Soran University

Faculty of Science
Department of Petroleum Geosciences

Introduction to geochemistry : thermodynamic and crystal chemistry

Lecturer: Mohammad Pirouei
Socond Year Students
2014-2015

Geochemistry(Thermodynamic and crystal

chemistry)

Table of contents

Free Energy
The States Of Matter
Electronegativity
Coordination Number
Isomorphism And Polymorphism
Atomic Substitution

Geochemistry(Thermodynamic and crystal chemistry)

Thermodynamic
A thermodynamic system is characterized by certain

fundamental properties, divisible in two type:

1:extensive or capacity properties, such as mass, volume
which deepened on the quantity of matter in the system.
2:intensive properties, such as temperature and pressure,
which are independent of the amount of matter in the
system

Geochemistry(Thermodynamic and crystal chemistry)

Thermodynamic

Eternal energy: the total energy of all kinds

contained within a system is called its
eternal energy.

Change in internal energy:

If a system undergoes a change as state and
E1 is the internal energy in the first state and
E2 the internal energy in the second state
then the change in internal energy is
E=E2 E1

Geochemistry(Thermodynamic
Geochemistry(Thermodynamic and
and crystal
crystal
chemistry)
chemistry)

Gibbs Free Energy (Free Energy)

The Gibbs free energy is specially significant in concern with processes

that take place at constant temperature and pressure:
G = E + pV TS
where:
E is the internal energy (SI unit: joule)
p is pressure (SI unit: pascal)
V is volume (SI unit: m3)
T is the temperature (SI unit: kelvin)
S is the entropy (SI unit: joule per kelvin)
Entropy, in thermodynamics, is a measure of the energy in
a thermodynamic system not available to do
useful work.

Geochemistry(Thermodynamic
Geochemistry(Thermodynamic and
and crystal
crystal chemistry)
chemistry)

Gibbs Free Energy (Free Energy)

If Temperature and Pressure for reaction be constant:
1: G=0
there is a reversible reaction with a state of equilibrium,
so free energy of the reactant and products is equal.
2: G<<<0
a large negative value of G means that the reaction as
written tend to proceed nearly to completion
.
3: G>>>0
a large positive value of G means that the reaction
tend to proceed in the opposite direction.

Geochemistry(Thermodynamic and crystal chemistry)

Example

Solid

liquid

Solid

liquid

Solid

liquid

saturation

undersaturation

G=0

G<<<0

supersaturation G>>>0

Geochemistry(Thermodynamic and crystal chemistry)

The effect of temperature and pressure on Volume and density of material

High pressure favor the existence of

material of small volume, that is high density.
The volume a substance become greater at a higher
temperature and lower pressure.

Temperature

Pressure

Volume ?
volume ?

density?
density?

Geochemistry(Thermodynamic and crystal chemistry)

Effect of temperature and pressure on Solubility of

material

The solubility of solids in liquids increase as a

rule with increasing temperature but is usually
diminished by high pressure.

Temperature

Pressure

solubility?
solubility?

Geochemistry(Thermodynamic
Geochemistry(Thermodynamic and
and crystal
crystal
chemistry)
chemistry)

The States Of Matter

Solid

Order

liquid

Gas

Disorder

The state of matter ranges from complete atomic disorder in gasses to complete order in crystals.
Complete order exists only in perfect crystals at absolute zero.
absolute zero is defined as 0K on the Kelvin scale and as 273.15 on the Celsius .

At any temperature above absolute zero the kinetic energy of the atom causes them to vibrate about
their main position in crystal lattices
.
If the kinetic energy of the atoms becomes sufficiently large , the crystal lost its rigidity , that is, its
melt or decomposes.

All matter strives to reach equilibrium with its environment to accomplish this
the atoms try to arrange themselves in such a way that free energy of system be minimum.
Glasses are metastable phases, and they tend to change in to crystalline forms during times.

Geochemistry(Thermodynamic and crystal

chemistry)

atomic radius

The atomic radius of a chemical element is a

measure of the size of its atoms, usually the
mean or typical distance from the nucleus to
the boundary of the surrounding cloud of
electrons.

Geochemistry(Thermodynamic and crystal

chemistry)

Electronegativity
Electronegativity: The ability of one atom
in a molecule to attract electrons to itself.
Pauling set electronegativities on a scale from
0.7 (Cs) to 4.0 (F).
Electronegativity increases
across a period in left to right
and
Down to up in a group.
Atomic radius

electronegativity

Geochemistry(Thermodynamic and crystal

chemistry)

Electronegativities of
Elements
Electronegativity

Geochemistry(Thermodynamic and crystal

chemistry)

Coordination number
Coordination number: The coordination number of a
specified atom in a crystal or compound is the
number of other atoms directly linked to that
specified atom.
The coordination number depends upon to radius ratio
between cat ion and anion. Rc/Ra
The coordination is some extent controlled by the
temperature and pressure at which crystallization took place.
High temperature and low pressure favor low coordination
and low temperature and high pressure favor high
coordination.???????????

Coordination
Number and
Radius Ratio
Radius Ratio is
Rc (cation) / Ra (anion)

fromModified
K&D from K&D

Geochemistry(Thermodynamic and crystal

chemistry)

Coordination

We always consider coordination of anions

about a central cation
Halite

Na
Cl
Cl

Cl
Cl

Geochemistry(Thermodynamic
Geochemistry(Thermodynamic and
and crystal
crystal
chemistry)
chemistry)

ISOMORPHISM

Existence of different substances in one crystalline form is known as

"ISOMORPHISM"
Examples:
1) Na2SO4 & Ag2SO4 both exist in Hexagonal crystalline form.
2) KBF4 & BaSO4 both exist in Orthorhombic
Properties of Isomorphic Substances
1) Isomorphic substances have same atomic ratio
For example
CaCO3

NaNO3
1:1:3
1:1:3
NaF
MgO
1:1
1:1
2) They have different chemical properties.

Geochemistry(Thermodynamic and crystal

chemistry)

The basis of Isomorphism

The basis

of phenomena is that

anion and cation of the same relative size

(i.e., showing the same coordination) and in
the same number tend to crystallize in the
same structure type.

Geochemistry(Thermodynamic and crystal

chemistry)

Polymorphism

Existence of substance into more than one crystalline forms is

known as "POLYMORPHISM".
In other words: Under different conditions of temperature and
pressure, a substance can form more than one type of crystals.
This phenomenon is called Polymorphism .
Example: Calcium carbonate (CaCO3) exists in two types of
crystalline forms.

a. Orthorhombic (Aragonite)

b. Trigonal
Polymorphous substances have similar chemical properties but
different physical properties.

Geochemistry(Thermodynamic and crystal chemistry)

Polymorph's of Quartz

Geochemistry(Thermodynamic and crystal

chemistry)

Type of polymorphism
1:enantitropy:
The change from one polymorph to another is reversible
and take place at a definite temperature and pressure,
867
Quartz
tridymite

1 atm

2:Monotropy:
The change from one polymorph to another is not
reversible.
Marcasite
pyrite.
In monotropy one polymorph is stable and can not
reverse to another form without destroying its structure
by melting or solution.
What about diamond and graphite?

Geochemistry(Thermodynamic and crystal

chemistry)

Atomic Substitution

A substitution is a reaction
in which an atom or a group of atoms
is replaced by another atom or group
of atoms.

Geochemistry(Thermodynamic and crystal

chemistry)

Rules of substitution

This substitution depends primarily by 3

factors:
Ionic radius
Ionic charge
Electronegativity

Geochemistry(Thermodynamic and crystal

chemistry)

Rules of substitution
1: Valences of substituting ions are no more
different than 1
Na+1 for Ca+2
Al+3 for Si+4

2: Difference in the size of substituting ions

must be <15% (at room temperature)

24

Geochemistry(Thermodynamic and crystal

chemistry)

Rules of substitution
3 : Electronegativity
if the electronegativity (numbers) between the preferred
element and the substituting element is too great the
substitution will not occur.
An example is Cu+1 substituting for Na+1 in a Na mineral as
NaAlSi3O8--even though both ions have the same ionic size and
both have the same valence, +1, the electronegativities are
quite different (Cu = 1.9and Na = 0.9).
a slight difference in electronegativities would allow
substitution to occur as a 0.1 or 0.2 difference.

--hence , the substitution of Cu+1 for Na+1 will not

occur.

Geochemistry(Thermodynamic and crystal

chemistry)

Solid Solution

A solid solution is a solid-state solution of one or more

solutes in a solvent.
when homogeneous mixtures of two or more kinds of
atoms occur in the solid state, they are known as solid
solutions
Solvent: the more abundant atomic form is referred as
solvent.
Solute: the less abundant atomic form is referred as
solute.

Geochemistry(Thermodynamic and crystal

chemistry)

TYPES OF SOLID SOLUTIONS

Solid solutions are of two types:

(a) Substitutional solid solutions.
(b) Interstitial solid solutions.

Geochemistry(Thermodynamic and crystal

chemistry)

Substitutional Solid Solutions

If the atoms of the solvent or parent metal are replaced in
the crystal lattice by atoms of the solute metal then the
solid solution is known as substitutional solid solution.
Substitutional Solid Solutions can be either disordered
or ordered.

Geochemistry(Thermodynamic and crystal

chemistry)

Interstitial Solid Solutions

In interstitial solid solutions, the solute atom does not

displace a solvent atom, but rather it enters one of the holes
or interstices between the solvent atoms.

Geochemistry(Thermodynamic and crystal

chemistry)

Table of contents

Geochemistry(Thermodynamic and crystal

chemistry)

Some substitutions are simple

1 for 1 substitution of ions of equal charge

Some substitutions are coupled

Substitution involves 2 or more ions
Necessary to balance different charges

Examples:

Carbonates: Simple
solid solution
between Magnesite
(MgCO3) and Siderite
(FeCO3)
Plagioclase feldspar:
Coupled solution
between Albite
(NaAlSi3O8) to
Anorthite (CaAl2Si2O8)

32

Geochemistry(Thermodynamic and crystal

chemistry)

Geochemistry (Isotopes)

References
Exsolution

Exsolution, process through which an initially

homogeneous solid solution separates into at least two
different crystalline minerals without the addition or removal
of any materials.
In most cases, it occurs upon cooling below the temperature
of mutual solubility or stability of the solution.
The sodium-rich feldspar albite (NaAlSi3O8) and the
potassium-rich feldspar orthoclase (KAlSi3O8), for example,
may exist in a homogeneous solid solution above 650 C
(1,200 F), but below that temperature exsolution will occur.

In perthite Typically the host grain is orthoclase,

and the lamellae are albite. If sodic feldspar is
the dominant phase, the result is an antiperthite.