Environmental Biogeochemistry of Trace metals (CWR6252)

WEEK-2

THE EARTH SYSTEM: LITHOSPHERE-

HYDROPHERE INTERACTIONS
PART -I
 I - Earth’s Layers
Classification based on physical
properties and composition

CRUST
Solid Rocks

MANTLE
Molten Rocks

OUTER CORE
Liquid-like
Ni and Fe

INNER CORE
Solid
1. Seismic compressional waves (P)all media
2. Seismic shear waves (S)solid only dominated by Ni and Fe
The Earth's Crust is like the skin of
an apple. It is very thin in comparison to
the other three layers.

•About 3-5 miles (8 kilometers) thick

under the oceans (oceanic crust) and about
25 miles (32 kilometers) thick under the
continents (continental crust).

•The temperatures of the crust vary from

air temperature on top to about 1600
degrees Fahrenheit (or 8700C) in the
deepest parts of the crust.

•It is made of solid rocks

 WHAT ARE ROCKS?

• Rocks are cohesive aggregates made up of

one or more minerals.
• Minerals are homogeneous, naturally
occurring, inorganic solids with well-defined
chemical composition and a characteristic
crystalline structure. A mineral may be a single
element or a compound made up of a number
of elements.
THE 3 ROCK GROUPS AND THE
ROCK CYCLE
1. Igneous Rocks
Extrusive igneous rocks:
• Natural Glass—very fast lava cooling at the Earth’s
surface – No mineral crystal formed
• Volcanic rocks—fast cooling of the lava at or near
surface to produce dark rocks. BASALT is the most
common extrusive IR found in sea floor and locations of
cooling magma on continents
[Minerals: olivines, Pyroxenes, amphiboles, Plagioclase
feldspar, Alkali feldspar, and quartz. [Fe, Mg, Ca, Si, Na, K, Al,
O, H]

Intrusive or PLUTONIC ROCKS: formed by slow

cooling of the magma deep in the crust resulting in the
formation of light pink igneous rocks (e.g. granite, gabbro,
granodiorite). The slow cooling process allows the
formation of big mineral crystals.
Minerals: olivines, Pyroxenes, amphiboles, Plagioclase feldspar,
Alkali feldspar, and quartz. [Fe, Mg, Ca, Si, Na, K, Al, O, H]

MANTLE: RISING MAGMA

 2. Sedimentary Rocks
Formed at low temperature
by LITHIFICATION, a set 2.1. Clastic
of processes transforming Sedimentary
sediments to sedimentary Rocks [from
rocks. sedimentary rock Greek “klastos”
types include: = broken] are
made from the
broken bits of
other rocks.

2.3. Organic
Sedimentary Rocks:
cemented remains of
2.2. Chemical living things such as
Sedimentary Rocks: clamshells, plankton
formed only by precipitation skeletons, dinosaur
or growth from solutions bones, and plants.
 3. Metamorphic Rocks
Metamorphic rocks are formed where
plates are coming together; rocks are
heated and are under high pressure.

D
C

Contact Metamorphism
Regional Metamorphism
GRANITE

Schist
PART -II
II - DISTRIBUTION OF CHEMICAL
ELEMNTS IN ROCKS

HOW CAN WE PREDICT THE OCCURRENCE /

DISTRIBUTION OF CHEMICAL ELEMENTS IN
GEOLOGICAL MATERIALS?

EXAMPLE 1: THE PERIODIC TABLE AS A PREDICTIVE

TOOL

EXAMPLE 2: THE GOLDSCHMIDT’S GEOCHEMICAL

CLASSIFICATION
 1. OBJECTIVES
• Understand the distribution of the
elements in different rock types and the
reasons for such distribution.

• Develop the ability to predict the

occurrence of trace elements based on
knowledge of bedrock geology
 2. Goldschmidt’s Geochemical
Classification
• Approach based on a hypothetical question:

– If the Earth at some time in the past was largely molten and if the molten
material separated itself on cooling into a (1) metal phase, (2) sulfide
phase, and (3) a silica phase—how would the elements distribute
themselves among these three materials?
• Answer formulated based on (i) theoretical arguments
and (ii) the following 3 types of observations:

– Composition of meteorites (assumes similarity with primordial Earth)

– Analysis of metal slag (silicate) and matte (sulfide) phases in

metallurgical operations

– The actual composition of silicate rocks, sulfide ores, and the rare
occurrence of native iron in the Earth’s crust
2.1. THEORETICAL APPROACH: Expected distribution of the elements
between metallic iron (Fe0) and silicates, in a system with iron in excess – DGf
of oxides are used as best approximation due to limited availability of DGf of
silicates (DGf per oxygen atom)

DGf (kJ), 250C DGf (kJ), 8270C

CaO -604.0 -520.8 Elements above
MgO -569.4 -481.6 Fe go into oxide
Al2O3 -527.4 -442.7 (surrogate for
UO2 -515.9 -447.2 silicates)
TiO2 -444.7 -371.9
SiO2 -428.3 -356.8
MnO -362.9 -304.3
K2O -322.1 -203.2
ZnO -320.4 -237.9
WO2 -266.9 -195.0 ???
SnO2 -259.9 -176.5 ???

FeO -251.1 -199.5

MoO3 -222.7 -156.7
CoO -214.2 -154.9
Elements below
NiO -211.7 -140.7
Fe go into the
PbO -188.9 -109.2
metallic phase
Cu2O -146.0 -86.9
 2.1.1.Theoretical approach: Conclusions

• This thermodynamic approach predicts that metals that are more chemically
active than Fe would possibly combine with silica to form silicates.

• The remaining silica will react with Fe until total to near total Si depletion

• Metals less active than Fe would therefore have no chance to form silicate
minerals, but would remain as free metals with the uncombined excess iron

• Similar tables could be drawn for element distribution between (i) metal and
sulfide phases with iron in excess, and (ii) sulfide and silicate phases with
silica in excess

• Ambiguities: A few problems exist.

• e.g., W and Sn stand above Fe at low temperature (T) and below Fe at high T
• Also, the approach requires several assumptions, and therefore, used numerical values
are not always very helpful
 2.2. OBSERVATIONAL STUDIES

• 2.2.1. ANALYSIS OF METEORITES

– Elements above iron in previous Table found primarily in silicate
phases
– Elements below are strongly concentrated in sulfide phases
• 2.2.2. SILICATE ROCKS, SULFIDE ORES, NATIVE
IRON
– The distribution of rare elements determined here found to be in
good agreement with the distribution in meteorites and smelter
materials
• Note: No complete agreement is obtained with any of the above two
approaches. The conditions of formation of sulfide ores in nature are quite
different from the conditions under which sulfides would separate from an
artificial melt for example
 2.3. Goldschmidt’s Geochemical
Classification
SIDEROPHILE: They occur with native iron
Fe, Co, Ni, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Mo, Ge, Center of the
Sn, C, P, (Pb), (As), (W) Periodic Table
(mostly noble metals)

CHALCOPHILE: Concentrated in sulfides

Cu, Ag, (Au), Zn, Cd, Hg, Ga, In, Tl, (Ge), (Sn), Right of the
Pb, As, Sb, Bi, S, Se, Te, (Fe), (Mo), (Re) Periodic Table

LITHOPHILE: Associated with silicates

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

ATMOPHILE: prevalent in gas phase

H, N, (C), (O), (F), (Cl), (Br), (I), He, Ne, Ar, Kr, Xe Extreme right of
the Periodic Table
3.Distribution of Elements in Igneous Rocks

Objective: Find out how the behavior of trace elements could

be related to the differentiation-crystallization sequence of a
rising magma
 3.1.Mineral Formation During Differentiation &
Crystallization of a Silica Melt
K-feldspar: KAlSi3O8
Quartz: SiO2
FELSIC:
BIOTITE
formed from
Lower T magma rich in Si, K(Mg,Fe)3AlSi3O10(OH)2
Na, Al, K Na-plagioclase
Hornblende NaAlSi3O8
Ca2Mg5Si8O22(OH)2
MAFIC: formed
from magma rich in
Ca, Mg, Fe – poor in Pyroxene (Mg,Fe)SiO3
Si Or Ca(Mg,Fe)Si2O6

ULTRAMAFIC: Ca-plagioclase
Olivine
formed from magma rich CaAl2Si2O8
in Fe and Mg (Mg, Fe)2SiO4
High T

MANTLE: RISING MAGMA

 3.2. Igneous rocks: Rules of
distribution
• Elements and mineral crystallization
1. For an element to crystallize in a mineral of its own, it is necessary that
the element be present in the melt in appreciable amounts
2. If only a few ions of an element are present in the melt, they can be
taken up by the crystal structures of the major silicates. Such
incorporation of ions in the crystal structure is dictated by following
rules:
– (a) Random inclusions: depends on the characteristics of the ions. For
instance, K+ (major) and Rb+ (trace) are so similar that Rb is
accommodated as replacement of K in K-feldspar. Random inclusion
can have the following implications:
» K/Rb  high abundance of K and high similarity w/ Rb leads to
no Rb mineral formed
» Zr  lack of similarity leads to formation of its own mineral
(zircon)
» Be, B, Cu, and U accumulate in residual melt that gives rise to
pegmatites and quartz sulfide veins
– (b) Isomorphous replacements: unlike random inclusions, isomorphous
replacement follows a few specific rules other than the simple similarity
of ions
 3.2.1. Rules of Isomorphous Replacement

• RULE 1 – A minor element may substitute extensively for a major element if the
ionic radii do not differ by more than ~15%
– e.g., Cd2+(0.95Å)/Ca2+(1.00Å) and Cr3+(0.615Å)/Fe3+(0.643Å).

• RULE 2 – Ions whose charges differ by one unit may substitute for one another,
provided their radii are similar and provided the charge difference can be
compensated by another substitution

Element in original mineral Elements after replacements

Na+/Si4+ Ca2+/Al3+

• RULE 3 – Of two ions that can occupy the same position in a

crystal structure, the one that forms the stronger bonds with its
neighbors is the one with the smaller radius, higher charge, or both
– Example: Li+ (0.76Å) which substitutes for Mg2+ (0.72Å) forms
weaker bonds than the double charged Mg2+ and would then
concentrate in late forming Mg-minerals (e.g. micas of
pegmatites) and is rather absent in minerals formed early in the
differentiation-crystallization sequence (e.g., olivine)
Rules of Isomorphous Replacement (Cont’d)

• The above 3 rules (rules 1, 2, and 3) work well for elements in the
first three columns of the periodic table. For the other elements,
predicted and observed trends are less satisfactory

– For example: Hg2+(1.02Å)/Ca2+(1.00Å). Despite the similarity in

radii and ionic charges, Hg is usually not found in Ca-rich
minerals or rocks

– This difficulty is explained by “RULE #4”, which involves the

bond character

• RULE 4 – Substitution of one ion for another may be

very limited, even when the size criterion is fulfilled, if
the bonds formed differ markedly in covalent character
 3.2.2. Regularities of Distribution of Elements in Igneous
Rocks: Features revealed by rock analysis

• 1. INCOMPATIBLE ELEMENTS
– (a) The Large-ion-lithophile or “LIL” group:
– Large radii
– Low electrical charge
– Tend to substitute mostly for K and are therefore concentrated
in felsic rocks
– They include Rb, Cs, Ba, Pb, Tl. REEs also included in this group,
but substituion is primarily for Ca rather than K
– (b) The High Field-Strength Elements or “HFSE”
– Small radii
– High charge
– Concentrated at the felsic end series due to poor substitution
– Include U4+, Th4+, B3+, Be2+, Mo6+, W6+, Nb5+, Ta5+, Sn4+, Zr4+
– Build up in residual melt could lead to minerals of their own
• 2. Several transition group elements substitute readily for Fe
and Mg, hence are abundant in the earlier members of the differentiation
sequence

• 3. Chalcophiles: Mostly left to accumulate in the residual solutions that

may form sulfide ores. A few substitute to some extent for major cations in
silicate structures. Examples: Pb2+ and Tl+ for K + ; Zn2+ for Fe2+; and Mg2+
and Bi3+ for Ca2+.

• 4. Near Perfect Isomorphism: Normal differentiation can’t separate

elements due to strong similarities in size and chemical properties (e.g.,
Ga/Al, Rb/K; and Cd/Zn)

• 5. REEs: Group of 15 elements divided into LREEs (La—Sm) and HREEs

(Eu—Lu)

Some minor elements are so similar in size and chemical properties to

major elements that normal differentiation cannot separate them effectively
from their major relatives. Gallium (Ga) is a good example – present in
aluminum minerals and almost inexistent in a mineral of its own. Other pair
examples: Cd/Zn, Hf/Zr and Rb/K.
 Igneous Rocks: Summary
The distribution of trace (or minor) elements in igneous rocks can be
explained fairly well by assuming a slow crystallization of an orderly
sequence of minerals from a melt, usually leading to differentiation.
The main conclusions are as follows:

– Chalcophile elements may separate early, either in an immiscible sulfide liquid

or as sulfide crystals

– Most of the trace elements are taken up by the crystallizing silicates,

substituting for the major elements in mineral structures largely on basis of
ionic size

– Many details of the distribution of the elements can be correlated with ionic
properties, size, charge, and tendency to form covalent bonds

– Some elements like U and Zr have ions so different from the major elements
that little substitution is possible, and hence may form separate minerals even
when only small amounts are present

– The REEs = group of incompatible elements with ions of similar size and
charge—often used to track down the origin of igneous rocks
 4. Distribution of Elements in Sedimentary
Rocks (SR)

•Similar to IR, element distribution in SR can be studied in relation with: (1)

ionic size, (2) ionic charge; (3) bond character; and (4) precipitation rxns that
affect the distribution of certain minor elements

•Most minor elements are concentrated in fine grained rocks (e.g., shale) due
to Ionic substitution; Incorporation of metal bound to organic matter; and
Sorption based on the fact that: (i) small ions strongly sorbed than bigger ions;
(ii) multivalent ions strongly sorbed than univalent ions; and (iii) polarizing ions
sorbed more than non-polarizing ions
 Distribution of Elements in Sedimentary Rocks (Cont’d):
Classification based on Ionic Potential (IP)

•In addition to the above parameters, the accumulation of minor elements in SR

can be linked to the concept of IONIC POTENTIAL (IP) = [Electrical charge
(z)]/[Ion radius (r) in angstrom (Å)] and metal solubility in water
H
(+) O Men+
H (-)

If H—O stronger than Me—O: Me will remain in solution (poor incorporation in

rocks)
If Me—O stronger than H—O: Me appropriates one or more O from water
molecules forming oxyanions and releasing H+:
Se+6 + 4H2O  SeO42- + 8H+
If H—O roughly equal to Me—O: leads to the formation of an insoluble hydroxide:
Zn2+ + 2H2O  Zn(OH)2 + 2H+
IP<2.5 2.5IP<9.5 IP>9.5
(low IP) (Intermediate) (High IP)
Ba, Li, Rb, Sr REEs, Cu, Ni, Pb, U, Zn, Zr, Tl, As, B, Mo, Se
(remain in solution) Sc, Ge, Cr, Co,….(will precipitate) (will form oxyanions)
 Distribution of Elements in Sedimentary Rocks (Cont’d)

1. Role of Redox Chemistry:

Redox sensitive Mn and Fe vs. Substitution

U and V in the presence of organic matter

Sulfide (e.g., S2-) driven metal precipitation (chalcophiles)

2. Average concentration of minor elements in sedimentary rocks:

•Handout

•Shales (fine-grained rocks, high conc. of minor elements)

•Sandstones (clastic rocks, enriched with Sr and Mn (isomorphous
replecement and substitution); Zr and Ce (by mechanical conc. of the bits of
zircon (ZrSiO4) and cerium minerals (e.g.,CePO4 )
•Carbonates (formed by precipitation and enriched with Sr (by Ca
replacement), P and Cl (by precipitation), Mn, Y, some REEs (by ionic size
similarities)
 5. Distribution of Elements in
Metamorphic Rocks

•A the exception of a few cases where extreme changes occur,

metamorphism causes only minor changes in element distribution

•When present, changes dependent on: (1) composition of initial rock;

(2) composition of fluid that comes in contact with the rock; (3)
pressure; (4) temperature; (5) rock porosity; and (6) permeability.

OVERALL CONCLUSION: To fully understand the distribution of elements

for a particular rock requires knowledge of the geologic history of all the
chemical processes that have acted on the rock – However, observed
patterns follow theoretical expectations very well.
PART -III
CHEMICAL BACKGROUND
EQUILIBRIUM THERMODYNAMICS
 LECTURE OUTLINE
1. GIBBS FREE ENERGY
 Equilibrium thermodynamics and environmental chemistry
 Gibbs free energy and energy measurement
 Energy of reaction
2. GIBBS FREE ENERGY AND SOLUBILITY PRODUCT
(Ksp)
 Equilibrium constant (Keq) and solubility product (Ksp)
 Effect of temperature on K : The Van’t Hoff Equation
3. DEPARTURE FROM EQUILIBRIUM: MEASUREMENT OF
DISEQUILIBRIUM
 Activity Product (AP) and Ion Activity Product (IAP)
 Saturation Index (SI)
 Saturation Ratio (SR)
4. ACTIVITY-CONCENTRATION RELATIONSHIPS
 Ionic Strength (I)
 The Debye-Huckel theory
 1. GIBBS FREE ENERGY (G)

 Equilibrium Thermodynamics
 Provides a good approximation to the real world
 Indicates the direction in which changes can take place
 Is the basis for calculation of rates of natural processes
 G = Appropriate measure of energy
 At constant T and P
 Is expressed in kJ/mol or kcal/mol and is related to enthalpy
(H in kJ/mol or kcal/mol) and entropy (S in kJ/mol.K or
kcal/mol.K) as follows:
 G = H – TS
 For energy changes at constant T and P
 DG = DH – TDS
 If DG < 0  spontaneous process
 If DG = 0  process at equilibrium
 If DG > 0  energy consuming and non-spontaneous reaction
 1.1. Energy of Reaction
1. Example problem: Calculate the DGr0, DHr0 and the
DSr0 of the following reaction:

6Fe2O3 (hematite)  4Fe3O4 (magnetite) + O2

 Solution Strategy
 First, find data on standard free energy of formation (DGf0), standard
enthalpy of formation (DHf0) and the standard entropy (S0) associated
with each species using tabulated thermodynamics data.
 Second, determine the free energy (DG 0), enthalpy (DH 0 ) and entropy
r r
(DSr0) of reaction:
 Standard free energy:
DGr0 = SGf0(products)– SGf0(reactants)
 Standard enthalpy:
DHr0 = SHf0(products)– SHf0 (reactants)
 Standard entropy:
DSr0 = SS0 (products)– SS0 (reactants)
In these calculations the stoichiometry of rxn should be taken into account
 Solution
6Fe2O3 (hematite)  4Fe3O4 (magnetite) + O2
Reactant Product-1 Product-2

Fe2O3 (hematite)………….Fe3O4 (magnetite)… O2

 (DGf0 in kJ/mol)………. -742.8…………….. -1012.9…………0

 (DHf0 in kJ/mol)………. -824.7…………….. -1116.1………....0
 (S0 in kJ/mol.K)…………….+0.0877……………..+0.205…….+0.0604

 DGr0 = SGf0products – SGf0reactants
 = [4*(-1012.9)+(0)] – [6*(-742.8)] = +405.2 kJ/mol

 DHr0 = SHf0 products– SHf0 reactants = +483.8 kJ/mol

 DSr0 = SS0 products– SS0 reactants = 0.3532 kJ/mol.K

 2. DG and SOLUBILITY PRODUCT

 Example problem:
 Calculate the solubility product (Ksp) of gypsum
(CaSO4.2H2O) at 250C

 Solution Strategy
 (1) - write the chemical equation of the above dissolution reaction,
find tabulated data on free energy of formation for each species.
 (2) - determine the standard Gibbs free energy of reaction: DGr0

 DGr = DGr0 + RTlnKeq
 At equilibrium the Gibbs free energy =0 (DGr = 0), and therefore
DGr0
log K eq 
2.303RT
 DGr0 = - RTlnKeq  
 DGr0 
  
 2.303 RT 
R=gas constant= 8.3143 J/mol.K or 1.98717 cal/mol.K K eq  K sp  10  
 Calculate the solubility product (Ksp) of gypsum (CaSO4.2H2O) at 250C.

(1) Write the chemical equation of the above dissolution reaction,

find tabulated data on free energy of formation for each species

 CaSO4.2H2O <==> Ca2+ + SO42- + 2H2O

 -1797.36 -552.8 -744.0 -237.14 (DGf0 in
kJ/mol)
 .
 (2) Determine the standard Gibbs free energy of reaction:

 DGr0 = SGf0products – SGf0reactants


 = [(-552.8)+(-744.0)+2*(-237.14)] – [(-1797.36)] = +26.28 kJ/mol

 At equilibrium: DGr0 = - RTlnKsp

And Ksp = 10-4.60

The DG and Solubility Product Constant
(Cont’d)

 Ksp at temperatures, T within 200C or so of

the standard state (T=250C)

 VAN’T HOFF equation is used

DH 0r  1 1 
log K sp T 2  log K sp  T1    
2.303R  T1 T2 

In this case, if temperatute T2 is far different from

temperature T1, variation of DHr0 with changing T
must be calculated from heat capacity data
 3. MEASUREMENT OF DISEQUILIBRIUM
For a chemical reaction: aA + bB  cC + dD
[ C] c [ D ] d
K eq 
[A]a [B]b
ACTIVITY PRODUCT (AP) AND ION AP (IAP)
When ([C]c[D]d)/([A]a[B]b) is different from Ksp, this ratio is called AP,
and if species involved are ions  IAP
Used to predict the direction in which change is taking place
 AP/Ksp = 1  reaction at equilibrium
 AP/Ksp >1  reaction will go to the left (e.g. precipitation)
 AP/Ksp <1  reaction will go to the right (e.g. dissolution)
SATURATION INDEX (SI)
SI is simply the log(AP/Ksp) to indicate how far a given system is far
from equilibrium, and with SI=0 at equilibrium.
SI>0 saturation and for SI<0 under-saturation
SATURATION RATIO: normalization to number of ions (n) involved
1
in the reaction  AP  n
SR   

K
 eq 
4. ACTIVITY-CONCENTRATION
RELATIONSHIP

 4.1. Ionic Strength (I)

I  0.5  S(mi  zi2 )

 Where mi = molar concentration and zi = ionic charge

 Example: Calculate the ionic strength (I) for a 1M

solution of Na2SO4

Na2 SO4  2 Na   SO42

I  0.5  S(mi  zi2 )
 0.5  ((2 12 )* (1 (2) 2 ))  3
 4.2. Activity Coefficient (gi)

 Activity (ai) and fugacity (fi)

ai
gi 
mi
Where mi = molal units
4.3. The Debye-Hückel Model
 Debye-Hückel Equation (1)
 Allows the determination of activity coefficient for a single ion on the basis of the effect
ionic interactions should have on free energy. This model works for solution with I up to
10-3
log g i   Azi I 2

 Debye-Hückel Extended Equation & Guntelberg eq. (2)

 The above model fails for I>10-3. In such cases, the extended equation is
used. The use of the latter is valid only for I values up to 10-1and when
Bao=1, the equation is called the Guntelberg Equation

 Azi2 I  Azi2 I
log g i  and log g i 
1  Ba0 I 1 I
 The Davies Equation (3)
 Applicable to solutions with I> 10-1. In the Davies’ equation the value of b =
0.3
 Azi2 I  Azi2 I
log g i   bI and log g i   bI
1  Ba0 I 1 I
g = activity coefficient; I=ionic strength, A & B =constants depending only on P and T, z = ionic charge,
a0=hydrated radius of the ion in consideration, and b = constant specific to the individual ion (or general),
Variation of the activity coefficient of Ca2+
according to the three forms of the Debye-
Hückel equation

gCa2
+
(3)

(2)

(1)

0.001 0.1

Ionic Strength (I)

Example Problem #1

 A water sample has a Ca2+ activity of 10-3.5 and SO2-4 activity of 10-1.5.
 1. By how much is the water either under or over saturated with respect
to gypsum (CaSO4.2H2O)?
 2. By how much would it have to be concentrated or diluted for it to be in
equilibrium with gypsum?

Solution strategy

1. Write the chemical equation of the dissolution of gypsum

2. Calculate the activity product from given activities
3. Calculate Ksp = Keq from tabulated DG of formation data
4. Calculate the ratio IAP/ Ksp and conclude on satuartion status
5. Calculate the saturation ratio (SR = (IAP/Keq)1/n) and determine
the concentration or dilution factor as 1/SR
Solution
1. Write the chemical equation of the dissolution of gypsum
CaSO4.2H2O 2H2O + Ca2+ + SO2-4

2. Calculate the ion activity product from given activities

IAP = [Ca2+ ][SO2-4] =10-3.5*10-1.5 =10-5
3. Calculate Keq from the equation of DG
Keq = Ksp = 10-4.6 (based on DGfo data)

4. Calculate the ratio IAP/ Ksp and conclude on satuartion status

IAP/ Ksp= (10-5)/ (10-4.6 )=0.4
Or SI = Log[(10-5)/ (10-4.6 )] = -0.3979  -0.4
Since SI<0, the solution is under-saturated and the above rxn is moving to the
right = dissolution

5. Calculate the saturation ratio (SR = (IAP/Keq)1/n) and determine the

concentration or dilution factor as 1/SR

(SR = (IAP/Keq)1/n) = [(10-5)/ (10-4.6 )]1/2=0.63

The factor by which this solution needs to be concentrated to reach
saturation is 1/SR = 1/0.63 = 1.58

For the above chemical rxn, the energy released by dissolution of each
mole of gypsum can be determined as:

RTln(IAP/Ksp) = -2.28 kJ/mol

 Table 1
Example Problem #2 Analyzed mg/L (ppm)
compounds
A water sample from the Rio Grande has the
Ca2+ 109
chemical composition shown in Table 1 at 25oC:
Mg2+ 24
What is the ionic strength (I) of the solution? Na+ 117
What are the activity coefficients of Ca2+ and SO2-4,
based on the extended Debye-Hückel equation? K+ 7
By how much is the water under-saturated with HCO3- 183
respect to gypsum (CaSO4.2H2O)?
SO42- 238
Cl- 171
H4SiO4 48

Your solution strategy?

 SUGGESTED REFERENCES
• Introduction to Geochemistry (3rd edition) –
Chap.20
– Authors: Konrad B, Krauskopf and Dennis K. Bird
– McGraw-Hill, NY – 1995
– ISBN 0-07-035820-6

• The Geochemistry of natural Waters: Surface

and Ground waters (3rd edition) – Chap. 2.
– Author: James L. Drever
– Prentice-Hall, Inc. – 1997
– ISBN: 0-13-272-790-0