ES 310 : Applied Geochemistry

Books to be Referred:
1. Introduction to Geochemistry - K.B Krauskopf
2. Introduction to Geochemistry- K.B Krauskopf & D.K.Bird
3. Geochemistry An Introduction : F. Albarede
4. Introduction to Geochemical Modeling - F. Albarede
5. Geochemistry of Natural Waters J. I. Derver
6. Modern Analytical Geochemistry Robin Gill (Ed.)
7. Essentials of Geochemistry J.V.Walther
8. Geochemistry Course Notes:
W. M. White
9. A Treatise on Geochemistry (9 Volumes) : H. D. Holland (Ed.)

Journals :
1. Geochimica et Cosmoctimica Acta: Pergamon-Elsevier Publ. (GCA)
2. Chemical Geology: Elsevier Publ. (ChemGeo)
3.Earth and Planetary Science Letters: Elsevier Publ. (EPSL)
4. Applied Geochemistry: Elsevier Publ.

40% MTE

20% CW+Practicals

40% ETE

Geochemistry - Definition:
The field of geochemistry involves study of the chemical composition of the
earth and other planets; chemical processes and reactions that govern the
composition of rocks and soils and the cycles of matter and energy that
transport the earths chemical components in time and space.
We use the tools of chemistry to solve the geological problems; that is, we use
chemistry to understand the earth and how it works
The most important fields of geochemistry are :
1. Determination of the relative and absolute concentration of the elements
and their isotopes in the earth and earths surface.
2. Examination of distribution and movement of elements in different parts of
the earth (crust, mantle, hydrospace etc.) and in minerals with the goal
to determine the underlying legalities of distribution and movement.
3. Analysis of the distribution of elements and their isotopes in the cosmos
(Cosmochemistry).
4. Study of rock processes and compounds that are derived from living and/or
once living organisms (organic geochemistry).
5. Applications to environmental and hydrological studies.

Broad Areas:
Atmospheric Chemistry
Geochemical Thermodynamics
Isotope Geochemistry
Marine Chemistry
Trace Element Geochemistry
Soil Chemistry
Hydrogeochemistry etc.
Geochemistry was first used by Swiss Chemist, Schobein in 1838
Quantitative, dominated Earth Science during 2nd half of 20th Century
Every aspect of earth science studies has been advanced because of
geochemistry helped by enormous progress in analytical
instrumentation

The electronic structure of atoms and the entire organization of the

periodic table is determined by quantum mechanics and the quantization
of energy; angular momentum, magnetic moments, and spin of electrons

Four quantum numbers called the principal, azimuthal, magnetic and spin
quantum numbers and conventionally labelled n,l.m and ms control the
properties of electrons associated with atoms

The Pauli Exclusion Principle requires that no two electrons in an atom

may have identical values of all four quantum numbers

IONIZATION POTENTIAL, ELECTRON AFFINITY,

ELECTRONEGATIVITY, BONDS

A thermodynamic system is that part of the universe we are considering,

everything else is referred to as the surrounding
An isolated system
can exchange
neither energy (heat
or work) or matter

Closed system may

exchange energy in
the form of both heat
and work with their
surroundings but can
not exchange matter

Transient or Time-Invariant Systems

An adiabatic
system can
exchange energy in
the form of work but
no heat or matter
with its
surroundings

An open system
may exchange both
energy and matter

Chapter 1 : Chemical Equilibrium

Earth: or huge chemical machine Two fold
what is the end-result of convection and differentiation ?
how much time ?
Questions:
- Peridotite Basalts Granite Peridotite
- Hour long convection and differentiation going on, take ?
- Hour et all began ?
- Gold, Cu, Ni in some rocks, liquid he in others ?
Complex, need to have a background of chemical principles and geologic
observation on which understanding of the Earth chemistry can be built

Equilibrium Constants
-It provides a background for attacking problems related to weathering,
sedimentation, digenesis, metamorphism and hydrothermal and magmatic
processes
Two variables of major importance Temp. & pressure.?

P T diagram in Earths crust

Regional
Metamorphism
(high P and T)
Weathering
and
sedimentation

Diagenesis
2

Contact
metamorphism
(low P, high T)
0

200

400
600
Temperature (0C)

20

10

Approximate Depth (km)

Magamatic
process
)

Pressure kbar

30

(Melting
of dry ba
salt

Blue schist
metamorphism
(high P, low T)

d granite)
e
t
a
r
u
t
a
s
HO
(Melting of 2

10

Volcanic activity
800

1000

1200

Geo
th

Pressure kbar

u bdu

c t io n

2
m
rtz
a
er
u
h
Q
ot
+
e
e
tit G
ite
n
n
o
so
um
w
a
a
L
L

0
O
2
H
+

n
Geotherm for Co

200
r
fo
c

400

t
on
in
t
en
s

z one

tact metamorphism

600
Temperature (0C)
(Melting

of dry ba

20

800
1000

10

Approximate Depth (km)

salt)

Musco
vite +
Quart
Melting of H2O
z
K-feld
saturated granite
s par +
Sillima
ni t e +H
2O

or s

6
erm
f

Three Geotherms
10
30

1200

Quantitative treatment Chem. Equil Two Norwegian Investigators of mid 19th

Century . Cato Maxmilan Goldberg and Peter waage from studies of many reaction:
Drive Force of a reaction is primarily dependent on the mass of each substance
taxing part.
Law of Mass Action: The rate of a reaction in directly proportional to the
concentration of each reacting substance.

Reversible reaction :
A+B

Y+Z

Both reactions, forward and backward (reverse) go until their driving forces
become equal.
Driving force of forward reaction : k1 [ A ] [ B ]
Driving force of forward reaction : k2 [ Y ] [ Z ]
k1 [ A ] [ B ] = k2 [ Y ] [ Z ]
or
[Y] [Z]
[A ]

[ B]

k1
k2

K Equilibrium constant

k1 ( A ) ( B )
(Y) (Z)

k2 ( Y ) ( Z )

=
=

( A) ( B )

k1 =

k2

When a reversible reaction has gone as far as it can, The quotient obtained by
multiplying the concentration of the products and dividing by the concentration of
reactants is a constant quantity This relation is experimentally verifiable.
A more general equation for a chemical reaction is,
a A + b B +..
y Y + z Z +..

Coefficient

Chemical

Reversible

Example of Equilibrium
1. Hydrogen Chloride
H2 + Cl2
2 HCl
K

( HCl) 2
( H2 ) (Cl2)

Gas unit : mol Lit ? ?

partial pressure in bars !

K HCl = 2.6X108 or 108.4 (at 10000C)

If H2 and Cl2 are present each at 1 bar, hour much HCl ? ?
If (HCl) = 0.1 bar and (Cl2) = 10-5.0 bar, H2 = ? ?
The formula for the equilibrium constant depends on how the chemical equation is
stated.
2HCl
H2 + Cl2
K1

PH2 PCl2
P2HCl

K1

1K

H2 + Cl2 = HCl

( HCl )

= K11

(K1/2)

(H2 )1/2 (Cl2)1/2

An equibibrium constant has no meaning except in terms of or specified chemical
equation
We Dont Say: Equilibrium constant of HCl.
Kequil. : Function of temperature ?
convention : at 250C and 1 bar pressure

Example ii: carbon dioxide in water

H2O + CO2
Keq. =

( H2CO)

H2CO3
= 10-1.5

(or 0.031)

(H2O) (CO2)

0.3% = 0.0003 bar (10-3.5)

(H2CO3) = 10-1.5 x 10-3.5 = 10-5.0 m

Example iii: Calcium sulfate

CaSO4

Ca2 + SO42-

Keq. = (Ca2+) (SO42) Solubility Product

(CaSO4)

1
Ba2+ + CaSO4

Solubility
Ca2+ + BaSo4

Keq. = (Ca2+)
(Ba2+)

Formation of Hematite from Magnetite

2Fe3O4 + O2

Fe2O3

Keq. = 1 / PO21/2

Example : CaSO4

Ca2+ + SO42-

Keq. = 3.4x10-5
What is the Solubility ?
Is Solubility affected by Presence of a common ion ?
What is the Solubility, for example, of CaSO4 in a Solution of 0.1m CaCl2 ?

Let x be the Solubility, then the Concentration of Ca2+ in solution will be

(x + 0.1), since CaSO4 contributes x mol/Kg and CaCl2 contributes 0.1

Concentration of SO42- will be x

Keq. = (Ca2+) (SO42- ) = (0.1+x) (x) + 3.4x10-5

x = 3.4x10-4 m
Ca in pure water = 5.8x10-3m common-iron effect

Le Chateliers Rule:
Equilibrium responds to any disturbance by trying to undo or reverse the effects
that the disturbance causes !
Endothermic
KAl2(AIS3O10) COH) + SiO2
muscovite

quartz
KAISi3o8 + AI2SIO5 + H2O
K- feldspar

Silimanite

water

Exothermic
Endothermic reactions are favored by a rise in temperature, exothermic reaction by
a fall in temperature
Effect of Pressure:
Equilibrium has been establistied and we raise the pressure on the
entire system ?
How will the equilibrium respond to the disturbance ??

# The reaction must be favored which will lead to a lowering of pressure

or
Favor the reaction that gives the smaller total volume.
H2O
H2O
Liquid
Solid
density 1.0
density 0.92 g/cm3
Increased P leads to formation of liquid water, since liquid water has smaller volume
or higher clensity.

Increased P
Laumontite Lawsonite + Quartz + H2O
Lower Volume
Limestone at granite contacts Three solids and gas
CaCO3 + SiO2
CaSiO3 + Co2
Calcite
Quartz
wollastonite gas
Large Volume
High P, prevents formation of wollastonite

Stability: Qualitative & Quantitative (Later ! )

A stable substance is one that does not react readily in a partiailar environment
Sani dine (K-feldspar) : stable at high T
Adularia (K-feldspar) : stable at Low T
Stability has no meaning except when referred to particular external conditions
Iron is unstable X
Stable with respect to Particular conditions of temperature and pressure, and
particular kinds of associated substances
Galena : Mencum (Stable)
Field (unstable), outcrops of veins
PbS + 2O2
Galena
Slowness
of
reaction

PbSO4
Anglesite

apparent stability

To Remember :
1. For a reversible reaction aA + bB + yY + zZ + ,the equilibrium constant
is defined as Keq. = (y)Y (z)Z
(A)a (B)b
2. Keq. Has a definite value for a particular chemical equation, not for a particular
substance or a particular process.
3. Values of K are customarily given for 250C and 1 bar total P, unless other t and p
are specified.
4. Concentrations of gases in the equilibrium constant formula are generally
expressed as partial pressures in bar (Atm. Pascal).
5. Concentration of solutes in aqueous solution are given as mols of per Kilogram of
water (mol/L, mol fraction).
6. Concentration of solid and liquids, and of water in liquid aqueous solution, are
represented in terms of mol fractions, so in equilibrium constant they do not
appear in the formula if they are pure phases.
7. An equilibrium is called homogenous if all reacting substance are in a single
phase, heterogeneous if they are in or more phases. Most equilibria of
interest in geology are heterogeneous.
8. A mixture is chemically stable either because it is at equilibrium or because
reactions are Slow. The first meaning is generally understood unless the is
specified.

Free Energy :
Change in Enthalpy :
H2 + O2 H2O + 68.3 Kcal
H = Hprod. - HReac. = -68.3 Kcal
2H2 + O2 2H2O

H = -136.6 Kcal

Exothermic reaction : H = - ve
Exothermic reaction : H = +ve
N2 +O2 = 2 NO H = +43.2Kcal.
NaCl
= Na+Cl- H = +0.9Kcal.
If the equation reverses, the sign changes.
Heat of Formation of a reaction: can be added/substracted.
H2S + 3O2
2H 2O +SO2
H2 +S H2S H = -4.8Kcal.
H2 + O 2 H 2 O
H = -68.3Kcal.
S +O2 SO2 H = -71.0Kcal.
Change in equilibrium constant with temperature:
Vant Hoff equation:
dlnK / dT
=
H / RT2
R = Gas constant , PV = nRT
(1.99cal/ mol)

d In K = In K = H/ R

dT/ RT = - H/T2 + C

Where C in a c constant of integration

log

K =

- H +
2.303RT

2.303 x 1.99 x 298 (250C) = 1,364 cal or 1.364 KCal

How to use this equation ?
CO + H2O = CO2 + H2 at 4170C, K = 10
H = - 10.2 KCal
From Table
Putting these values, integration constant C can be found out,
log 10 =
+10.2
+C
2.303x0.00199x690

0.00458
C = - 2.24

(Kcal/mol)

Now to find K at another temperature, say 25 C, the equation can be used with the
value of C
logK = 1.2/ (0.00458 x 298) - 2.24 = 5.26
K = 105.26 = 1.82 x 10 5 (at 25 C)
K = 10 at 4170C
Kequil. Decreased with increase in temperature
300

10

2.0

logSiO2 (ppm)

ppm SiO2

100

Solubility of silica
as a
function of temperature

1.0
0.003 1/T 0K
25 c

0.002
200c

Enthalpy changes as a measure of radioactivity

KNO3 K+ + NO3-

H = +8.4 Kcal.

Enthalpy - not an infillible measure of the tendency of a reaction to take place

A + B A, B
H = 0
Tendency to react = H - D
The measure of degree of disorder is a quantity called Entropy
( = quotient of energy divided by absolute temperature)
D = TS
S = q/T
F = H -T S
H2 + O2 = H2O
F = -56.7Kcal.
H2O = H2 + O2

F = +56.7Kcal

2H2O = 2H2 + O2

F = +113.4Kcal

Free energy of formation :

SO2 + CO2 =
SO3 + CO
-71.7 -94.3
-88.4
-32.8
F = ?
Free energy as a criterion of equilibrium:
F < 0 , Spontaneous reaction
F > 0, Energy to be supplied
F = 0, Equilibrium

 Relation :

F K equili.

F = -RTlnK +RTln [Y]y[Z]z/ [B]b[D]d....

F0 = -RT lnKa
= -2.303 x 1.99 x 298 x log Ka =0, at unit activity
= -1.364 log K (F 0 in Kcal)
CaSO4 = (Ca2+) (SO42-)
Kequil = 3.4 x 10-5
F = ?
Predict the reaction !
Oxidation of galena to anglesite
PbS + 2O2 = PbSO4
F = -171.8 Kcal.
-22.1
0
-193.9
K=?
PbS + SO4= = PbSO4 + S= F0 = +26.1 Kcal.
-221.1 -177.3
-193.9
+20.6
K=?
PbS +2H+ = H2S +Pb2+
F0 =+9.8 Kcal.
-22.1 0
-6.5 -5.8
K =?

Free Energy Changes for activities other than unity?

PbS + 2H+ = H2S + Pb+2
F0 = +9.8 Kcal.
F = -RTlnK + RTln [H2S] [Pb2+] / [H+]2
= F0 + 1.364 log [H2S][Pb2+] / [H+]2
If [H+] = 10-3 M, [H2S] = [Pb2+] =1M
F = ?

If

[H2S] = [Pb2+] = 10-4 M

[H+] = 1M

F = ?

Oxidation Potential :
Oxidation : Increase in positive valence
Zn + Cu 2+ Zn2+ + Cu
Zn Zn 2++ 2 eCu2+ + 2 e- Cu
H2 H + + e-

E0 = 0.00volt

Zn + 2H+ Zn2+ + H2

E0 = 0.76 V

Fe2+ Fe3+ + eMn2+ + 2H2O MnO2 +4H + + 2e-

E0 =+ 0.77V
E0 = +1.23V

MnO2 + 4 H+ + 2 Fe2+ = Mn +2H2O + 2 Fe3+

E0 = -0.46V

Voltages are not multiplied!

-Voltage : Spontaneous reaction
F = nfE
F ? in Mn-Fe reaction!
E = F / nf = (F0/nf) +(RT / nf) ln {[Y]y [Z]z ../ [B]b [D]d }
= E0 + (2.303RT /nf ) log [Y]y [Z]z./ [B]b [D]d
0.059

Nernst Equation

E = ? In Mn Fe reaction at pH =3 and unit concentration of other ions

E0 = F0 / nf = -2.303 RTlog K /nf = (-0.059 / n ) log K

Redox Potentials: Eh
Eh = 0.5 in Fe2+ -Fe3+ (0.77V)
Which is the dominant ion?
Ability to supply electrons to an oxidising agent or to take up electrons from a
reducing agent.

Aqueous Solutions
Water, sublte but important agent of geologic change
Major influence on the course of weathering, diagenesis, metamorphism, magmatic
processes and rock deformation
On surface, -Transporting agent
All other common liquids lie alcohol, acetone, gasoline and CCl4 increase in density
regularly as temperature falls, and freezes to solids denser than liquids, whereas in
contrast water has its greatest density at 40C above its melting point and freezes to a
solid that will float on the liquid
High Dielectric constant dissolves substances and keeps them in dissolved state.
Electrolytes

Representative concentratons of major chemical components in natural waters: (mg/l)

Sea Water
Rain Water
Meteoric Spring meteoricgeothermal
water
water
Temp
20 C
10 C
6 C
300 C
Ph
8.2 5.6
8.82
7.09
Chloride
19,350
1.14
3.14
21.1
Na+
10,760
1.02
22.6
187
SO422,710
1.48
10.9
102.7
Mg2+
1,290
0.24
2.39
0.004
Ca2+
411 0.4
5.06
0.5
K+
399
0.51
1.01
26.6
HCO3142 44.0
245
SiO2
0.5-10
1.2
17.4
777

Acids and Bases

Acids have been described as substances with a sour taste and possessing the ability to
dissolve many substances, to change the color of vegetable dyes like litmus and to
react with bases to form salts. (Robert Boyle, 1663)
Arrhenius (1859-1927) proposed that acids differ from other hydrogen containing
compounds in that they partially dissociate when dissolve in water to set free H + ions.
Bronsted (1879 - 1947) : H+ is an isolated proton and hence couldnot possibly exist by
itself in presence of H2O, and is hydrated forming hydronium ion H3O+.

HCl + H2 O H3O+ + ClHCl H+ + Cl-

Hydronium ion : H3O+ , H5O2+ , H7O3+

Acid is a substance containing hydrogen which gives free hydrogen ions when
dissolved in water
Base : Whose water solutions have a slopy feel, bitter taste, ability to neutralise acids
and the property of reversing the color changes that acids produce in vegetable dyes.
Ammonia, metal oxides, carbonates, hydroxides
Arrhenious : Property common to all bases are ascribed to hydroxide ion, OHNaOH, Ca (OH)2
Ca(OH)2 Ca2+ + 2OHBase is a substance containing the OH group that yields OH- on dissolving in water
Alkali: Arabic term, bitter extract produced by leaching the ashes of a desert plant, bitter
tasting salts Na2CO3
Strong bases, NaOH, KOH, Ba(OH)2
Any solution containing appreciable OHGeologic useage:
Acid Oxide: Oxides of non-metals which dissolve in water (CO2, SO3)
SiO2 :Acid oxide, acidic rocks

Quartz- rich rock : felsic or silisic

Basic rock: Mafic
Na and K-rich : alkaline / alkalic rock

The pH:
NeutralisationHCl + NaOH H2O + NaCl
H+ + Cl- + Na+ + OH- H2O + Na + +ClOH- + H + H2O
What happens if a solution containing exactly 1 equivalent of acid carefully neutralized
with 1 equivalent of base?
Neutral solution = (H+) = (OH-) = 10-7M
H2O = H+ + OH- Kwater = mH +mOH- = 10-14
More precisely = 10-13.998 at 250C

Orders of magnitude variation

-8
ar
5Kb

-10

1Kbar

Saturation
(Liquid-Vapor equilibrium)

-12

-14

-16

Critical point
374.15 C, 220 bars

100

200
Temp c

300

400

500

The product mH+ +mOH- is constant for all water solutions

-H+ is present in strongly basic solution
&

-OH- is present in strongly acid solution

IN solution of a strong acid has mH+ ,
- Neutral solution 10-7mH+
- Strong base

10-14mH+

Discard 10s pH
pH of a solution = negative logarithm of the hydrogen -ion concentration
1 N solution strong acid pH =0, neutral pH =7 Strong base Ph = 14
pHin nature : 4 to 9
Streams in humid regions = 5-6.5
Arid
= 7-8
Soil water
= <4
Sea water
= 8.1 to 8.3

Dissociation Constants of weak acids

Compare: HCl
strong acid

&

H2CO3

Weak acid

Strong and weak depends on extend of dissociation

10

log K

-5

-10

Acids
HC
l=

+C

l-

HSO4 = H+ + SO42-

H2 SO =
HSO - + +
4
H
4

H2CO3 = H+ + HCO3HCO3- = H+ + CO32-

-15
100
Temp.0c

200

300

Bases
5
NaOH = Na+ + OHAl(OH)2+ = Al3+ + OH-

log K

-5

-15

Al(OH)4- = Al(OH)2+ 3OH-

-25
Al(OH)3 (Gibbsite) = Al3++ 3OH-35
100
Temp. c
0

200

300

Weak acids dissociate in steps:

H2CO3 = H+ + HCO(1)
HCO3- = H+ + CO32-

(2)

mH+ mHCO3- / m H2CO3- = K1 = 10-6.4 = 4.2X 10-7

(3)

mH+ mCO3- / m H2CO3- = K2 = 10-10.3 = 5.0X 10-11(4)

Dissociation constant equilibrium constant
To calculate pH of a solution of 0.01M H2CO3:
0.01M refers to total carbonate (mCO32-)
mCO3,total = mH2CO3- + mHCO3- + mCO32- = 0.01mol / kg H2O (5)
(0.01m H2CO3 means a solution obtained by dissolving 0.01mol of CO 2 in a kilogram of
water)
Another equation (neutral electrical solution):
Conc. of +ve charges = Conc. of ve charges
mH+ = mOH- + mHCO3- + mCO32- ?
(6)
Another equation, mH+ + x mOH- =10-14

(7)

To solve : - algebraic computer

- Approximations?
K2 is almost 10,000times smaller than K1 H+ comes entirely from (1)
since mCO32- is very small, mH+ =mHCO3If we assume that mCO32- and mOH- are small enough to be neglected.

(3) Becomes, mH+ / mH2CO3

=10-6.4

(8)

And (5 becomes, mH2CO3 + mH+

=0.01
(9)
Two equations, two unknowns, can be solved. mH+ = 10 -4.2 or Ph = 4.2
Find out concentration of other ions?
If the first dissociation constant of a weak acid is greater than the second by a factor
of 104 or 106 such that,
HnA = H+ + Hn-1 A1- then
mH+ = (mA, total x K1 )1/2
mA , total denoting total concentration of A.
H2 S, K1 = 10-7and K2 = 10-13 , the hydrogen ion concentration of a 0.01m solution is
mH+ = (0.001 X 10-7)1/2 = 10 -5m
pH = 5.0
Salts dissolve in water to give neutral solutions. Eg. NaCl, K2SO4 anions of a strong

acid
Cations of a strong base
NH4Cl, Fe2 (SO4)3
K2 CO3 , NaS2

Cation-weak
Anion-weak
Hydrolysis: Reaction leading to excess of H+ or OH -

Estimating Ionic concentration

Given pH, dissolved carbonate H2CO3 , HCO3- or CO32- ?

Given pH , Fe as Fe3+ , Fe2+ , FeOH2+ or Fe(OH)2+?

Dissolved Zn, Zn2+ , Zn OH+ , Zn (OH)3- , Zn(OH)42- ?

Example: Distribution of carbonate species

Dissolved carbonate: - H2CO3 in acid solution
- CO32- in basic solution
- HCO3- in intermediate range
From eq (1) and (2)
mHCO3/ mH2CO3 = 10-6.4/ mH+ and

mCO32- / mHCO3-=10-10.3/ mH+

mH2CO3 = mHCO3 when mH+ =10-6.4

mCO32- = mHCO3- when mH+ = 10 -10.3

Hence H2CO3 is the dominant carbonate species with pH <6.4

HCO3 -

6.4 TO 10.3

CO32-

> 10.3

pH = 6.4 , total carbonate of all 3 carbonate species???

What is the concentration of CO32- and HCO3- in a solution containing 0.001 m total
dissolved carbonate and a pH = 8.0 ?

Intermediate range , where most of the dissolved carbonate exists as HCO3- . So that
this ion may be assigned a concentration of approximately 0.001m.
Eq.(2) becomes, Mco32- / 0.001 = 10-10.3 / mH+
And (1) becomes 0.001 / m H2CO3 = 10 -6.4 / mH+
If mH+ = 10 -8 then Mco32- = 10-5.3
and mH2CO3

= 10

-4.6

To generalise the result, we rewrite the equations in logarithmic form:

Log Mco32- - (-3) = -10.3 log mH+
and (-3) logmH2CO3 = 6.4 log m H+
Log Mco32- = -13.3 +pH
Log m H2CO3 = 3.4 pH

-2

HC
O

-6
CO32H 2CO 3

log Conc.(m)

250C, 1 bar

-10
1

pH

13

Buffers:
Sea water pH = 8.1 to 8.3

Acid
pH~8.0

Acid
pH~2.0

Sea water

Distilled water

Consider: a solution containing roughly 0.01m H2CO3 and 0.01m NaHCO3

Principal substances in solution:
Na+ , HCO3-, H2CO3 (Equal amount of H2CO3 and HCO3- =0.01m)
From , fig a solution with equal amounts of H2CO3 and HCO3-should have a pH of 6.4
Also from Eqn : mH+ = m H2CO3 / mHCO3- K = (0.01 / 0.01) K =10-6.4m
When acid is added
H+ + HCO3 = H2CO3
Changes the ration , but not enough
If we add enough acid, to change ratio to 2, then mH+ =2x 10-6.4 =10-6.1, pH =6.1
Distilled water: Changes immediately to pH =2.5 why?
HCO3-takes up enough H+, So that free H+ in solution is slightly increased.
If a srong base is added OH-reacts with H2CO3
H2CO3 +OH- HCO3- +H2O
Solutions capable of absorbing considerable H+ or OH- without showing much changes in
pH, are called Buffers
In general, a buffer consista of approximately equal amounts of weak acid (like H 2CO3 )
and a salt of the acid (like NaHCO3)

Complexes:
In electrolyte solutions, some of the ions and molecules exist in the form of complexes
which refer in most general deinition, refers to any combination of two or more atoms
that can exist in solution.
e.g. OH- , SO42- , H2CO3

 In common usage, however, the word refers to more unusual atom combinations,
e.g.
PbCl+ , NaCl(aq.) , HgS22- , UO2(CO3)22-

Chloride complexes:
Cl- forms a wiide range of complexes with cation of alkali, alkaline- earth and
transition metals
Relative stability of chloride complexes has an important influence on the solubilities
of rock- forming minerals and on the ability of aqueous solutions to tansport metals
Low temp. / P high dissociation
High temp. / P 5000c &500 bars density and
Dietric constants of water are small , solvation in reduced and NaCl complex forms.

Table: The dissociation constant for the reaction

NaCl (aq.) Na++ Cl- and the molal volume (v, cm3/mol), density (, g/cm3) and dielectric
constant (E) for water at pressure (bars) and temperature (0c) corresponding to
conditions typical of weathering (1bar, 25 0C), regional metamorphism (5000bar, 500
0c) and contact metamorphism (500 bar, 5000c)
P(bar) T (0c)
log KNaCl
VH2O
h2o
EH2O
1
5,000
500

25
500
500

0.93
-0.65
-5.07

18.07
20.74
70.12

1.00
0.87
0.26

78.47
18.56
3.94

0
ZnCl+ = Zn 2++ Cl-

-2

log K

-4

ZnCl20 = Zn2+ + 2Cl-

-6

ZnCl3- = Zn2+ +3Cl-8

-10
0

ZnCl42- = Zn2+ +4Cl-

100
Temp.( 0C)

200

300

Ag, Au, Cu, Pb, Zn, Fe and Hg form a variety of chloride complexesin aqueous solutions
Cl- complexes of Zn: ZnCl+ , ZnCl2(aq.) ZnCl3- and ZnCl42Effect of Zn chloride complexes on the solubility of the ore mineral sphalerite ()ZnS?
Ability of aqueous chloride solution to transport Zn in shallow hydrothermal
environments??
ZnS
Zn2++S2At 2500c and pressure equal to liquid vapor equilibrium for H 2O, the equilibrium constant
is ,
K= m Zn2+ mS2- = 10-18.86
If the solution contains small amount of S2- ion (10 -10m), Zn2+ = 10-18.86 / 10-10 = 10-8.86m
This is a very small amount if Zn is not complexed with any anion.
The figure is so low that, the ability of such a solution to transport enough Zn to form an
ore deposit is questionable.
Zn is associated with chloride (fluid filled inclusions)
(deposited)
mZn, total =mZn2+ = mZnCl+ +mZnCl2(aq.) +mZnCl3- +mZnCl42From the figure (dissociation reactions,)
mZnCl+ =mZn2+ m Cl-/ K ZnCl+
m ZnCl(aq.) = mZn2+mCl2- / KZnCl3And mZnCl42- = mzn2+ mCl3-/ kznCl42-

Lets estimate the total concentration of Zn in a solution at equilibrium with sphalerite that
contains 0.1m total Cl- and 10-10m s2- ?
ZnS = Zn2+ + S2K = mZ2+ mS2- = 10-18.86
mS2- = 10-10, hence mZn2 = 10-8.86m
Putting this value in the previous equation involving Zn Cl, complexes,
mZnCl+
= 10-8.86mCl- = 10-4.06mCl10-4.8
mZnCl2(aq.) = 10-8.86m2Cl- = 10-3.6m2Cl10-5.5
mZnCl-3

= 10-8.86m3Cl- = 10-2.86m3Cl10-6.0

and mZnCl42-

= 10-8.86m4Cl- = 10-2.46m4Cl-

10-6.4
From these equations, we see that the concentration of Cl- is several orders of
magnitude greater than the concentration of any of the Zn-chloride complexes, Hence
can be neglected.

Cab be simplified by approximation to,mCl- = mCl-, total = 0.1m

The total concentration of Zinc in the solution is calculated from previous equations,
results in
mZn(total) = 10-5.35m

. Thus the total amount of Zinc dissolved in a solution in equilibrium with sphalerite is
increased from 10-8.6m to 10-5.35m, an increase of more than 3 orders of magnitude,
with the addition of any 0.1mCl- to the solution.

.This example illustrates the importance of the chloride complexes on the potential for
aqueous solution to transport metals in groundwater systems in sedimentary basins
and sub volcanic environments where chloride concentrations often exceed 0.1m.
.Chloride in the only anion to from complexes, other are So42-, S2-, HS- , CO32- ,HCO-3
and Na32How complex forming anions affect this solubilities of rock-forming minerals ?
In Later Section

Activity and Activity coefficient !

CaCo3

Ca2+ + Ca32-

+ Nacl

Na+ + Cl-

Ca2 in center of a cluster of water molecules and Cl- irons

Ca32- as center of a cluster of water molecules and Na+ iron
Protective Shields
Divalent > Monovalent
0.1MgSO4 > 0.1m Nacl
Solubility of CaCo3 should be increased more than the solubility of Agcl if
both are put in NaNo3 solution
Quantitatively we can
express
I =
mi the
i2 concentration of an electrolyte solution a
ionic strength
i

Where mi
i

concentration of an iron in mol/kg

charge

For a solution containing 0.1m Bacl2 and 0.04m NaNo3, the ironic strength would be,
I = (0.1 x 4 + 0.2 x 1 + 0.04 x 1 + 0.04 x 1) = 0.34
Effect of electrolytes on Solubility
Solubility Product = Activity Product activity

BaSo4
Ba2+S042250C,I atm

Solubility
X 105

11
7

Extrapolated Solubility at
zero ionic strength =1.0 x 10-5 m

3
1
0.0

0.1

I 1/2

0.3

0.5

aCaCO3(aq.) = YCaCO3(aq.)

mCaCO3(aq.)

Activity Coefficient
.In very dilute Solution (I < 0.001), Y is close to 1.
aCa2 + aCO32- = K ~ mCa2+ mCO32.As ionic strength of Solution increases, activity Coeff. decrease
Calculation of activity coefficient: (Debye-Hucel Theory)
- log Y = A z i2 I1/2

Constant depends on temp.and dielectric constant of the solvent, equal to

approximately 0.51 in water at 250C
Activity Coefficients Calculated
from Davies equation
Charge

I
1
0.001 0.97
0.01 0.90

2
0.87
0.66

3
0.73
0.40

0.01
0.2
0.7

0.36
0.28
0.23

0.10
0.06
0.04

0.78
0.73
0.63

-log Y = A z 2 ( I1/2

1+I 1/2

0.2 I)

Pressure
(Kbar)

Ga
Pe rnet
ri d
oti
te

30

Solidus
60

el ite
n
i
S p r i dot
pe

10

Plagioclase
Peridotite

Crystals
&
LIquid

0
0

500

Temp.( 0C)

1500

20

Depth (km)

100

moho
Low velocity zone

200
Pyroxene garnet transitions
Olivine transition

Depth (km)

400

600
Mg Garnet Olivine
800

1000
3.0

3.4

3.8

Density (g/cm )
3

4.2

Solution Mineral Equilibrium: I Carbonates

Give information on:
(i) how lime stones and dolomites are formed ?
(ii) Condition of formation of carbonate mineral as cements in soil, sandstones, vein
fillings

Solubility of calcite:
CaCO3 in nature Calcite (most Stable)
Aragonite
Vaterite (artificial)
rare in nature
Strong acid:
CaCO3 + 2H+ Ca2+ + H2O + CO2
Weak acid:
CaCO3 + H+ Ca+ + HCO3(Natural condition: acid solution from weathering of pyrite encounter limestone)
the reaction can be reversed by any process that user H+, e.g. if a base is added:
Ca2+ + HCO3- + OH- C aCO3 + H2O
(calcite)

Solubility of CaCO3 dependent on pH

CaCo3 + H2CO3 Ca2+ + 2 HCO3calcite

Two different sources

From
CaCO3 + H+
dissociation of
H2CO3
Forward reaction : When limestone is dissolved to from caves when marble is dissolved
by are bearing solutions in the walls of a fissure
Reverse reaction: - Precipitation of CalO3 in sea
- as commenting mater in sed. Rocks
- droplets evaporate at the tip of a stalactite
Effect of pH : At low pH, where most dissolved carbonate

Exist as H2CO3, the forward reaction is favored.

At high pH, reverse reaction leads to precipitation.

H2CO3 concentration is determined by concentration of CO2
H2O (1)+ CO2 (g)
H2CO3(aq)
Any process that increases the amount of CO2
Available to the solution makes more CaCO3 dissolve.
Any process that decreases the amount of CO2 causes CaCO3 to precipitate.

In heterogenous equilibria, (
), where forward (
at the same rate, the equilibria are controlled by:
Temperature

-9.0
lc
Ca

-8.6

ite

e
nit
o
g
Ara
ite
r
te
a
V

-8.2

-7.8
20

40

60

Temp.0C

80 100

) and reverse reactions are going

Solubility of Calcite and other crystal forms of CaCO 3 in pure water decreases as
temperature rises.
Opposite in behavior to many rock forming minerals.
CO2 is less soluble in hot water than in cold water

Mostly it in CO2 dissolution than tem.

Calcite dissolves at great depths in the ocean, where the water is perenially
cold, but precipitates near the surface, especially in the tropics,
Where the water is warm.
Pressure:
The effect of pressure by itself, independent of its effect on CO 2, is to increase the
solubility of calcite slightly.
Local changes in CO2 , Forest fire, industrial plants, volcanic erruption.

Organic Activity:

Shells of organisms CaCO2

Small changes in pH CaCO3 precipitation

Green plants cause precipitation by removal of CO 2 from water by photosynthesis

Abundant green algae in warm waters of the Bahama Banks aid in

precipitation of limy mud.
Decay: - Decay of organic matter produces CO2 making CaCO3 in the vicinity more
soluble.

In summary the solubility of calcite (and other carbonates) in nature is controlled by

fairly simple equilibria involving H2CO3 , HCO3 ,CO32- AND WATER. The principal
equilibrium is very sensitive to changes in the amount of dissolved CO2, and this is
dependent on a varielty of influences. Much surface and ground water is
approximately saturated with calcite and such water can either dissolve or precipitate
the carbonate, depending on slight alterations in external conditions.
Calcite and Aragonite:
(Ca++ )(CO32-) = 4.5 x 10-9 for calcite
(Ca2+) (CO32-) = 6.0 x 10-9 for aragonite
Slow conversion of solid aragonite into solid calcite
Seed crystals for nucleation of calcite
Aragonite is unstable with respect to calcite under ordinary conditions. It
becomes the stable form of CaCO3 at high p (density average. = 2.9 g/cm3,
cal =2.7)
Why aragonite forms at all?
Aragonite, high temp., presence of Sr2+, Mg2+
Aragonite
Calcite
In old rocks and shells aragonite is a rare mineral.

Supersaturations: extended periods

Mechanical disturbances
Dust particles
Materials of the container
Unevenness of surface in contact with solution
Laboratory, two time supersaturation
In nature, upto 5 times.

Grain sizes:

Size of crystals exposed to a saturated solution

Tiny grains, greater solubility
Recrystallisation and increase in grain size of many rocks formed originally
as fine chemical precipitates.
The course grains of some lime stones and the development of chalcedony
or quartz from opal are common examples.

Effect of other electrolytes

May change the solubility by tens or hundreds of times
Uni, di-, tri-, tetravalent etc.

Ion Association: Formation of complexes

Ca2++ CO32-

CaCO3(aq.)

Effect of organisms on solubility

K = [CaCO3(aq.) / [Ca2+] [CO32-]] = 103.2

Precipitationof CaCO3 in sea water

Ca2+ = 0.01 M , CO3 2- = 0.0002M
(Ca2+ )(CO3 2-) = 2 x 10 -6
Activity product of calcite [Ca2+][CO32-] = 4.5 x 10 -9
X 400, is sea water supersaturated with CaCO3 ?
Aragonite x 300
Y ca2+ = 0.28
YCO32- = 0.20
[Ca2+][CO32-] = 0.01 x 0.28 x 0.0002 x 0.2 = 1.1 x 10-7
X 20 times
Ca2+ SO4291%
CO32- Mg 2+
9%
0.9 x 0.09 x 1.1 x 10-7 = 9x 10-9
Saturated with 4,5x 10-9

The dolomite Problem???

Origin of the double carbonate dolomite?

Commonest of sedimentary materials, appearing as thick and extensive beds in
strata of all ages: Precambrian to Cenozoic.
No evidence for its formation under unusual P&T cond.
Laboratory X
No dolomite is observed to be forming in nature in ordinary sedimentary environment.

-Crystallography : double carbonate of Mg2+ and Ca2+ Ca Mg(CO3)2 distorted Nacl

Framework
- anions are Co32-+ groups and cations are regularly alternating ca2+ and
Mg2+
-In Lab, calcite , hydromagnesite
- Dolomite is readily prepared in Lab, above 1000C
high temp. Speed up the movement of ions

Solubility data: Ions do not recombine precipitate

K = [Ca2+] [ Mg2+] [CO32-] = 10-15 (10-17 to 10-19)
CaO3+ Mg2+ + 2HCO-3 = CaMg(CO3)2 + H2CO3
2CaCO3 + Mg2+ = CaMg(CO3)2 + Ca2+
CaMg(CO3)2 Ca2+ + Mg2+ + 2CO2-3 (congruent solution)
CaMg(CO3)2 CaCO3 + Mg2+ + CO2-3 (congruent solution)
poor preservation of fossils, (Originally in CaCO3)
Coarseness of grain, cavities and pore spaces
Indicate: Mg2+ + CaCO3

Mineral Equilibria : II Silicates

- Silica and silicates, most abundant in rocks, soils, sediments
- Silicate minerals make up >90% of Earths crust.
Quartz Solubility
Quartz crystals, amethyst, agate, opal : Si2
Aqueous solution origin??
Silica: - quartz, quartz, tridymite, cristobalite, stishovite, coesite,+ various
amorphous forms.
Chert: impure form of microcrystalline quartz (Chalcedony)
Opal : amorphous silica with some water.
Minerals (SiO2) : 12% of Earths crust

50

Coesite

- Quartz

30

Liqui
d

Pressure
(Kbar)

- Quartz

Tridymite

10

400

800

1200
Temp. 0C

1600

2000

Crystobalite

-1.0

5000

2000
-2.0
Am

h
orp

s
ou

-3.0

-q

SiO2+ 2H2O H2SiO4

ica
l
i
S

K = a H4SiO4 ~ m
500

rtz
a
u

100

-4.0

-5.0
100

200

300

400

H4SiO4

H2SiO4 H+ +H3SiO4K = 10-9.9

H3SiO4-

20

Most stable lowest

solubility

H2SiO42- + H+

K = 10 -11.7
mSiO2 = mH4SiO4 +
mH3SiO4- + mH2SiO42-

0
250C, 1 b

Log mSiO2

-1

H2SiO4

-3

H4SiO4
Quartz

-5
2

10
pH

14
H3SiO4-

Dissolved Silica, SiO2 ppm

1000

Amorphous
Silica

5000

200

50
Quartz

10
2
6
pH
10
12

Press
ure

0b 00 0
0
0
5
30200
0
100 0b
75

log mSiO2

-1
-2

-3
200

400

600

-1
log mSiO2

-4
0

-2

ne
o
Z
al
t
n
n
e
tio ontin
c
du C
b
ic
Su
n
a
c
vol
b
u
S

-3
-4
0

200

400

600

Consider pore fluids that undergo decompression and cooling as they rise
through the upper portion of the Earths crust.
<400 0c, solubility of quartz decreases as the fluid moves upward and quartz
may precipitate
>400 0c, the solubility of quartz increases and supersaturation caused by
cooling can occur only below this temperature.
Measured temperature of formations of the numerous quartz veins in
sub-volcanic environments are uniformly below 9900c.
Hot springs in regions of volcanic activity provide a natural example of the
transport and deposition of silica by aqueous solutions.
Estimate temp. in geothermal reservoirs.
Crystal Chemistry
Minerals : Naturally occuring homogeneous solids, for the most part
inorganically formed, with definite chemical compositions and specific
arrangements of atoms.
>3800mineral species.
Only 12-50 minerals make up greater part of common rocks and these
aremade up of only 8 elements: O,Si,Al,Fe,Mg,Ca.\,Na,K
These 8 elements make up >99% of the mass of Earth crust.
Only two minerals Quartz and Feldspar make almost two- thirds of the
crustal volume
Quartz +Feldspar +Pyroxene + Olivines And Hydrated Silicates make
up > 90% volume.
Diamond and sulfur are constructed of un-ionised atoms.
Asphalt: made up of molecules
Rocks: made up ofmostly ionic solids

Earths crust
Composition (weight %)

Silicon(27.3%)

Others(0.9%)

Oxygen(45.6%)

Potassium(1.8%)
Sodium(2.3%)
Magnesium(2.8%)
Calcium(4.7%)
Iron(6.2%)
Aluminium(8.4%)

Lithology (volume %)

Granites
Granodiorites
Diorites
(22%)

Gneisses
(21.4%)

(42.7%) Basalts
Gabbros
Amphibolites
Eclogite
Dunites
Peridotites

Schists (5.1%)
Marbles(0.9%)
Clays & shales(4.2%)
Sands & sand stone(1.7%)
Carbonates(2.0%)

Mineralogy (volume%)

Pyroxenes
(11%)

Micas(5%)
Amphiboles(5%)
Olivines(3%)

Plageoclases
(39%)

Clay minerals(4.6%)
Magnetite(1.5%)
Calcite(1.5%)
Dolomite(0.5%)

Alkali
Feldspars
(12%)

Quartz
(12%)

Others(4.9%)

Structure of NaCl:

Arrangement of ions: Cubic

Every Na+ is surrounded by six Cl ions at the corners of an octahedron and every Clby six Na+ ions.

Na+
Cl-

Na+

Cl-

Ions?
Orbitals: regions of probability of finding electrons.
Sizes of ions? :
58.5 g of NaCl contains 6.02 x 1023 molecules of NaCl
i.e. 6.02 x 1023 Na+ ions & same Cl- ions.
Density of NaCl = 2.16 g/cm3 , hence vol. = 58.5 /2.16 = 27 cm3
Voume of a single ion = 27 / 2x 6.02 x 1023 = 22 x 10 -24 cm3
Diameter = (22 x 10 -24 cm3)1/3 = 2,8 x 10 -8 cm3
Radius = 1.4 x 10-8 cm or 1.4 Angstroms
Cl- = 1.8
and
Na+ = 1.0

Radii of common ions in rock- forming minerals:

Cations
Radii
Coordination with O2Anions
K+
1.38
8,12
S2 = 1.84
Na+
1.02
6,8
Cl- = 1.81
Ca 2+
1.00
6,8
O2- = 1.40
Mn2+
0.83
6
OH-= 1.40
Fe2+
0.78
6
F- = 1.33
Mg2+
0.72
6
Fe3+
0.64
6
Ti4+
0.61
6
Al3+
0.535
4,6
Si4+
0.26
4
C4+
0.15
3
Octahedral radii
Crystal Energy : The amount of energy needed to peas apart a molecule to individual
ions.
Other ionic solids.:

Radius Ratio Coordination Number

1

12

0.73 1

0.73 0.41

0.22 0.41

0.15 0.22

Atomic Structure
Eg: CsO

Eg: CsCl
Eg: NaCl

Eg: ZnS

Co ordination number??
In minerals, commonest anion is O = 1.40
Common cations = 0.6 to 1.1
Radius ratio = 0.43 -0.79
Most frequent coordination numbers in minerals = 6
Radius ratio:
Cs+ = 1.19
Rb+ = 1.08
K+ = 0.98
Na+ = 0.73
Ca2+ = 0.71
Fe2+= 0.56
Al3+ = 0.38
Si4+ =0.81

Sr2+ = 0.84
Mg2+ = 0.51

Predicted and observed C.N.

Ion
R.R
Predicted
Observed
Limiting
(Ion/O2-)
R.R
Cs+
1.19
12
12
Rb+
1.08
12
8-12
___________________________________________________1.00
K+
0.98
8
8-12
Sr
0.84
8
8
Na
0.73
8
8
___________________________________________________0.73
Ca
0.71
6
6,8
Fe
0.56
6
6
Mg
0.51
6
6
___________________________________________________0.41
Al
0.38
4
4,6
___________________________________________________0.22
Si
0.18
3
4

Covalent Bonds:

Ca2+ = 1.00
Cd2+ = 0.95
With Oxygen (1.4 ), interionic distances are 2.4 for CaO and 2.34 for CdO.
For sulphides (S = 1.84 ):
CaS = 2.8 ,

CdS =2.51 ?

Electrons are shared.

Covalent bond compounds: Low solubilities
Stable compounds Cl2,CH4,SO2
with little attraction for one another.
Low melting and boiling points little strenght and hardness.
Alternately, such bonds may give continuous 3-dimentional structures in which atoms
are linked to others on all sides, as in diamond (high m.p. &
exceptional
hardness.)
Neither ionic nor Covalent, slight displacement polar bonds
Na
:
Cl
H
:
Cl
Cl
:
Cl
Ionic
Polar
Covalent
So much Ionic or so much Covalent
Electronegativity:
Cl2 is electronegative, forms negative ions easily.
Na is electropositive, forms positive ions easily.

Electronegativity of an element is related to its ionisation potential for cations and its
elctron affinity for anions.
Quantitative values from** bond strength (an measured by heats of formation)
Pauling
1960
** - % of ionic character from ionization potential and electron affinities
(Povarennykh,1956)
Ion Electronegativity %ionic character
Cs+ 0.7
89
Na+ 0.9
83
Ba2+ 0.9
84
Al3+ 1.5
60
Ca2+ 1.0
79
Cu2+ 1.9
71
C4+ 2.5
23
Cl
3.0
S
2.5
O
3.5
Electronegativity diff. NaCl = 2.1
CaS = 1.5
CuS =0.5
Increasing Covalent Character
CS2 = 0.0

Purely covalent , if electronegativities are similar

Largely ionic : electronegativities are different.S

Slicate Structures
Si is a non-metal of intermediate electro negativity, Oxid.no-4, Coord.no.4
SiO44- (SiO44-) fundamental unit
Mg2SiO4
Si, although non-metal has properties between metals and non-metals
as tarnishing versatility rings, chains, sheets etc.
S+6 = 0.12Ao, P5+ = 0.17Ao, Non-metals
Si4+ = 0.26Ao
AI3+ = 0.53Ao, Ti4+ = 0.61Ao Smallest metals
Nesosilicates : Olivine
Sorosilicates : Hemimerphilte Zn4, Si07, (OH)2-, H2o
Inosilicates
: Si/O = 1/2 Single chain Pyroxenes
Si : O = 4 :11 double chain amphiboks
Phyllosilicates : Si : O = 2 : 5 MIcan
Tcestosilicates : Si :O : 1 : 2

General rules about bond type:

-For a given cation two different anions, the bond with the larger anion is more
covalent (MgS > MgO)

-For a given anion and two different cation, the bond with smaller cation covalent
(MgO > BaO)

-For iron of similar size and different charge, the one with highest charge forms the
most covalent bonds (CaO > Na2O)
Metallic Bond: toms do not have sufficient valence electron to fill completely a given
shell of 8 either by or transfer.

-Electrons capable of moving along a metal under the influence of an electric

potential differences e.g. sulfide mineral (some)

Polymorphism :
Isomorphous: Similar crystal structures but different chemical formulas
Polymorphous: Similar formulas but different structures
CaCO3 Calcite
SiO2

AI 2SiO5 Andalusite

Aragonite

kyanite

Aragonite

Silimanite

B-gonite

Triolymite
Cristobalite

Polymorphism : Iron making up a compound can be arranged in two or more different

patterns

Rb+ with ironic radius between CS+ and Na+ forms a chloride (Rbcl) with the
8.coordinated (SCI) structure of NaCI at ordinary P.
MgCO3 calcite structure

CaCO3 Both

increasing

SrCO3

size of cation

BaCO3

Aragonite Structure

T P
Rhombic S is Stable < 960C
monoclinic above

High T polymorphs have more open structure with higher symmetry

Higher prenere polymorphs _ more closed structures Imparities ?
from: rate of crystalisation
Cristobalite > 1470C, found in cavities in low temp, imparities

Cristobalite > 1470C, found in cavities in low temp, imparities

Pressure (Kbars)

10
6
8

Kyanite

Silimanite
4
2

Andaunite

200

600
Temperature ( 0C)

1000

Isomorphism :
Olivine (Mg, Fe,)2 SiO4
Mg, Fe, ration variable
Mg, Fe, to Si ration is constant
Mg2SiO4 (Forsterite) and Fe2SiO4 (Fayalite) have similar crystal from and structure

Olivine Isomorphous mixture of two end members

Olivine Solid solution of fayalike and forsterite
Mg2+ substitutes Fe2+ in crystal structure
When two compounds differ only in a single constituent and when the two
kind of irons that play the role of this constituent have similer size, the two
could substitute for one another in crystallographic sites
Mg2+ = 0.72AO
Fe2+ = 0.78AO
A similar Isomorphous relationship between Mg2+ and Fe2+ is common in other silicate
.
Pyroxenes (diopside - hedenborgite)
Ca(Mg Fe)Si2O6
Amphiboles (actinolite)
Ca2(Mg Fe)5(Si4O11)2(OH)2

All pairs of Mg and Fe compounds are not Isomorphous

Little Mg is found in Pyrite (FeS2)
and very little Fe in epsomite MgSO4.7H2O

Reason : Slight difference in size

- In olivine, the two metals can substitute for one another in any proportion

-solid solution are completely miscible

- Limited substitution if the difference in ionic size between the irons is greater
than 15%
- Substitution depends on temperature .
At high temperatures, the added thermal energy server to increase the
vibratory motion of irons, expanding the structure and making it more tolerant for
foreign particles.
800

Temp OC

600

Two
feidspars

400
250
Albite
NaAlSiO3O8

0.5

1.0
K-feldspar KAlSI3O8

Isotope geochemistry :
Nacl: All a toms of Na and Cl in Nacl, we assumed to be identical any sample
of the salt would show precisely the same solubility, melting point, heat
conductivity and so on as any other sample

This is not quite true

All atoms of an elements are very nearly the same, but may show minor
differences.

Given information on:

Ages of rocks and minerals
temperature of rock formation
Places where rock and ores and fluids have their origins

Isotopes: ?
Atoms of elements same number of electrons outside the nucleus and the
same number of protons within the nucleus (Atm. No.)
But the nuclei may contain differing number of neutrons
Thus atoms may differ in mass(P+n) and hence differ slightly in properties.
An elements may consists of a mixture of substances with slightly different
chemical and physical behavior.
The separates varities of the elements are its

ISOTOPES

Single isotope: F,Na,Co

Most have two :
Eight or more : Sn,Xe,Te
Artificial bombardment can create isotopes of all elements except Hydrogen.
Isotopes of elements have different chemical and physical properties, but vary only
slightly.
Chemical properties depend on nuclear charge and arrangement of electrons.
Properties are not very similar that ordinary chemical reactions either in the laboratory or
in nature, lead to practically no separation of isotopes.
Only a few lighter elements, H,C,O,S have isotopes with a sufficient percentage
difference in aomic mass to cause appreciable separation in nature.
Radioactive, spontaneous radiation, change to nuclei of other elements
Radiation - particles (He nucelus, Zp &Zn)
Isotopes
particles (e-)
gamma radiation (high energy radiation)
Daughter products (radiogenic)
Stable.

The accumulation of radiogenic isotopes by the decay of radioactive parents provides a

powerful means of establishing absolute ages of earth materials
Sr,Pb, Nd yielded information on :
Differentiation of planetory substances
Stable isotopes: measuring tempe. And drawing inferences about sources of rockes,
ores, fluids.
Radiogenic isotopes: Age dating
- Radioactive decay goes on at a constant rate
- Unaffected by T,P or chemical combinations
- hence, reliable clock for measuring geologic time
- Once imprisoned in a crystal structure, constant decay, ratio of daughter to parent
increases constantly from which time elapsed since crystal was formed can be
calculated.
Assumption: Mineral has not altered since the formation
To ensure no alteration geologic evidence
age determined by one or more parent daughter pair.
Altered due to metamorphism time and nature of metamorphic event.
Equations of decay:
Decay follows a statistical rule: The ratio of decay or the number of atoms that decay, is
proportional to the number of parent atoms present.
-dP /dt = dD/dt =P -dP/P = dt

P number of parent atoms remaining at any time t,

dD/dt rate of formation of daughter atoms
decay constant
Integration gives,
-lnP = t +C
Integration constant C may be expressed in terms of the original number of parent atoms
when t =0
(time when rockor mineral was formed) or
C = -lnP0 , substitution gives,
lnP-lnP0 =- t.
Thus P =P0 e- t or P0 = Pe+ t
The number of daughter atoms produced by time t(D*)is the difference between P0 and
P:
D* = P0 P = Pe+ t P = P (e+ t-1)
Now at time t=0, some daughter atoms amy have been present and the total number
existing at time t is therefore this original number plus those produced by radioactive
decay. If the original number is D0, the total will be :
D =

D0 + D*

D0 + P(e+ t-1)

(total) (initial) (produced)

Rearranging, t =1/ ln[(D D0/ P) +1]

t =1/ ln[(D D0/ P)] +1

This is the time during which an amount of the daughter represented by D has
accumulated, leaving undecayed an amount of the parent represented bt P.
Value of D and P can be found to by analyzing the rock or mineral in which the
radioactive isotope occurs.
If we can also find out values for and D0 , age of mineral or rock can be found out.

Decay constant is found by laboratory measurement of decay rate.

Precise determination of is difficult for isotopes whose radioactivity is feeble, decay
is very slow.
As methods of measurement improves, values of for the geologically important
isotopes are refined and calculated ages that depend on must be revised.
More easily visualized than is a related quantity called *halflife, which is the time
required for any given amount of an isotope to decay
If P0 has decreased to 1/2P0 in time t1/2
P0 = P0 e- t1/2 or t1/2 = lnP0 / ( 1/2P0 )x 1/ = ln2/ = 0.693/
The measured value of for 238U is 1.537 x 10-10yr-1
,half life is 4.51 x 109 yr, roughly equal to age of the earth
D0 the amount of daughter isotope that may have been present initially when the rock or
mineral was formed can be estimated in various ways.
* If little or none of the daughter product is present , D0 can be set equal to zero.

*D = P (e+ t-1) + D0
If D is plotted against P (y against x), for a number of rocks or mineral formed at the
same time, the values should lie on a straight line. Whose intercept on the Y axis is
D0 and whose slope is e+ t-1.
Samples of same age
*Isochron: The straight line plot of D version P for samples of rock materials formed at
the same time
Steepness of the slope is a measure of the length of time during which decay has

Sr
r/ 0.74
7
S
8
86

10
x
17
00

0.78

t=

t=3
700
x 10 6
y

been 0.82
going on.

t=

C
0x
6
4

D
10

A
t=0
0.70

2
3
87
Rb/ 86Sr

Use of calculating ages: Assumptions

The value of is a property of atomic nuclei, unaffected by extreams of T or P or by
chemical combination in ordinary geologic environemnt.
E rock or mineral has been a closed system since its formation. i.e. neither parent nor
daughter has been added to or lost from the system.
This is questionable???
Ages based on the assumption when its validity is uncertain are commonly called model
ages, meaning that the ages refer only to a particular model of geologic history which may
or maynot be consistant with other geologic evidence.

Rubidium-Strontium Dates:

Rb 87Sr
Ratios are more easily measured, divided through by the amount of a stable and non
radiogenic isotope.
87Sr = 87Sr + 87Rb (e t -1 )
0
Total
Initial
produced
(87Sr/86Sr) = (87Sr0/86Sr) + (87Rb/86Sr) ) (e t -1 )
Measured
initial
produced
t = 1/ ln [( (87Sr/86Sr) - (87Sr0/86Sr) / (87Rb/86Sr) ) +1]
= 1.42 x 10-11 yr-1 t1/2 = 4.88 x1010 yr
87

Sr0/86Sr =0.704 is used, an average of ratios found in recent volcanic rocks.

Useful to date Rb-rich minerals of Paleozoic or older age lepidolite, muscovite, biotite, Kfeldspar
Rb forms no minerals of its own, but substitutes extensively for K because of the close
similarly in properties between Rb+ & K+.
87

Uranium- Thorium- Lead dates:

Natural U : 238U (mostly) + 235U (0.72%)
234U formed from decay of 238U
238U 206Pb + 8He + 6
t1/2 = 4.51 x109yr
238U 207Pb + 7He + 7
t1/2 = 0.71x109yr
Most of the Earths original 235U has vanished, whereas half of 238U remains.
U- bearing minerals also contain a little Th, which decays as
232Th 208Pb + 6He + 4
Three independent age- determinations:
238U - 206Pb
235U - 207Pb
232Th - 208Pb
The helium produced in all 3 reactions would seemingly be the basis for still another age
estimates, but unreliable as the gas escapes from minerals too readily.
The amounts of Pb, U and Th are customarily expresses as ratios of the isotopes to the
nonradiogenic isotopes of lead, 204Pb.
238U - 206Pb:
(206Pb/204Pb) = (206Pb0/204Pb) + (238U/204Pb) ) (e t -1 )

t = 1/ ln [( (206Pb/204Pb) - (207Pb0/206Pb) / (238U/204Pb) ) +1]

Similar equations can be written for other two isotopes.

To minimise possible inaccuracy due to Lead content, it is desirable to use a mineral

which contains substantial amounts of U and Th but is known to exclude most Pb
during crystallisation.
Best example is Zircon separated from igneous rocks
Uraninite,titanite,apatite and monazite
All three ages should be calculated simply from ratio of 207Pb to 206Pb.
This ratio is not sensitive to loss of Pb, because the two isotopes behave the
same chemically and would be lost at the same rate.
So, if the discrepancy in calculated age is due to loss of Pb, an age calculated from
207Pb/206Pb should be closer to true age than any of the others.
206Pb*/ 238U
207Pb*/ 235U
and

Where 206Pb* is the amount of radiogenic 206Pb produced from 238U and 206Pb* is the
amount of radiogenic 206Pb produced from 235U.
These quantities increase with time at different rates.
206Pb/ 238U = e 1t -1
and 206Pb/ 238U = e 2t -1
1 = Decay constant of 238U
2 = Decay constant of 235U

206

Pb*/238U

Concordia
0.8
3.0

0.6
0.4
0.2
0.0

2.5
2.0

Discordia

1.5
1.0

0 10 20
207

Pb*/235U

30 40

-No Pb is lost, ideal system

Concordia
Pb is lost Discorida, if Pb is lost in a
Single episode, all points should lie on
A straight line, if this line is extended
Until it intersects the concordia, the
upper Intersection gives the age of a
mineral.

Potassium-Argon Dates:
40K (makes up about 0.1% of naturally occuring K) decays.
(89%)

K
(electron emission)
40K
(Electron capture, 11%)
40Ca
common isotope of calcium
40Ar
Common method of age determination
K, common element in rocks.
Major drawback, radiogenic product is a gas, which may in part escape from the
mineral in which it forms.
The total decay constant for 40K may be written as the sum of the constants for the
decay paths to Ca and Ar
40Ar = 40Ar + ( / ) 40K (e t -1)
0
a
40

= total decay constant , 5.305 x 10 -10 yr-1

a = Constant for decay to Ar, 0.585 x 10-10 yr-1
a/ = 0.110
40Ar is generally zero,
40Ar = 0.110 40K (e t -1)
t = (1/ ) ln(( 40Ar/ 40K)(1/0.110) +1)
Necessary measurements, 40Ar, 40K
Most reliable hornblende
Biotite and muscovite: good, but diffuses (Ar) easily.

- Time of metamorphismrather than age

- Good for volcanic rocks, basalts
39Ar - 40Ar
(Irradiation of a sample with neutrons)
for complex metamorphic histories.
Samarium Neodymium Dates
147Sm 143Nd rare earth group, very similar chemical properties not likely to Dating
igneous,
be differentially removed by accident of weathering or
rocks,
hydrothermal alteration.
( 143Nd/144Nd) = (143Nd /144Nd) + (147Sm/144Nd) (et -1)
Measured
initial
produced
= 6.54 x 10-12 yr-1
t = 1.06 x 1011 yr
Useful for dating mafic rocks, in which Zr is absent (U for Pb) dates and Rb- Sr
concentrations are so slow.
Carbon-14 Dates:
14N 14C
Neutron from cosmic- ray collisions.
14C 14N
t1/2 = 5730y
A = A0 e-t

A and A0 are measured as numbers of disintegrations per minute per gram of carbon.
t= 19,035 log10 (A0 /A)
max: 70,000y
Radiogenic isotopes: Petrogenesis
-wide application toother geologic questions, history of rocks and minerals.
Strontium:
-Original 87Sr/86Sr, meteorites 0.699 is the most probable 87Sr/86Sr ratio of Earths
original Sr.
UR Uniform Resrvoir
Sr2+ resembles Ca2+, distributed more evenly in crust and mantle.
More Rb in crust, means production of 87Sr has been faster in crust than in mantle.
This difference in isotope ratios, gives us a means of distinguishing igneous rocks
that have formed by partial melting of crustal rocks from those that have their origin in
partial melting of mantle material.
Present mantle 87Sr/86Sr ratio from xenolithic or of recent basalts and gabbros from
oceanic environments

0.702 to 0.706
Rb concentration in mantle 0.027%

Cru
st

0.710

87

Sr/ 86Sr

0.708

0.700

Depleted mantle
5

By before present
Neodymium
147Sm 143Nd, 143Nd/144Nd 0.5068
Present day 0.5126
CHUR Chondrite Uniform Reservoir
Differentiation mantle/crust, Nd isotope ratio would have change in a
direction opposite to that of the Sr ratio
Nd goes more readily than Sm into a felsic differentiate

143

ma
ntle

Faster growth in
mantle
Slower in crustal
materials

Dep
lete
d

Nd/ 144Nd

0.516

0.512

0.508
5

CHUR
4
3

Crust
2

By
To know?
Used from which an igneous magma wasformed?
High ratio mantle

 Sr = [((87Sr / 86Sr)m /(87Sr/ 86Sr)R) -1] x 104

Measured value

Uniform reservoir

Nd = [((143Nd/ 144Nd) / ( 143Nd/ 144Nd)R ) -1] x 104

+ve value: enrichment, -ve: deficiency
-50
0
B
R
MO
0.5130

Sr
+50

n
pa
a
J

sa
a
B

lt

y
rra
a
le

n
e
tin
n
Co

lt+10
a
as
b
l
ta

Nd
0

14
3

Nd
/

14
4

Nd

nt
a
M

100

Peru & Chile Basalts

0.5122

-10

0.702

0.706
87
Sr / 86Sr

0.710

The composition of the earth

(William F. McDonough)
Comparable to undifferentiated meteorites C Chondrites
Present configuration (three-layered, metal-rock-water system)

Age of Earth :46Gy

Core? Iron meteorites, low P differentation
Evaluation of solar system:
Gravitational collapse of a rotating interstellar cloud (supernova)
Series of collisional processes
Dust grains small particles planetesimals protoplanets.

Structure of the Earth

The major and distinctly different units:
Core, Mantle- Crust system, Atmosphere- Hydrosphere Systems
Products of Planetary Differentiation, distinct compositions
Mass of core: 1/3 Mass of the Earth
Volume of core: 1/8 Volume of the Earth
Radius of Core: of the Earth
Core: Fe- Ni alloy with lesser amount of other siderophile elements and ~10% by
mass of a light element
Crust- Mantle system: mixture of silicates containing primary magnesium, iron,
aluminum and calcium
Atmosphere- Hydrosphere system: mass of oceans
Atmosphere= 80/20: N2:O2

Information from

Earths seisomlogical profile

Magnetic field
Orbital behavior coefficient of the moment of inertia
Less direct info: Meteorite, Silicate Earth

31%
68.3%
0.7%

Density- depth

Bulk sound velocity of average density and mean atomic number

Mohorovicic discontinuity between crust and mantle
Density immediately below Moho: 3.3 mg/m3
Olivine dominated mineralogical assemblage containing pyroxene and an aluminous
phase (plagioclase, spinel, garnet depending on pressure)
Deeper level olivine to -Spinel phase giving rise to the 410km depth seismic
discontinuity
At still deeper levels, olivine component breaks down into Mg- Peorvskite and
Magnesiowustite giving rise to the 660 seismic discontinuity, upto Core- Mantle
boundary.
These is a dramatic change in seismic profile for both P (compressional) and S
(shear) waves
The average density increases from about 6Mg/m3 in mantle to over 10Mg/m3 in core
Fe- rich
Final Seismic discontinuity 5120km transition from fluid core to a solid inner core,
S- waves do not propagate through outer core (liquid)

The composition of silicate Earth : & core

Core
(g/g & %)
H
100
600
Zn
55
0
Li
1.6
0
Ga
4
0
Be
0.07
0
Ge
1.1
20
B
0.3
0
As
0.05
5
C
120
200
Se
0.075 8
N
2
75
Br
0.05
0.7
0%
44
0
Rb
0.60
0
F
15
0
Sr
20
0
Na%
0.27
0
Y
4.3
0
Mg%
22.8
0
Zr
10.5
0
AI%
2.35
0
Nb
0.66
0
Si%
21
6.0
Mo
0.05
5
P
90
3500
Ru
0.05
4
S
250
19000 Rh
0.001 0.74
CI
17
200
Pd
0.004 3.1
K
240
0
Ag
0.008 0.15
Ca%
2.53
0
Cd
0.04
0.15

Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
W
Re
Os

0.25
1.25
0.41
0.15
0.54
0.10
0.67
0.15
0.44
0.068
0.44
0.068
0.28
0.037
0.029
0.0003
0.003

0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.47
0.23
2.8

Sc
Ti
V
Cr
Mn
Fe%
Co
Ni
Cu

16
1200
82
2625
1045
6.26
105
1960
30

0
0
150
9000
3000
85
2500
52000
125

In
Sn
Sb
Te
I
Cs
Ba
La
Ce

0.01
0.03
0.006
0.0012
0.01
0.021
6.6
0.65
1.68

0
0.5
0.13
0.85
0.13
0.065
0
0
0

Ir
Pt
Au
Hg
Ti
Pb
Bi
Th
U

0.003
0.007
0.001
0.01
0.004
0.15
0.003
0.08
0.02

2.6
5.7
0.5
0.05
0.03
0.4
0.03
0
0

Composition of earth :
0% : 29.7, Na% : 0.18, Mg% : 15.4, A% : 1.59, Si% : 16.1, Ca% : 1.71, Fe% : 31.9

oxides%
SiO2
TiO2
AI2 O3
Fe2 O3
FeO
MnO
MgO
CaO
Na2 O
K2 O
P2 O 5
H2 O

WholeEarth
47.9
0.02
3.9

Mantle

8.9
0.14
34.1
3.2
0.25
0.02

8.0
0.14
38.4
3.1
0.4
0.1

45.7
0.09
3.4

Continentalcrust
60.2
0.7
15.2
2.5
3.8
0.1
3.1
5.1
3.0
2.9

Andesite
57.6
0.77
17.3
3.1
4.3
0.15
3.6
7.2
3.2
1.5
0.21
1.0

0
th
p
De )
(km

Crustal
Geotherms

Mantle Geotherms

100

20
ar)
b
k
P(
40
60

200
100

500
T0C

900

1300

Distribution of the elements

Goldschmidts geochemical classification of elements

Igneous rocks
Sulfide rocks
Carbonate sediments
Salt deposits
Need to classify elements, properties related to geologic behavior

Earth metal phase, sulfide phase, silicate phase

Information from meteorites
Analysis of metal, slag (silicate) and matte (sulfide) phases in metallurgical operations

Consider distribution of elements between metallic iron and silicates in a system with
iron in excess
Metals more chemically active (higher free energy of oxidation) than Fe would presumably
combine with silica to form silicates and the remaining silica would react with Fe

Data on free energy of formation of silica is not complete, but approximately can be
used for oxide whose data exist and,
Me + O2 = MeO is much larger than
MeO + SiO2 = MeSiO3

Free energies of formation of oxides peroxygenatous , KJ

25% 827 C
CaO -604.0 -520.8
MgO -569.4 -481.6
AI2O3 -527.4 -442.7
UO2 -515.9

-447.2

TiO2 -449.7

-371.9

SiO2 -428.3

-356.8

MnO -362.9
K2O -322.1

-304.3
-203.2

ZnO -320.4
WO2 -266.9

-237.9
-195.0

SnO2 -259.9

-176.5

FeO -251.1
MOo3

-199.7
-222.2

CoO -214.2
NiO -211.7
pbO -188.9
Cu2O -146.0

-154.9
-140.7
-109.2
-86.9

-156.7

Similarly can be drawn for, metal phase and a sulfide phase with iron in
excess, and between a sulfide phase and a silicate phase with silica in
excess

Elements that preferentially occur with native iron Siderophile

Concentration with sulfides Chalcophile
Silicates Lithophile
Air/ Natural gases- Atmophile

Siderophile:
Fe, Co, Ni, Ru, Rh, Pd, Re, Os,Ir, Pt, Au, Mo, Ge, Sn, C, P, (Pb), (As), (W)

Chalcophile:
Cu, Ag, (Au), Zn, Cd, Hg, Ga, In, Ti, (Ge), (Sn), Pb, As, Sb, Bi, , Se, Te, (Fe), (Mo),
(Re)

Lithophile:
Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, (Pb), B, Al, Sc, Y, REE (C), Si, Ti, Zr, Hf, Th,
(P), V, Nb, Ta, O, Cr, W, U, (Fe), Mn, F, Cl, Br, I, (H), (Ti), (Ga), (Ge), (N)

Atmophile:
H, N, (C), (O), (F), (Cl), (Br), (I), He, Ne, Ar, Kr, Xe

Distribution of elements in igneous rocks

Various origin of igneous rocks but similar predictions about distribution

of trace elements
Most igenous rocks formed by differentiation of basaltic magma
Mafic minerals settle out first to form ultramafic rocks and remaining melt change
composition through,

Gabbro Diorite Granodiorite Granite Pegamtite

Early formed minerals of high n.p.: Olivine, Ca-Plagioclase

Late formed minerals: alkali feldspar, biotite
Residual Fluids: Pegmatitic composition
Predictions: analysis is surprisingly good

Rules of Distribution

Differentiation of silicate melt at low pressure

Olivine and Ca- Plagioclase crystallize first

Olivine reacts with the melt to form Pyroxene

Amphibole

Biotite

Ca- Plagioclase become Sodic Plagioclase

At the end of crystallization:

Quartz, Potash Feldspar appear along with sodic plagioclase

If oxygen fugacity is low the scheme is attered

abundant Fe remains longer in the melt ferrous silicates continue to crystallise
until a lake stage
If abundant water is present:
Formation of hydrous minerals
Abundant cI2, F2, or B :
unusual minerals containing these elements
At higher Presser:
dominant early-crystalising mineral would be garnet and soda-rich pyroxene
rather than olivine and plagioclase
Present Purpose: usual pattern of differentiation
Most of Mg and Ca leave the melt in early stage
alkali metals later
iron may be largely concentrated in early minerals or may appear at all stages
aluminum drops out in feldspars & micas
How less common elements are related to these changer ?

Crystaillise on its own ?

Rb+ goes for K+ in micas and feldspars and no Rb+ separate mineral forms.
Zinreconicusm forms accessory mineral Zircon even in very small amounts
Be, B, Cu, and U are capable neither of forming their own high T nor substitute
appreciably in silicate structures and so are counteracted in residual solution that
give rise to pegmatite's and quartz-sufficed venue.
what characteristics ? Miner elements,
substitution (miner element may substitute a major element) if the ironic radii do not
differ by >15%
Irons whose charges differ by one unit may substitute for another, provided their radii are
similar and provided the charge difference can be compensated by another
substitution.
In play. Feldspar Na+ readily substitutes for Ca2+ and the charge difference is
compensated by substitution of Si4+ for AI3+
Of two irons that can occupy the same position in a crystal structure, the one that
stronger bonds with its neighbors is the one with smaller radius higher charge or
both.
Substitution is limited if the bonds formed differ markedly in covalent character .

Ba2+ commonly substitute for K+, Cr3+ for Fe3+, Y+3 for Ca2+
Near absence of Li in olivine and common presence as a substitute for Mg in mica
of pegmatites. Because ?
iron of smaller radius and higher charge would have the higher melting point
(strong bond) and therefore would appear curlier in a crystallization sequence.
Hence a minor element like Li, which substitutes extensively for Mg because of
the similarity in their ionic radii, is concentrated in lake forming Mg mineral
rather than early ones, because its single charge forms works bonds than the
double charge on Mg2+
Forsterite has a higher melting point has fayalite and is enriched in early crystals.
(Mg2+<Fe2+)
Early crystals of plagioclase are ca-rich, lake crystals Na-rich
Cu+ is similar in size and charge to Na+, but copper shows no enrichment in sodium
minerals.
Hg+2 closely resembles Ca2+ but is not concentrated in ca-minerals.
Cu & Hg forms bonds of less ionic character than Ca & Na

World average : (%) major elements

radius
ultramafic
(AO)
Si4+ 0.26
19.0
AI3 0.54
0.5
Fe3+ 0.64
9.9
Fe2+ 0.78
Mg2+ 0.72
25.9
Ca2+ 1.00
0.7
Na+ 1.02
0.6
K+ 1.38
0.03

mafic

internuclicate

Felsic

24.0
8.8
8.6

26.0
8.9
5.9

32.3
7.7
2.7

4.5
6.7
1.9
0.8

2.2
4.7
3.0
2.3

0.6
1.6
2.8
3.3

.69
0
Ni
2+

Mn 2
+
0.6
7

Pb

Cr 3+
0.6
15

0.
6

2+

9
1
.
1

3+

Ba

1.

Ga

52
1,
Rb
+
2+

35

F
Fe 3+ e 2+ 0.
0.5 6
Mg 2+ 5
0.72

Cu +
Ca 2+
S
Al 3+
2
r
+
0.7
1.0
0.5
1
.
0
7
18
35

38
.
1

V 3+0
.64
Ti3+0.67

Li

7
0.

Regularities of distribution
Cations with large radii and low electric charges tend to substitute for potassium
(K+ = 1.38AO). Hence are concentrated in felsic rater than mafic rocks.
These are Rb,Cs, Ba, Pb,TI
Large Ion lithophile Group (LIL)
Their abundance in a rock series in a good indication of the extent to which
differentiation has sorted out constituents of the original igneous material
REE substitute in later stape Ca2+
several cation cations with smaller radii and mostly with higher charges U4+, Th4+,
B3+, Be2+,Mo6+,W6+, Nb5+, Ta5+, sn4+, Zr4+, also are concentrated at the felsic end of
the series, not because their size and charge make their substitution for any major
iron in common silicate minerals difficult.
-later residuals solutions
-From minerals of their own, uraninite, beryl, columbite, Zircon
-because of small size and high charge electric field anociated with these
ions is unusually strong
High field-strength elements (HFSE)
Both LIL and HFSE ,because their irons do not fit readily into the uisual positions
available in silicate structure are described as Incompatible Elements.

Many elements whose ions have intermediate radii, especially metals of the
transition groups, substitute readily for iron and Mg, hence are abundant in the
earlier members of the differentiation Sequence.
Cr, Ni, Co, enriched which Mg in ultramafic rocks
Mn, Ti, V gabbros and basalts
Among chalcophite element, a few substitute for major cations in silicate structures
Pb2+ and TI+ for k+
Zn2+ for Fe2+ and Mg2+
Bi3+ for Ca2+
But mostly these elements are left to accumulate in the residual solutions,
eventually form sulfide ores.
Some minor elements size and chemical properties

Many elements whose ions have intermediate radii, especially metals of the
transition groups, substitute readily for iron and Mg, hence are abundant in the
earlier members of the differentiation Sequence.
Cr, Ni, Co, enriched which Mg in ultramafic rocks
Mn, Ti, V gabbros and basalts
Among chalcophite element, a few substitute for major cations in silicate structures
Pb2+ and TI+ for k+
Zn2+ for Fe2+ and Mg2+
Bi3+ for Ca2+
But mostly these elements are left to accumulate in the residual solutions,
eventually form sulfide ores.
Some minor elements size and chemical properties major elements
Ga3+ always present in AI3+ minerals
Rb and K, Hf and Zr, Cd and Zn
Partition Coefficient
KMe = [Me mineral
[Me melt
Incompatible elements in silicate minerals < 1

Rare- earth Elements

Periodic table: third column, sixth period
Despite their name, the REE are not especially uncommon in earth
materials
The group as a whole makes up > 200ppm of average crsut
Some elements are more abundant than Pb and cu
Except Eu, are more concentrated in granite than basalt
Incompatable with the common ions of igenous magmas, LREE (La- Sm)
more incompatible than HREE (Eu- La)
Active metals, +3 oxidation number
High oxidation number and large ionic radii (0.86- 1.10)- incompatible in
common minerals of igneous rocks
Incompatibility varies from mineral to mineral and element to element
Do not substitute for Fe2+ (0.78) and Mg2+ (0.72) but with Ca2+ (1.00), but
the difference in oxidation number keeps substitution limited
Concentrate to form their own minerals (monzite, Xenotime, Allanite) in alkali
granites and pegmatites

Rare Earth Elements (Lanthanides)

Lanthanum
Cerium
Praseodymium
Neodymium
Promethium
Samarium
Europium

Gadolinium
Terbium
Dysporosium
Holmium
Erbium
Thulium
Ytterbium
Lutetium

Ions
La3+
Ce3+
Pr3+
Nd3+
Pm3+
Sm3+
Eu3+
Eu2+
Gd3+
Tb3+
Dy3+
Ho3+
Er3+
Tm3+
Yb3+
Lu3+

Radii ()
1.03
1.01
0.99
0.98
0.97
0.96
0.95
1.17
0.94
0.92
0.91
0.90
0.89
0.88
0.87
0.86

100

Ratio:
Rock/
Ch

ondrite
s

10

0.1
La

Ce

Pr

Nd

Eu

Tb
Nb
Tm
Lu
Sm Gd Dy Er Yb

A: Earth material not greatly Differentiated from the original Meteoritic composition
(Peridotite from mantle)
B: Basalt from MOR, partial melting of upper mantle.
C: Rhyolite (Differentiated.)
D:Granite.
E: Anorthosite
F: Shale, repeated differentiation of both igneous and sedimentary processes.

Distribution in Sedimentary Rocks

Weathering and sedimentation

Huge and inefficient chemical separatory process
Silical, alumina, iron, carbonates
Placer deposits, of gold, platinum, monazite, zircon
Magnetic rich layers in sandstone- less resistant
Solubility, adsorption, organic activity

(ppm)
Ba
Li
Rb
Sr

Shales Sandstones
Carbonates
600
10-100 10
60
15
5
140
60
3
400
20
610

As
B
Mo
P
Se

10
100
2
750
0.6

1
35
0.2
170
0.1

1
20
0.4
400
0.1

Ionic
potential=
<2.5

Ionic
potential=
>9.5

Most rarer elements- more abundant in shales

Sr, Mn Carbonates Sr2+ for Ca2+
Zr & REEs Sandstone

Resistant
Most of the minor elements sow marked preference for fine grained
sedimnets, Why? Substitution
Mn & Li (Mg in sediments), Ba (for K in illite), Ga (for Al) in clays
Minor elements in organic matter more abundant in finer sediments
Sorption small ions more strongly sorbed than big ones, multivalent ions >
univalent
Ionic Potential
Different than ionization potential
Tendency of an ion to precipitate as hydroxide
I.P= Charge/ Radius
Water : bipolar
Me- O- H
If Me-O is weak, compared to O-H
Me remains free in solution

Precipitation, Oxidation, Reduction

Separation of minr elements from others by direct precipitation of low

solubility compounds
Phosphorite B
Mn carbonates N
Evaporate deposits I
Mn precipitates as oxidation
U, V reduced in organics (lower oxidation states are much less soluble)
Organic matter rich in V, Mo, Co, As, Cu, Br, I
Used by organisms in life process
Adsorption of trace metals
V & Mo : Asphalt
U & Cu : Black shales
Ge
: Coal

Distribution in Metamorphic rocks

Information during metamorphism and hydrothermal alteration is meager

Sometimes, only small changes
Fine grained to hornfelses and phyllites no changes unless permeated by
solutions
Guess pre- metamorphic material
Dehydration and decrabonation H2O and CO2
Addition of or removal of elements metasomatic mass transfer
H- Metasomatism: acid solutions react with feldspar to form sericite or clay
minerals
K- Metasomatism: formation of orthoclase in porphyry copper type deposits
Na- Metasomatism albitization
Ca- Metasomatism formation of epidosites
Me- Metasomatism chlorite and smectite