Lec 12.

Ion Exchange processes in soils

-cation cxchange
Ability of Soils to Hold Ions Against Leaching Loss

 The most important soil chemical attribute?

 Holds nutrients in ecosystems

 Keeps pollutants out of groundwater and surface water

 Ion exchange

is defined as the reversible process by which ions are interchanged between

solid and liquid phases in equivalent proportions

Exchange of ions may be of

The process of migration of cations between the two soil phases in contact
(ie. solid and solution phases) is termed as cation exchange and anions as
anion exchange

Cation exchange capacity

 It is defined as the capacity of soils to adsorb and exchange cations

 Scientifically it is related to the surface area and surface charge of the clay

CEC = Sxσ

Where S= specific surface

σ= surface charge density
 Depending upon the concept & type of charges

CECp CEC attributed to permanent charges, & importance in 2:1 layer

types of minerals

CECt Total CEC (or) CEC produced by both permanent and variable
negative charges

CECv Variable charge CEC (or) CEC caused by variable negative

charges. It is CECt – CECp

ECEC Effective CEC, which equals ΣNH4 acetate exchange bases + 1N

KCl extractable Al
 Determination of cations on the exchange complex

1. Stripping technique

(a) soil in equilibrium with solution is washed free of soluble salts with alcohol
and is extracted in a salt solution (~1N)
(b) soil with equilibrium solution is centrifuged, the supernatant liquid is collected
for analysis and the equilibrium solution left in the soil is measured.
Exchangeable cations =
(total cations extracted in the salt solution ) – (cations in the
left over equilibrium solution)
 2. Isotopic dilution technique

 given amount of soil with a known volume of untagged equilibrium solution

mixed with an equal volume of tagged solution of same composition (1:5 ratio)

 fully dispersed and equilibrated for 48 hrs on a shaker

 equilibrated soil suspension is centrifuged and the radioactivity is measured

 amount of adsorbed cation (Ax) is calculated using the following equation

Ax = [CPM control / CPM test -1] x (A)

CPM - counts per minute

A - total amount of species X in solution
Approaches to describe cation exchange equilibria

 Thermodynamic approach

 Law of mass action based approach

 Diffuse double layer approach

 Empirical equations of cation exchange
1) Adsorption equations (isotherm) –
a line on a map connecting points having the same temperature at a given
time or on average over a given period.
PHYSICS
a curve on a diagram joining points representing states of equal temperature.

 Freundlich equations
 Langmuir – vegeler equation

2) Mass action Law equations of cation exchange

 Kerr’s equation
 Vanselow’s equation
 Gapon’s equation
3) Kinetic equations
 Approaches to describe cation exchange
equilibria
1. Thermodynamic approach
preferential adsorption of cations by an exchanger (soil) is described on the basis of sign
and magnitude of the free energy change of exchange reaction

The exchange reaction between adsorbed cation B of valence ZAand solution cation A of
valence ZB is

ZA Bx + ZB A ZB A x + ZAB

X is the adsorbed phase

is the reversibility of the reaction

The thermodynamic free energy is the amount of work that a thermodynamic

system can perform. The concept is useful in the thermodynamics of chemical
or thermal processes in engineering and science. The free energy is the
internalenergy of a system minus the amount of energy that cannot be used to
perform work.
The free energy change of reaction  Gr, may be written by equation
aAXzB.aBzA

 Gr =  Gr0 + RTln
aAzB.aBxzA

Where  Gr0 is the standard free energy change of the exchange reaction

R - gas constant
T - absolute temperature
aA, aB - activities of cations A & B is solution phase
aAx, aBx - activities of cations A & B is the adsorbed phase

ZA & ZB are valence of cations A & B respectively

Under equilibrium situation, at constant temperature & pressure Gr
becomes zero and equation is written as

 Gr0 = - RT ln aAXzB.aBzA

aAzB.aBXzA eq (eq : equilibrium state)

(or)
 Gr0 = - RT ln K
Where K is micro dynamic equilibrium constant

The activity of ions in solution is the product of activity coefficient & molar
concentration of ions in respective phases
Activity coefficient, in chemistry, the ratio of the chemical activity of any
substance to its molar concentration.
Molar concentration (also called molarity, amount concentration or
substanceconcentration) is a measure of the concentration of a solute in a
solution, or of any chemical species, in terms of amount of substance per unit
What is the activity coefficient?
An activity coefficient is a factor used in thermodynamics
to account for deviations from ideal behaviour in a mixture
of chemical substances.
What is meant by the activity of an ion in solution?
Jump to: navigation, search. In chemical
thermodynamics, activity (symbol a) is a measure of the
"effective concentration" of a species in a mixture, in the
sense that the species' chemical potential depends on
the activity of a real solution in the same way that it
would depend on concentration for an ideal solution.
The activity coefficient () is calculated using Debye - Huckel equation

-log i = Azi2 √ I

1+B√ I
I = ionic strength of solution (moles L-1)

 = Ionic size parameter ie mean diameter of hydrated ion in Ao units

A & B are constants for the solvent at a particular temperature

The ionic strength of solution (I)

I = 0.5  CiZi2
Where C is concentration of ion, i in solution (mol L-1) and Z is valency

 indicates summation of product of C and square of valency of all ions

(cation and anion) present in the solution
Ionic Strength - a quantity representing the strength of the electric field in a
solution, equal to the sum of the molalities of each type of ion present
multiplied by the square of their charges.
 Mean diameter of important hydrated ions

Ions Mean dia (A0)

Monovalent ions (charge 1)
H+ 9
Li+ 6
Na+, HCO3-, H2PO4-, CH3COO- 4
OH-, F-, CNS-, CNO, HS-, ClO3-, MnO4-, K+, Cl-, Br-, I-, 3
CN-, NO2-, NO3-, Rb+, Cs+, NH4+, Ag+, H2-
Divalent ions (charge 2)
Mg2+, Be2+ 8
Ca2+, Cu2+, Zn2+, Sn2+, Mn2+, Fe2+, Ni2+, Co2+, 6
Sr2+, Ba2+, Ra2+, Cd2+, Hg2+, CO3 2-, SO3 2-, MoO42-, 5
Hg2 2+, SO4 2-,SeO4 2-,Cr O42-,HPO42- 4
Trivalent ions
Al3+,Fe3+,Cr3+, Se3+ 9
PO43-,Fe(CN)63- 4
 2. Law of mass action based approach

 absorbed ions and the solutions ions are definable and can be experimentally
determined

 on the basis of the diffuse double layers these are not definable as separate entities

a. Cation exchange equations for homovalent system

distribution of cations of equal valency in solution and adsorbed phases at equilibrium, is represented by a cation
exchange equation known as Kerr equation

AX = K ker aA

BX aB

Where AX and BX are the amounts of cations A and B of the same valency in the adsorbed phase

aA, aB are their activities in the equilibrium solution

KKer is the Kerr selectivity coefficient

 minimum distance approach of different cations towards the surface of the adsorber depends upon the size of
cation

 It is larger for the larger cation and vice versa.

 size of the hydrated cation plays an important role in relative preference of the exchanger for the two cations
competing for the exchange sites

 general order of preference is Cs > Rb > K = NH4 > Na > Li

 preference of the exchanger for

monovalent cations follows lyotropic series

divalent cations, the selectivity co efficient has been found to be slightly larger for Ca – Mg
exchange than the Mg –Ca exchange
 b. Cation exchange equations for heterovalent system

most widely used empirical equation for heterovalent system is Gapon equation
(1933)

KG = (aB)1/2 .NA
(aA).NB

KG - gapon co efficient
a – activity in solution
N – Equivalent fraction of the cation in the adsorbed phase
 3. Electric double layer Approach

soil colloidal system at pH above 6 possesses a net negative charge.

At the interface the electrical force exist.

When such particles with net negative charge are immersed in aqueous solution,
cations from the solution are attracted towards the charged surfaces and anions are
repelled due to columbic forces.

Hence thermal motion of cations, occurs tends to equalize the concentration of ions
in the system.
 Assumptions of this theory

 charged particle has flat surface without edge effect

 exchange sites are uniformly distributed over the entire planar surface
 dielectric constant of water in the aqueous solution phase is constant
 ions acts as point charge
 interaction between ion is negligible and the charged surface and ions
interacts electro statically
 charge on the surface is neutralized by the excess of oppositely charged
ions in the diffused double layer.
For a mixture of monovalent and divalent salt solutions, gouy’s theory of diffused double layer has been
used to obtain the relative amounts of cations adsorbed on the clay surface

The fractional saturation of the exchange complex by the monovalent cation has been shown to be a
function of

 surface charge density of the exchanger,

 cationic composition of the equilibrium solution and
 interaction between the diffuse layers on adjacent clay plates.

Such relationship was simplified and explained by Bolt, in 1955.

 Empirical equations of cation exchange

1) Adsorption equations

 Freundlich equations
 Langmuir – vegeler equation

2) Mass action Law equations of cation exchange

 Kerr’s equation
 Vanselow’s equation

3) Kinetic equations
 1. Adsorption equations
a. Freundlich equation

x = KC1/n

Where x = amount of cations adsorbed per unit amount of absorbent

C = equilibrium concentration of the added cation
K, n = constants

 This equation is not exactly a formulation of cation exchange reactions

 It pertains to formulation of adsorption of cations and

 no exchange parameter is included in the equation.

b. Langmuir – Vageler equation

x
------ = kC / (1 + kC)
xo

Where X = amount of cations absorbed per unit weight of exchanger

xo = total exchange capacity
C1 = concentration of added cations in moles per L
k = affinity coefficients

The k can be determined as

k= x / [C(xo– x)]
 2. Mass action Law equations of cation exchange
a. Mono-monovalent cation exchange reaction-Kerr’s equation

Na+ + K-soil Na- soil + K+

or
Na+ + KX NaX+ K+

Kerr’s equation for the above reaction = NaX (K+)

=k Eq.1
KX ( Na+)
Ratio of the activity
b. Divalent & monovalent cation exchange reaction product of reaction
and that of the
Ca X +2 K+ 2 KX + Ca2+ reactants is constant

the equation is
= KX 2 (Ca2+)
=k
CaX ( K+) 2
By taking sq.root of kerr equation

[ KX ] (√Ca+)
------------------------ = k (gapon equation)
[√ CaX] ( K+)

Gans (1913), Rothamund and Kernfield also developed mass action

equation but used concentrations in their equation and assumed that
activities are essentially equal to concentrations
Vanselow’s equation (1932)

He thought that activities of the exchangeable cations might be proportional to

their mole fractions in the exchange material and KX of the Kerr’s equation becomes
Kx NaX
Proportion of K / Na adsorbed= andNaxwillbe
Kx + Nax Kx + NaX
The equations for monovalent ions is

NaX
(K+ ) =k
Kx + NaX

for divalent monovalent ions pairs

KX
(Ca 2+) =k
Kx + CaX

[ ] denotes adsorbed cations

Mole fraction is a unit of concentration, defined to be
equal to the number of moles of a component divided by
the total number of moles of a solution. Because it is a
ratio, mole fraction is a unitless expression. Themole
fraction of all components of a solution, when added
together, will equal 1

In chemistry, the mole fraction or molar fraction (xi)

is defined as the amount of a constituent (expressed in
moles), ni, divided by the total amount of all constituents in
a mixture (also expressed in moles), ntot: x i = n i/ n t o t
 3. Kinetic equations
a. Gapon equation

amount of a given liquid will be taken up by a solid through exchange will be

proportional to the surface occupied by that liquid &

cation exchange is analogues to the replacement of one liquid by another from these
surface liquid.

e1F2
=k
e2 F0 – F2

F0 = entire surface
F2 = parts of the surface occupied at equilibrium
e1 & e2 = liquids at equilibrium

Gapon applied only to the exchange between divalent & monovalent ions

The amount & kind is determined solely by temperature. This has the same form as of
Kerr’s equation.
 b. Jenny’s equation (1936)

exchangeable cations oscillates about the centre of the particle.

when cation of a solution, normally in a state of thermal agitations chances to pass

between an exchangeable cation and the centre of the electric charge, exchange takes
place.

The cations previously in solution becomes exchangeable and simultaneously an

exchangeable cations becomes a solution ion.

Jenny developed the equation (ie.it depends on chance to pass between exchangeable
cations and surface of a solid).

Zw (Vb) =W

(Zb) Vw

Where W= No. of cations taken up or released at equilibrium

ZW & Zb : No. of exchange monovalent (W) & divalent (b) ions in solid

Vw + Vb = Oscillation volumes of the two kind of cation when in the

exchangeable form.
Davis (1945) developed an equation based on Jenny’s oscillation volume equation,
for exchanges between monovalent and divalent cations.

W= mono valent
b = divalent

Zw(Nb) ½ =k

(Zb) ½. Nw

ZW & Zb : No. of exchange monovalent (W) & divalent (b) ions in solid
Nw & Nb - No. of W & b ions in the solution
 Equations based on Donnan theory

Solution I Solution O
Na+
Na+
Cl-
Na clay Cl-
Semipermeable membrane only permeable to Na
and Cl ions

(Na+)i (Cl-)i = (Na+)o (Cl-)o

Soil solution-plant root relationship
(Na+)i (Cl-)i
------ = -----
(Na+)O (Cl-)0
If it is mono and di valent cation
(Na+)i2 (Ca2+) i
------ ------------=k
(Na+) o2 (Ca2+)o
Donnan assumes k=1
(Na+) i2 (Ca2+) i
------ ------------=1 or
(Na+)o2 (Ca2+)o

(Na+) i (√ Ca2+) i
------ =---------=k
(Na+) o (√ Ca2+) o
 Factors affecting cation exchange

 Rate of reaction
 Temperature
 Ratio of soil to solution
 Effect of concentration
 Relative replacing power of cation
 Kind of exchange substance
 Ion size
 Hydration of ion
 Colloidal constant
 Effect of organic matter
 Effect of clay minerals
 Effect of surface charge density
 Factors affecting cation exchange equilibria in soils

affected by two types of factors (i) soil factors and ii) solution factors

I. Soil factors

 Effect of clay minerals

 Effect of Organic matter
 Surface charge density

II. Solution factors

 Effect of total electrolyte concentration

 Effect of type of cations
 Effect of type of anions
Schofield ratio law:
Ratio of the products of adsorbed cations and
cations free in solution are constant.

Based on mass action and gapon equation

[Na+] (Ca2+)2
[Ca2+]2(Na+) =K

Ratio used to predict soil solution concentration

as affected by fertilisers and lime application
Base saturation

Percent base saturation (BS) is the percentage of the

total CEC occupied by the basic cations (Ca 2+, Mg
2+,Na+ and K+).

Acid cations - H+ and Al3+. At an approximate soil pH

5.4 or less, Al3+ is present in a significantly high
concentration that hinders growth of most plant
species, and lower the soil pH, the greater the amount
of toxic Al3+.

%BS = [(Ca2+ + Mg2+ + K+ + Na+)/CEC] × 100

Soils with a high percent base saturation are
generally more fertile because:

 They have little or no acid cation Al3+ that is toxic to

plant growth.

 Soils with high percent base saturation have a higher

pH; therefore, they are more buffered against acid
cations from plant roots and soil processes that
acidify the soil (nitrification, acid rain, etc.).

 They contain greater amounts of the essential plant

nutrient cations K+, Ca2+ and Mg2+ for use by plants.
 Depending on soil pH, the soil’s base saturation may be a
fraction of CEC or approximately equal to CEC.

 In general, if the soil pH is below 7, the base saturation is less

than CEC. At pH 7 or higher, soil clay mineral and organic
matter surfaces are occupied by basic cations, and thus,
base saturation is equal to CEC.

 Total base saturation gives a perspective on the soil's acidity or

alkalinity , and the need for liming.

Individual Base Saturation Levels

Individual base saturations can also be used to gauge the balance of cations
within the soil.
 SOIL pH % BASE
SATURATION
3.9 0
4.5 0
5.3 25
6.2 50
7.1 75
7.5 90
8.0 100
A favourable base saturation will be obtained if the soil pH is maintained
between 5.8 and 6.5.
 For a soil where the pH should be in the range 5.8 – 6.5, the
following base saturation levels can be regarded as being 'ideal'.

Potassium 2% - 5%
Calcium 50% - 75%
Magnesium 5% - 15%
Sodium 1% - 2%
For different crops, on varying soil types, these 'ideal' levels may
differ. (For example, 30% – 50% Ca for a peat soil is more
appropriate than the range 50% – 75%).

CEC and base saturation data is particularly useful in highlighting

differences in soil fertility between samples from the same farm;
and in determining lime requirements.