14/10/2019
Environmental Geotechniques
THEORIES OF ION EXCHANGE
Shruthija Sreeram Sarojini P Srujana T
M. Tech GTE M. Tech GTE M. Tech GTE
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Department of Civil Engineering Department of Civil Engineering Department of Civil Engineering
NIT Warangal NIT Warangal NIT Warangal
Presentation Outline
• ION EXCHANGE
• TYPES OF ION EXCHANGE
• EXCHANGE REACTIONS IN SOIL
• ION EXCHANGE SELECTIVITY
• ION EXCHANGE PROCESS
• THEORIES OF ION EXCHANGE
• FACTORS AFFECTING ION EXCHANGE
• CONCLUSION
• REFERENCES.
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ION EXCHANGE:
A reversible process by which cations and anions are interchanged or exchanged
between solid and liquid phases and between solid phases, if in close contact with each other.
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Figure 1 Ion Exchange in soil
TYPES OF ION EXCHANGE:
1. Cation Exchange
Exchange of positively charged ions.
Ca+2 ,Mg+2,K+,Fe+2,Mn+2 and Zn+2
2. Anion Exchange
Exchange of negatively charged ions.
Cl- and SO4-2.
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EXCHANGE REACTIONS IN SOIL:
•Soil colloids exhibit charges at mineral surface , balanced by counter ions of opposite
charge .
•The interaction varies from covalent bonding to weak electrostatic interactions.
•Ions attracted by weak electrostatic interaction can be replaced by other similarly
charged ions.
•Exchange reactions are rapid , if the site is solution accessible.
•They exhibit preferences among ions of different charge and size.
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•Exchange is a chemical reaction, and can be treated like any other mass action
expression.
For the reaction:
Equilibrium expression K has been named as the selectivity coefficient and also
exchange coefficient.
it can be defined as :
Selectivity coefficient =
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•If K is greater than 1 B is preferred over A.
•If K is less than 1 A is preferred over B
ION EXCHANGE SELECTIVITY:
•Valence
•Ion solvation
•Chelation by exchanger
• van der WAAL’S forces
•Sieve Action by exchanger
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•VALENCE:
Ions with higher valence are more preferred.
•ION SOLVATION:
Exchanger will prefer the ion that is less solvated with water molecules.
It will prefer an ion which is a structure breaker over which is structure maker.
•CHELATION BY EXCHANGER:
Divalent ions (or higher valent ions) generally form chelate structures whereas
monovalent ions do not.
Some environmental materials like proteins, humates, polyurinoides are likely to show
additional preferences for higher valent ions as they can form a multidentate complex with
ions.
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• van der WAAL’s FORCES:
Exchanger will prefer the ion with the greater number of “exposed” atoms which can
form dipole –induced dipole attractive forces between the exchanger and the ion .
•SIEVE ACTION BY EXCHANGER:
Smaller size ions are preferred than larger size ions.
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THE EXCHANGE PROCESS:
•A number of expressions have been proposed to quantitatively describe the equilibrium
between ions in bulk solution(pore water) and ions in aqueous solution immediately adjacent to
charged colloid surface .
•Exchangeable ions are thought to be loosely bound to the surface by forces in addition to
electrostatic forces while others are clearly dissociated from the surface and fully hydrated but
still held in the area by electrostatic forces.
•To measure exchangeable ions, we consider Exchange phase is at equilibrium with a solution of
exactly known ionic composition.
•Usually, we extract all pore water(including salts) as well as all the exchangeable ions.
•By subtracting the quantity of salt ions from total quantity of ions the quantity of exchange ions
in the sample is estimated.
•This approach will assume that there is only one type of charge in sample either cation
exchange or anion exchange. 12
THERMODYNAMIC EXPRESSIONS
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THEORIES FOR ION EXCHANGE
•Development of theories for equilibrium concentrations and the rate of ion exchange is
difficult because of the great complexity of the system and large number of variables
involved.
•Some of theories involve application of the mass law , kinetic theory, double layer theory
and molecular dynamics.
•Due to the difference in ion size and specific interaction energies ratio of counter ion
concentration in double layer is not same as in the equilibrium solution.
•In a system containing both monovalent and divalent cations the ratio of divalent to
monovalent cations is much higher in adsorbed layer than in equilibrium solution.
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•The Gapon equation is useful for estimating the proportion of monovalent and divalent
ions.
•If subscript s refers to the exchange complex of the soil, subscript e refers to the
equilibrium solution then, Gapon equation is given by;
where M and N are monovalent cation concentrations
P refers to the concentration of divalent ions
k1 , k2 are selectivity constants
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SODIUM ADSORPTION RATIO (SAR):
•The measure of amount of sodium relative to calcium and magnesium in the water extract
from saturated soil paste.
•It is calculate das the ratio of sodium to calcium and magnesium in the soil using Gapon
equation and is expressed as follows
•SAR can be determined by chemical analysis of pore water 16
EXCHANGEABLE SODIUM PERCENTAGE(ESP):
•The extent to which the adsorption complex of a soil is occupied by sodium.
•ESP is expressed as the ratio of exchangeable sodium to total cation exchange capacity .
where the concentrations are in meq/100 g soil
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SIGNIFICANCE OF SAR AND ESP:
•Good indicators of the stability of clay soil structure to breakdown and
particle dispersion.
•Soils with ESP greater than 2% may be susceptible to spontaneous dispersion
in water and behaves as dispersive clays.
•SAR decreases the infiltration and permeability of soil
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FACTORS AFFECTING ION EXCHANGE:
•Clay mineralogy
•Solution concentration
•Temperature
•pH
•Organic matter in soil
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CONCLUSION:
•Study of ion exchange help in treatment of contaminated soils
•Ion exchange in agricultural soils help in providing plant nutrients.
REFERENCES:
“FUNDAMENTALS OF SOIL BEHAVIOR” –JAMES K.MITCHEL AND KENICHI SOGA
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