in nature.
These metals have only one electron in their outer shell, therefore
they are ready to lose that one electron in ionic bonding with other
elements. The alkali metals are softer than most other metals.
Cesium and francium are the most reactive elements in this group.
Alkaline Earth The alkaline earth elements are metallic. All alkaline earth elements
Metals have an oxidation number of +2, making them very reactive.
Because of their reactivity, the alkaline metals are not found free in
nature.
Transition The transition elements are both ductile and malleable, and conduct
Metals electricity and heat. The interesting thing about transition metals is
that their valence electrons, or the electrons they use to combine
with other elements, are present in more than one shell. This is the
reason why they often exhibit several common oxidation states.
Other Metals The elements are classified as other metals, unlike the transition
elements, do not exhibit variable oxidation states, and their valence
electrons are only present in their outer shell. All of these elements
are solid. They have oxidation numbers of +3, +4, -4, and -3.
Chemical Properties of the Elements - Summary
Metalloids Metalloids are the elements found along the stair-step line that
distinguishes metals from no n-metals. This line is drawn from
between Boron and Aluminum t o the b order between Polonium and
Astatine. Metalloids have properties of both metals and non-metals.
Some of the metalloids, such as silic on and germanium, are semi-
conductors.
Non-Metals Non-metals a re not able to conduct electricity or heat very w ell. As
opposed to metals, non-metallic elements are very brittle. Th e non-
metals exist in two of the thre e states of matter at room temperature:
gases (such as oxygen) and solids (such as carbon). Th ey have
oxidation nu mbers of +4, -4, -3, and -2.
Rare Earth The thirty rare earth e lements are composed of the lantha nide and
Metals actinide series. The y are transition metals. One e lement of the
lanthanide series and most of the elements in the actinide series are
called trans-uranic, and are synthet ic or man-made
Halogens The term halogenmeans salt-formerand compounds containing
halogens are called salts.All halogens have 7 electrons in their
outer shell, giving the m an oxidation number of -1. The ha logens are
non-metallic and exist, at room temperature, in all three states of
matter
Noble Gases All noble gases have the maximum num ber of electrons possible in
their outer shell ( 2 for Helium, 8 for all o thers), making the m stable
and preventing them from forming compound s readily.
 What is the Solar System made of?

What is the relative abundances of the various elements throughout

the Universe?
This turns out to be a difficult task for one obvious reason.
Spectroscopic measurements of elements from the distant stars are
strongly biased towards only those elements in excited states at or near
the stellar surface. Those elements principally in the interior do not
contribute to surface radiation in the same proportions as actually exist
in a star.
The situation is better for the Sun. When element distributions are
stated as Cosmic Abundances, they actually are rough estimates made
from Solar Abundances .
What is the Solar
System made of?
From the figure, we see four
patterns:

An overwhelming
abundance of light elements
A strong preference for
even-numbered elements
A peak in abundance at
iron, followed by a steady
decrease.
Elements 3-5, Lithium,
Beryllium and Boron, are very
low in abundance.

These patterns have to do

with nucleosynthesis
(element formation) in the
stars.
 What is the Solar System made of?
If the Sun and Solar
System formed from the
same material, we would
expect the raw material of
the planets to match the
composition of the Sun,
minus those elements that
would remain as gases.
We find such a
composition in a class of
meteorites called
chondrites, which are
thought to be the most
primitive remaining solar
system material.
Chondrites are considered
the raw material of the
inner Solar System and
probably reflect the bulk
composition of the Earth.
What is the Earth
made of?
Relative abundance by
weight of elements in the
whole Earth and in the
Earths crust.
Differentiation has created
a light crust depleted in
iron and enriched in
oxygen, silicon, aluminum,
calcium, potassium, and
sodium.
 What is the Earth made of?

Crustal Element Distribution

The abundance of elements in the Earth's crust is much

different from the abundance of elements that are to be
found on the other planets and our Sun. The continental
crust of the Earth also differs radically from the overall
composition of the Earth.
Our Earth as a whole and its crust, in particular, have
extraordinary concentrations of elements, all associated
with silicate minerals like olivine, pyroxene, amphibole,
plagioclase, the micas, and quartz. Although there are a
vast number of silicate minerals, most silicate minerals are
made from just eight elements.
 What is the Earth made of?
Crustal Element Distribution

The two most common elements in the Earth's crust, oxygen and
silicon, combine to form the "backbone" of the silicate minerals,
along with, occasionally, aluminum and iron. These four
elements alone account for about 87% of the Earth's crust. This
silicate or alumina-silicate "backbone" carries excess negative
charge, however. Positive charge in the form of cations has to be
brought in to balance this negative charge. The four most
important elements that fit in the mineralogical structures of the
silicates are calcium, sodium, potassium and magnesium. Taken
all together, constituting nearly 99% of crustal elements, leaves
little room for all of the other elements.
As a consequence, all other elements are either nearly absent
from the Earth's crust or are found primarily in non-silicate rocks.
 What is the Earth made of?

The silica tetrahedron and the structure of silicate minerals

a. The silica tetrahedron

consists of a central
silicon atom bound to 4 b. In orthosilicates such as olivine, the tetrahedra are
oxygens. separate and each oxygen is also bound to other
metal ions that occupy interstitial sites between the
tetrahedra.
 What is the Earth made of?

d. In sheet silicates,
such as talc, mica, and
clays, the tetrahedra
each share 3 oxygens
and are bound together
into sheets.

c. In pyroxenes, the tetrahedral each

share two oxygen and are bound
together into chains. Metal ions are
located between the chains.
Problems!
1. Mempelajari apakah geokimia? Sebutkan beberapa sub disiplin
ilmu geokimia!
2. Informasi apakah yang dapat diperoleh dari konfigurasi
elektron? Berikan 5 sifat 20Ca!
3. Seberapa baik anda mengenal TPU? Berikan masing-masing 5
unsur untuk golongan berikut: Alkali tanah, transisi, gas mulia,
tanah jarang.
4. Berikan penjelasan tentang ikatan ion, kovalen, dan logam?
5. Kelompokkan benda-benda dibawah ini sesuai dengan
ikatannya yang paling dominan: garam dapur, kapur tohor,
cangkang telur, sendok stainless steel, paku, paku beton, kaca,
keramik, kain, sweater berbahan nylon, air, gas rawa, botol
minuman, penggaris mika, dan pensil.
6. Apakah yang dimaksud dengan energi ionisasi? Golongan
manakah yang memiliki energi ionisasi dalam TPU?
Problems!
7. Mengapa unsur-unsur kimia dalam bumi saling berikatan?
8. Senyawa apa yang paling banyak di bumi?