1

Ion exchange
Ion exchange reaction in soil:
According to Lambert Wiklander, ‘ion exchange is the
reversible process by which cation and anion are exchanged between solid
and liquid phases and between solid phases if in close contact with each
other’.0
Ion exchange in soils occurs on surfaces of clay minerals,
inorganic compounds, organic matter, and roots. The specific ion associates
with these surfaces depend on the kinds of minerals present and the solution
composition. In this ion exchange process a cation or anion in the solid
phase is exchanged with another cation or anion in the liquid phase. For
example,
K +NH4+ NH4+ + K+
Colloid solution colloid solution
If two solid phases are in contact, exchange of ions may
also take place between their surfaces. Ion exchange reactions in soils are
very important to plant nutrient availability. Therefore, it is essential that we
can understand the nature of the solid constituents and the origin of their
surface charge.
Based on counter ion, the ion exchange phenomenon can
further be divided into
i. Cation exchange; and
ii. Anion exchange.
Processes of ion exchange:
Ion exchange may takes place in the following ways:
i. Ion exchange between solid and liquid phase.
ii. Ion exchange between solid and solid phase
iii. Ion exchange between solid phase and root surface.
The processes are described below:
i. Ion exchange between solid and liquid phase:
Ions are strongly adsorbed on the colloidal surfaces.
Hence, the colloidal refers to solid particles. When the colloidal surfaces
come in contact with solution, ion from solution replace or exchange the
equivalent amount of ion from colloidal surface. This ion exchange
process/reaction obeys the law of chemical reaction, i.e. the law of mass
action.
K + NH4+ NH4+ + K+
Colloid Solution Colloid Solution
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ii. Ion exchange between solid and solid phase:

Ion exchange may take place by direct contact and
intermingling of double layers. This can be explained by ‘contact exchange
theory’. Kinetic theory of molecules or atoms proposes that each ion
adsorbed on the clay particle, due to kinetic energy, occupy a volume named
as oscillation volume. When two clay particles are very close come together,
then oscillation volume of two ions, adsorbed on either clay, overlaps and
exchange of ions takes place without involving of soil solution.

Clay-1
Clay-1

K
Na

Na
K

Clay-2

Clay-2

Fig: Contact exchange of ions by intermingling of double layers.

iii. Ion exchange between solid phase and root surface:

There are several acid-like compounds such as amino
acids, carboxylic acid, etc. in roots. These acids on dissociation produce H+
ions. So, root contains H+ ions. When roots come in close contact with solid
phase (clay particles), ion exchange takes place between two phases
according to contact exchange theory.
The oscillation volumes of H+ ion on root surface and
Na+, K+ or any other ion adsorbed on solid phase overlaps each other and
ion exchange takes place.
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Root surface-H+ + Colloid Na colloid H + Root surface – Na

*Ion exchange reaction is a physico-chemical process:

A simple example of ion exchange reaction is as follows-
H+
Ca²+ Micelle + 2H+ H+ Micelle +Ca²+

Here, Ca²+ is replaced by two H+ ions. By this reaction,

we can prove that,
i. Ion exchange is a physical process.
ii. Ion exchange is purely a chemical process.
I. Physical process:
The clay particles acquire charges because of
isomorphous substitution & pH variation. Cations are adsorbed on colloids
or clay surfaces to satisfy negative sites. Adsorption is the concentration of
substances on a surface without chemical reaction. It is a physical process.
The cations are held on the colloidal or clay surfaces by
van der Waals attraction force or weak electrostatic force. The rate of ion
exchange increases as the surface area increases. So, ion exchange is a
surface phenomenon and no new compounds are formed during ion
exchange, one ion adsorbed & another desorbed.
ii. Chemical process:
a. From the above reaction it is apparent that ion
exchange occurs in equivalent proportion, that is, ion
exchange reaction maintains a stoichemistry.
b. The ion exchange reaction obeys the rule of pure
chemical law, i.e. the law of mass action which refers
that the rate of a reversible chemical reaction is
proportional to the concentration of the reactants.
c. As a chemical reaction, the rate & direction of the ion
exchange reaction can be manipulated by changing
conditions.
d. Probably, the most important point in the above
respect is the development of charges on colloidal or
clay surfaces. Charges are developed due to
isomorphous substitution & pH variation.
From the above discussion, it is clear that ion exchange
holds the characteristics of both physical and chemical process. So, it is
conveniently said that ion exchange is a physico-chemical process.
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• Factors regulating adsorption:

There are three factors that regulate the adsorption of ion.
There are-
1. Surface potential
2. Valency, and
3. Hydrodynamic radius of the ion.

The more the charges on the colloidal surface cations will

be more attracted. That is, the higher the surface potential of a colloid,
higher valency cations will be more attracted to the surface.
A cation with a higher valency is attracted more to the
colloidal surface. Divalent cations are more attracted to the colloidal surface
than monovalent cations & trivalent > divalent.
An ion having small hydrodynamic radius is more
attracted to the colloidal surface (Due to charge density). Thus, having same
valency, an ion can be more attracted than another due to variation in
hydrodynamic radius.
The relative adsorption of ion occurs according to the
following series:
For monovalent cations: Cs>Rb>K>Na>Li.
For divalent cations: Th>La>Ba>Sr>Ca>Mg.
Here, Ca gets over the Mg due to its, smaller hydrodynamic
radius. Similarly,
K+>Na+; Mg++>K+, Ca++>Mg++>K+>Na+.
But, there is an apparent exception; the replacing capacity of
H+ is very high (higher than the other ions). Then the series could be,
H+>Ca++>…………………………………………
# Monovalent ‘hydrogen’ in this case behaves more like
trivalent lanthanum.
*Why does a soil contain more Ca++ than other cations & K+ than Na+?
Since clay colloids carry negative charges, cations are
attracted to the clay particles. The adsorption reaction depends on the
surface potential, valency & hydrodynamic radius of ion occurs among the
cations. The relative adsorption of ions occurs according to the following
series. (Lyotropic series):
H>Ca>Mg>K>Na.
The most important factor for the adsorption of an ion is
its valency. Divalent ions is general are retained more strongly than are
monovalent ions and trivalent ions are retained even more strongly.
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Moreover, an ion having small HDR is more attracted to the colloidal

surface.
---- So, Ca gets preference over Mg due to its smaller HDR. That’s
why; a soil contains more Ca++ than Mg++, as well as than other basic
cations.
---- As ions with smaller HDR are preferably adsorbed, soil colloid
reaction more K+ than Na+, because of K+ having smaller HDR than Na+.
*Explain the reason for using NH4OAl(CH3COONH4) solution at pH 7.0 in
the determination of CEC of soils.
Below pH 6.0, the charge for clay mineral is relatively constant.
This charge is considered permanent due to ionic substitution in the crystal
unit. But, above pH 6.0(at neutral pH), the charges on the mineral colloid
increases slightly because of ionization of hydrogen form exposed hydroxyl
groups at crystal edges. These charges are considered as pH dependent
charge.
Agricultural soil pH ranges between 5.0- 8.5 which are
favorable for the dissociation of functional groups and hence, negative
charges develop and the CEC reaches its maximum level. The pH 7.0 favors
the development of maximum negative charge, as well as the maximum
CEC.
This is the reason for using NH4OAl solution at pH 7.0 in the
determination of CEC of soils.
*Why the NH4+ ion is normally used for displacing other cations in the
determination of CEC?
To determine CEC, the ammonium ion is normally used for
displacing other cations from exchange sites for several reasons:
1. It is the most preferred of the cations in the lyotrophic
series; such selectivity is coupled with extremely
weak hydration, on per with that of the K+ ion
enables the NH4 ion to move rapidly to a well-defined
number of cation exchange sites.
2. Because it has to be used in concentrated solution for
efficient and rapid displacement of basic cations,
behind solubility, cheapness of all NH4+-salts is
relevant. (As concentrated NH4 is used for rapid
displacement, solubility & cheapness of NH4 salts are
relevant). (Generally 1M NH4OHAl is used because it
is more concentrated than the concentration of cations
in soil.)
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3. A portion of the negative charges in the minerals and

organic parts are pH dependent. NH4OAl, salt of weak
acid and weak base, is usually used for this purpose,
its pH being adjusted to the value most suited to the
investigation.
4. In the final stage of determination of other cations,
NH4+ salts interface least in flame and other
photometric methods; they are also relatively volatile
and can easily be removed from soil extracts if
necessary.
• Describe the experimental findings of Thompson and
way about ion exchange phenomenon in soil.
Perhaps the most important chemical property of soils
is their ability to retain and exchange ions on colloidal surfaces. The first
studies of ion exchange reactions were conducted by Thompson and way in
the early 1850s. ‘Soil has the capacity to hold ions’- this was established by
Thompson and way. The experimental findings of Thompson & way about
IER phenomenon in soil are
1. Soil, when leached with a solution of ammonium
sulfate [(NH4)2SO4] on a filter paper, release
predominantly calcium (Ca) and other cations like
magnesium (Mg) and potassium (k) in small amounts,
but retain ammonium (NH4+).
2. The total amount of calcium (Ca) and other cations so
released is equivalent to that of ammonium (NH4+)
retained.
NH4+
Clay Ca + 2NH4+ Clay + Ca²+
NH4+
3. The sulfate concentration remains unchanged.
4. The higher the concentration of (NH4)2SO4, the
greater is the release of Ca & other cations.
5. No appreciable effect of temperature is noticeable.
6. The ammonium taken up by the soil is released by
treatment with hydrogen, calcium, sodium or other
cations.
H4N NH4 Na Na
collid colloid + 4NH4 (in solution).
H4N NH4 Na Na
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7. On heating strongly, the soil losses its exchanging

power.
• Properties of cation exchange reaction (qualitative
aspects).
1. Reversibility:
Cation exchange reactions are reversible, or nearly so.
Although cations are preferred to various degrees by soil colloids, even
strongly adsorbed cations can normally be replaced through proper
manipulation of solubility conditions. In fact cation exchange reactions in
soil are not the same like pure chemical exchange.
An exception to this generalization is the preferential
retention of many polyvalent cations (especially the trace metals) by soil
organic matter. Such cations, which are thought to be partially covalently
bonded which are covalently bonded to organic matter, can be displaced
only by other polyvalent cations capable of forming even stronger covalent
bonds and their cation exchange reactions will be reversible. Otherwise,
these will be slightly irreversible.
Other exceptions include cation fixation reactions; cases
where large organic cations, such as the pesticides paraquat and diquat, are
physically prevented (sterically hindered) from approaching certain
interlayer exchange sites and cases where multivalent cations are
preferentially adsorbed, because they can simultaneously balance several
closely adjacent exchange sites.
Na
Micelle Ca + 2Na+ Micelle + Ca²+ (in soil)
Na
2. Stoichiometry:
Cation exchange reactions are approximately
stoichiometric, since the amounts exchanged are chemically equivalent. For
this reason, the sum of all exchangeable cations present at a specified pH,
the cation exchange capacity (CEC), varies only slightly with cation species.
As an example, the following exchange reaction can be
considered-
CaX + 2NH4+ (NH4)2X +Ca²+
Where, X designates an exchanger surface. Two
ammonium ions are required to replace a single ammonium ion, in order to
preserve thee Stoichiometry of the reaction. [Exchangeable cation
composition and CEC values normally are expressed as me/100 g or me/g.]
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3. Speed:
Exchange reactions are rapid. The exchange step itself is
virtually instantaneous, if the ions are in close contact. The rate-limiting step
often is ion diffusion to or from the colloid surface. This is particularly true
under field conditions, where ions may have to move through tortuous pores
or through relatively thick, stagnant water films on soil colloid surfaces to
reach an exchange site. [The need for diffusion can produce hysteresis
(reaction-direction dependence) for some ion exchange reactions.]
Under laboratory conditions, samples normally are shaken
during exchange reactions, to speed ion movement and to minimize the
thickness of stagnant water layers on soil particle surfaces.
4. Mass action:
Because of their reversibility, cation exchange reactions can be
driven in either the forward or inverse direction by manipulating the relative
concentrations of reactants and products. [In the laboratory, common
techniques for driving the reactions toward competition include use of high
(e.g.1N) concentrations of exchange cations, and maintaining low
concentration of product cations by leaching or repeated washings.
For example,

CaX + 2Na+ (high concentration) (Na)2X +Ca²+ (low concentration).

This reaction can be manipulated by forming insoluble

precipitates,
CaX+ Na2CO3 (Na)2X + CaCO3(precipitate)
Or, forming volatile gases,
NH4X+ NaOH Nax+NH4OH NaX +H2O+NH3(gas)
[New compound production is an agreement in chemical reaction, but
in ion exchange reaction no new one is produced, just ion rearrangement
occurs. For this reason it is not a chemical reaction. But, there energy loss
occurs in ion exchange reaction, which is a characteristic of chemical
reaction. That’s why law of mass action can be applied to exchange
reaction.]
5. Complementary cations:
Exchanging one cation for another in the presence of a third
(complementary) cation becomes easier as the reaction strength of the third
cation increases.
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For example, replacing calcium by ammonium is easier from

a Ca²+-Al³+ soil than from a Ca²+-Na+ soil. The ammonium can replace
considerably less aluminum (al) than it can sodium. Thus, more ammonium
remains in solution to replace calcium from the Ca²+-Al³+ soil than in Ca++-
NA+ soil, where more ammonium is utilized to replace Na+. So, rate of ion
exchange reaction can vary with the presence of complementary cation.
N.B. [Ca-Al & Ca-Na are two systems, replace Ca from Na by NH4+. It’s
found that, to replace Ca from Na is difficult than that from Al. Here, Al is a
third cation; Ca is in the same amount in the both cases. NH4 is also same, so
there is a third one for which the rate of reaction is not same for both of the
system, i.e. the amounts of Ca++ released are not same, because most of the
NH4 needed to replace Na+. A part of NH4 will replace Na, then its strength
will fall short and then it cannot replace the divalent Ca++. But, in the other
case, NH4 would not replace Al³+. In that case, more NH4 will remain in soil
to replace Ca++ from Ca-OH system. Here, the influence of third cation is
applicable.]
Anion effects:
The anion accumulated with a replacing cation can affect cation
exchange by having the exchange reaction further toward competition,
changing the direction of exchange reaction, if the end products are-
i. more weakly dissociated
ii. less soluble, or
iii. more volatile
An example of (i) is a reaction that forms weakly dissociated
H2O.
HX + Na+ + OHˉ NaX + H2O
This reaction proceeds more completely than the 1st if strongly
dissociated HCl had been formed instead
HX + Na+ + Clˉ NaX + H +Clˉ
The hydrogen on the right of this equation drives the reaction
back toward the left.
Here, in the first reaction, H2O is weakly dissociated, but HCl,
in the second reaction, is highly dissociated. So for the first reaction, the
possibility to backward is less, whereas in case of the second reaction the
possibility of backward reaction is high due to highly dissociation of the end
product HCl.
An example of (ii) is the formation insoluble Al (OH)3.
Al-X + 3Na+ + 3OHˉ 3Na-X + Al (OH)3(insoluble or slight soluble).
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This reaction proceeds more completely than one leading to the

formation of soluble Al (Cl)3.
Al-X + 3Na+ + 3Clˉ 3Na-X + AlCl3 (Al³+ + 3Clˉ)
st
[ Here, the end product of 1 reaction is insoluble or sparingly
soluble. That’s why the chance of reverse reaction is less. On the other hand,
AlCl3 is highly soluble. Therefore, for the dissociation of AlCl3, the second
reaction has more chance of reserve reaction.]
The high concentration of aluminum in solution drives the
reaction back toward the left.
An example of (iii) is the formation of volatile CO2
H-X-H + CaCO3 Ca-X +H2CO3 Ca-X+H2O+CO2
This reaction proceeds more completely than one leading to the
formation of nonvolatile H2SO4.
H-X-H + CaSO4 Ca-X + H2SO4
The lose of gaseous CO2 from the 1st reaction removes a
reaction product and drives the reaction toward the right.
Anions, such as SO4²ˉ, CO3²ˉ and HCO3ˉ can also lower cation
adsorption in an exchange reaction by forming complex ions or ion pairs
such as CaSO4, MgCO3 or CaHCO3+. They thereby lower the activities of
effective concentrations of the respective free cations.
Colloidal-specific effects:
Soil colloids of high charge density that is high charge or CEC
per unit of surface area, i.e. high surface potential, generally have the
greatest preference for highly exchanged cations.
For example, vermiculite normally retains more calcium than
does montmorillonite from a mixed Na+ - Ca²+ solution. Hence,
montmorillonite has higher exchangeable sodium percentage (ESP) then
vermiculite when the bulk solution Na+ and Ca²+ concentrations are the
same.
The monovalent cations NH4+ and K+ are exceptions to this
generalization because of their unusually strong preference by mica and
vermiculite.
Partially covalent bonding and/or complex formation may
contribute to a similar preference of soils high in organic matter for many
polyvalent cations.
[In organic matter present, it binds polyvalent cations through
covalent bonding and then to replace these. Other strong polyvalents are
required. In case of organic colloids, metal-organo-complexes (covalent
bonds) are formed. Thus, the reversibility of ion exchange reaction becomes
less.
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Raising soil pH can also change cation selectivity by increasing

CEC and thus increasing the preference for polyvalent versus monovalent
ions.
Valence Dilution:
For exchange between cations of unequal valence, dilution of
the equilibrium solution favors retention of the more highly charged cation.
The dependence of cation exchange on cation valence is called the valence
dilution effect. Cation with greater valency has high releasing capacity.
This can be shown by the experimental data of the following
table. Here, the percentage of calcium replaced by barium remained virtually
constant, but that replaced by ammonium decreased with decreasing
ammonium concentrations in accordance with the valence dilution effect.
Solution added Percent Ca++ replaced by
ml N Ba²+ NH4+
25 0.04 49.7 29.8
100 .01 50.2 20.8
200 .005 50.8 16.6
400 0.0025 52.7 15.2

[More the NH4+ is diluted its replacing capacity will be

decreasing. But in case of Ba++ inspite of the dilution replacing capacity
will be same.]
• Ion exchange reaction in the light of the law of mass action:
Ion exchange reaction is a reversible process by which cations &
anions are exchanged between solid and liquid phases & between solid
phases if in close contact with each other.
The law of mass action is- “the rate of chemical reaction at a
given temperature is proportional to the active mass of each of the reactants
present in the system.
The Ion exchange reaction can be described in the light of the law
of mass action. For this, the following ion exchange reaction between
monovalent ion attached to a colloid & another monovalent ion in soil
solution, can be considered:
X-Na + K+ X-K + Na+.
According to the law, the rate of forward reaction of any instant is
proportional to the concentration of the reactants.
So, Rate of forward reaction, V1 α [X-Na] [K+]
Or, V1 = K1 [X-Na] [K+]
Where, K1= velocity co-efficient (constant).
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Again, the rate of backward reverse reaction,

V2α [X-K][Na+]

V2 = K2[X-K] [Na+]
Where, K2= velocity co-efficient (another constant).
At equilibrium, the rate of forward reaction is equal to the rate of reverse
reaction, so,
V1=V2
K1 [X-Na][K+] =K2[X-K] [Na+]

[X-K] [Na+] = K1 = K
[X-Na] [K+] K2
Here, K is the equilibrium constant, for the above
reaction at a given temperature, which is equal to the ratio of the velocity
constant for the forward reaction & backward reaction.
• Why the CEC of agricultural soils are greater than AEC?
The CEC of a soil is the capacity of clays to adsorb and
exchange cations. The AEC is the capacity of clay to adsorb & exchange
anions.
Cation exchange capacity of a soil is generally more than
anion exchange capacity. It is dependent on the charges in electrolyte levels
& on soil pH. It is also limited to special types of clays.
The clay must be positively charged to be able to adsorb
negatively charged ions (anions). But, positive charges on clays occur clay
in acid conditions; (i.e. under moderate to extreme acid soil conditions, some
silicate clays & iron and aluminum hydrous oxides may exhibit positive net
charges; > Al-OH + H+ > Al-OH2+)
But, in agricultural soils, pH ranges between 5.0-8.5.
There is no constituent at this pH range which can develop positive charge.
Only minute quantities of charges develop in certain amino acids. At this pH
range, negative charges are dominant in soil colloidal surfaces, which are
originated from isomorphous unequivalent ionic substitution and pH related
hydroxy groups on the edges & surfaces of the inorganic & organic colloids.
Since, normally extreme acid conditions does not prevail
in soil, CEC of a soil is generally more than AEC.
• Why does CEC vary from soil to soil?
Cation exchange capacity is the sum total of the exchangeable
cations that a soil (or other substance) can adsorb.
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The CEC vary from soil to soil because of the several

reasons which are as follows:
1. Clay content:
Soils that contain high amount of clay minerals have more CEC
than soils that contain less clay mineral.

2. Type of clay:
CEC of soils also vary with the type of clay they contain. A soil
dominated by 1:1- type silicate clay & Fe-Al-oxides with have lower CEC
than the soil that contain 2:1- type clays, because expanding type minerals
show higher CEC than non-expanding type clay.
3. Organic matter content:
The higher is the organic matter content in soil, the higher is the
CEC of that soil. CEC also depends on the stage of decomposition of
organic matter. A soil containing completely decomposed organic matter, has
higher CEC than a soil containing partially decomposed or undecomposed
organic matter.
4. Soil pH:
At high pH values, negative charges develop and hence the
CEC increases. On the other hand, at low pH values, positive charges
develop & the CEC is lower.
5. Temperature:
The temperature has been found to increase slightly the rate of
the rapid ion exchange for the slower exchange. For this reason, in a
temperate zone, the soil has high CEC because temperature governs the
amount of CEC.
6. Soil Texture:
In general, the more the clay in a soil, the more is the CEC of
that soil. Finer texture soils tend to have higher CEC than sandy or coarser
textured soils.
• Factors controlling the CEC of soils:
The factors that influence/ control the CEC of soil are as
follows:
1. Clay minerals ( amount & type of clay)
2. Soil organic matter (nature & amount of organic matter)
3. Soil pH
4. Size of particles
5. Temperature
6. Soil Texture
Clay minerals:
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CEC of the soil varies with the amount & type of clay minerals
present in soil.

Amount of clay:
Soils that contain high amount of clay minerals have more CEC
than soils that contain less clay minerals. For example a soil that has 20%
kaolinite has higher CEC than a soil having 10% kaolinite.
Type of clay:
CEC of soils also vary with the type of clay it contains. A clay
soil dominated by 1:1 type silicate clays & Fe-Al-oxides will have lower
CEC than the soil containing 2:1 type clays, because expanding type
minerals show higher CEC than non expanding type clay. For example, a
soil containing 20% montmorillonite has more CEC (80-150 meq/100 g soil)
than the soil that contains 20% kaolinite (CEC 3-15 meq/100 g soil), though
the amount of clay minerals in the two soils are same.
Soil organic matter:
CEC depends on the amount & nature of organic matter in soil
& on the presence of functional groups in the organic matter.
Amount of organic matter:
CEC depends on the amount of organic matter present in soil.
The higher the organic matter content in soil, the higher is the CEC. For
example, soil containing 5% organic matter has higher CEC than a soil
containing 2% organic matter. There was a fairly definite increase in the
exchange capacity of sandy Florida soils of 2 meq for each 1% increase in
organic matter.
Nature of organic matter:
CEC also depends on the stage of decomposition of organic
matter. A soil containing completely decomposed organic matter has higher
CEC than a soil containing partially decomposed or undecomposed organic
matter.
The product of completely decomposed organic matter is
humus & its CEC is higher (150-300 meq/100 g soil). The CEC of partially
decomposed organic matter is near zero. As a result, CEC of a soil varies
with the different stage of decomposition.
Presence of functional groups on humus:
The reason for the higher CEC of humus is the functional
groups on humus particles. These functional groups are –OH, -NH2, -COOH,
etc. when the pH of soil solution increases, these functional groups
dissociate & form negative charges.
 15

OH + OHˉ Oˉ + H2O

NH2 +OHˉ NHˉ +H2O

Soil pH:
pH also influences the CEC of soils, at very low pH values, the
CEC is generally low. Under low pH conditions, only the permanent charges
of the 2:1 type clay & a small portion of the pH-dependent charges of
organic colloids, allophane, and some 1:1 clays hold exchangeable ions.
At high pH, the negative charges on some 1:1 type silicate
clays, humus, allophane and even Fe, Al oxides increases; thereby increasing
the CEC.
At natural or slightly alkaline pH, the CEC reflects most of the
pH-dependent charges as well as permanent charge.
To obtain a measure of the maximum retentive capacity, the
CEC is usually determined at a pH of 7.0 or above.
Size of particles:
The finer the size of the particles the higher is the specific
surface area, and so the higher is the CEC of the soil, and vice-versa. CEC is
a surface phenomenon. As a result, CEC increases with the increase in
surface area. Clay is a colloidal particle, so its CEC is higher than coarser
soil particle.
Soil texture:
The more clay in a soil, the more CEC is in that soil. Fine-
textured soils tend to have higher CEC than sandy or coarser textured soils.
Different CEC of different textured soils:
Sandy soil 0-5 meq/100g soil
Fine sandy loam 5-10 meq/100g soil
Clay loam 15-20 meq/100g soil
Clay 30 meq/100g soil
 16

It can be assumed that kaolinite has a cationic exchange

capacity of approximately 8 milliequivalents; illite, 30 meqs;
montmorillonite, 100 meqs, and humus (colloidal organic matter), 200 meqs
per 100 grams of material, on an oven-dry basis.
Temperature:
The temperature has been found to increase slightly the rate of
the rapid ion exchange for the slower exchange. So, ion exchange reaction is
accelerated as temperature is increased.
• Importance of cation exchange reaction:
The properties of ion exchange & the exchange reactions are
great fundamental & practical importance in soil science & other fields
where clay minerals are studied & used. ion exchange reactions are the most
important phenomena in the whole domain of agriculture. In fact, several
workers have shown that the capacity of soil to exchange ion is the best
single index of soil fertility.
The important roles of ion exchange reaction on soil fertility are
as follows:
1. Water holding capacity:
Soils with high CEC hold more water & better crop growth.
On the contrary, soils with low CEC hold small amount of water which is
inadequate for better growth of crops.
2. Nutrient availability:
Plant nutrient elements are held on soil colloids as
exchangeable ions and thus leaching loss of the nutrients is prevented. The
mineral ions Ca++, Mg++, K+, Na+, H2PO4ˉ etc are released to the soil
solution or adsorbed on the colloidal fraction through the process of ion
exchange. Their adsorption by plants and microorganisms are also occurred
through ion exchange reaction.
3. Physical property of soil:
Soil physical properties can be improved by ion exchange
reaction. A soil with low CEC will always have poor structure because it will
not hold Ca++ & Mg++ as exchangeable cations. A Ca-saturated soil is
granular in structure & porous. Ca-dominated clay ensures good aeration &
good drainage.
4. Soil Reaction:
CEC influences the soil reaction. Soil reaction means the
degree of acidity & alkalinity of a soil usually expressed in pH value. Soils
with Ca & Mg have high CEC which increases the soil pH. On the other
hand, hydrogen and aluminum containing soils have low pH (4-5). It is well
 17

known that pH affects the availability of several nutrients. So ion exchange

indirectly influences the availability of plant nutrients.

5. Microbial activity:
The predominance of desirable cations such as Ca++ in the
exchange complex favorably influences the microbial activity,
ammonification & nitrification.
6. Irrigation:
CEC of a soil helps to measure irrigation water efficiency
of a field. If the CEC of a soil is low, irrigation is needed for several
times with small amount of water, because water holding capacity of
this soil is low & vice-versa.
7. Efficient use of fertilizer:
A soil which has low CEC will hold small amount of
fertilizer nutrients than a soil with high CEC, because nutrient ions of
the fertilizer are adsorbed by soil colloid by the process of ion
exchange. So, the soluble inorganic fertilizers are not washed away
from the soil when added to the soil. Thus, the CEC of soil increases
the efficient use of fertilizer.
8. Reclaimation of acid soil:
Strongly acidic soils are not produce for most crops.
When lime is added to neutralize the acidic soils, most of
exchangeable H+ & Al³+ ions are neutralized after the pH.
H
Micelle + Ca (HCO3) Micelle Ca+ 2CO2 +2H2O
H

This is an ion exchange reaction. So, ion exchange can

bring a soil in favorable condition.
9. Reclaimation of Alkali soil:
Due to alkaline nature or high pH (>8.5), Na+ ions are
adsorbed by soil colloids. If H2SO4 or gypsum (CaSO4 .2H2O) is added, Na+
ions are released into solution which are subjected to drainage.

Micelle
Na Micelle
H
+ H2SO4 + Na2SO4
Na H

The acidification of soil is accomplished by ion exchange

reaction.
 18

• Importance of cation exchange phenomenon in agriculture:

Cation exchange is an important reaction in soil fertility in
causing & correcting soil acidity and alkalinity, in changes of soil physical
properties. Cation exchange is very important in soils because of the
following relationships:
1. The exchangeable k is a major source of plant K.
2. The exchangeable Mg is often a major source of plant Mg.
3. The amount of lime required to raise the pH of an acidic soil
is greater as the CEC is greater.
4. Cation exchange sites hold Ca++, Mg++, K+, Na+ and NH4
ions and show their losses by leaching.
5. Cation exchange sites hold fertilizer K+ and NH4+ and
thereby reducing their mobility in soils.
6. Cation exchange sites adsorb many metals, such as Cd++,
Zn++, Ni²+, Pb²+, etc, that might be present in waste waters.
Adsorption removes them from the percolating water,
thereby cleansing the water that drains into groundwater
from surface water.
• Exchangeable sodium percentage (ESP):
The extent to which the adsorption complex of a soil is
occupied by sodium. It is expressed as follows:
ESP= exchangeable sodium (c mol/kg soil) × 100
Cation exchange capacity (c mol/kg soil)
• Base saturation percentage (PBS):
The extent to which the adsorption complex of a soil is
saturated with exchangeable cations other than hydrogen & aluminium. It is
expressed as a percentage of the total cation exchange capacity.
The percentage of the CEC that is satisfied by the base
forming cations is termed as percentage of base saturation.
PBS= exchangeable base forming cations (c mol/kg soil) × 100
CEC (c mol/kg soil)
The proportion in any soil of the CEC satisfied by a given
cation is termed the percentage saturation for that cation. Thus, if 50% of the
CEC were satisfied by Ca++ ions, the exchange complex is said to have a
percentage calcium saturation of 50.
• Sodium adsorption ratio (SAR):
 19

The SAR gives information on the comparative concentrations

of Na+, Ca²+ and Mg²+ in soil solutions. It is calculated as follows:
SAR= [Na+] .
√1/2[Ca²+] + ½[Mg²+]
Where, [Na+], [Ca++] & [Mg++] are the concentration (in c
mol/kg) of the sodium, calcium & magnesium ions in that soil solution.
SAR of a soil extract takes into consideration that adverse effect
of sodium is moderated by the presence of calcium and magnesium ions.
The SAR is also used to characterize the irrigation water added to these
soils. This property is becoming more widely used in characterizing salt-
affected soils.
High SAR means large amount of Na+ and low SAR indicates
larger CA++ & Mg++ content.
Soil SAR
Normal < 13 to 15
Acid < 13 to 15
Saline < 13 to 15
Saline-sodic < 13 to 15
Sodic < 13 to 15
• CEC of montmorillonite >CEC of kaolinite:
The CEC of montmorillonite is greater than that of kaolinite.
The reasons are discussed below:
# 01. In case of montmorillonite, the negative charges arise mainly from the
isomorphous substitution. Isomorphous substitution of Mg²+ for some of the
Al³+ ions in the dioctahedral sheet accounts for most of the negative charges
for montmorillonite although some substitution of Al³+ for Si4+ have
occurred in the tetrahedral sheet. These substitutions account for the high
CEC of this clay mineral.
On the other hand, there is little or no isomorphous substitution
in kaolinite. Owing to the presence of exposed hydroxyl groups, kaolinite
has a variable of pH dependent –ve charge, due to dissociation of H+ ion
from the exposed OHˉ groups. The CEC of Kaolinite is, therefore, very
small & may change with pH.
# 02. Montmorillonite is an expanding mineral with the specific surface or
total surface area (external & internal) per unit mass of 700-800 m²/g, which
accounts for its high capacity to adsorb cations as well as high CEC. The
CEC of montmorillonite is 80-150 meq/100 g soil.
On the other hand, kaolinite is a non-expanding mineral. The
effective surface area of kaolinite is restricted to its outer face or to its
external surface area. The total surface area per unit mass of kaolinite is only
 20

05-20 m²/g. This accounts for its low capacity to adsorb cations as well as
low CEC. The CEC of kaolinite is 03-15 meq/100 g soil.
For the above reasons, the CEC of montmorillonite > that of
kaolinite.
• CEC of montmorillonite> CEC of illite :
The CEC of montmorillonite is greater/higher than that of
illite, because montmorillonite is a 2:1 type expanding clay mineral. The
total surface area per unit mass of montmorillonite is 700-800 m²/g, which
accounts for its high capacity to adsorb cations as well as its CEC.
Again, isomorphous substitution takes place in
montmorillonite; viz. Al³+ for Si4+, Mg²+, Fe++, Ni²+, Li+ for Al³+.
Isomorphous substitution of Mg²+ for some of the Al³+ ions in the
dioctahedral sheet accounts for most of the negative charges for
montmorillonites, although some substitution of Al³+ for Si4+ has occurred
in tetrahedral sheets. Thus isomorphous substitution causes high CEC of this
clay mineral. The CEC of montmorillonite is 80-150 meq/100g soil.
On the other hand, through the illite is a 2:1 type mineral, it
is non-expanding mineral. Therefore, its surface area is as low as only 70-
100 m²/g, which accounts for its low capacity to adsorb cation as well as low
CEC.
Again, isomorphous substitution takes place in illite. The
major source of negative charges of illite is in the tetrahedral sheet where
about 20% of the Si-sites are occupied by Al-atoms. This results in a high
net negative charge in the tetrahedral sheet. But, to satisfy this charge, K+
ions are strongly attracted in the interlayer space. Thus, K+ ions act as
binding agents preventing expansion of the mineral. For this reason, cation
adsorption is much less intense in illite (fine-grained mica) than in
montmorillonite. The CEC of illite is 10-40 meq/100 g soil.
For the above reasons, CEC of montmorillonite> CEC of illite.
Kaolinite Non-expanding mineral
Montmorillonite fully expanding mineral
Vermiculite limited expanding mineral
Illite Non-expanding mineral
[Origin of positive & negative charges on soil clays/ permanent & pH
dependent charges------------ from 2nd year note].
• Origin of negative clays in humus:
Negative charges are originated in humus due to
dissociation of the following groups:
 21

1. Dissociation of carboxyl (-COOH) groups occurring in the

polyuronides, aliphatic acids & in the side chain of lignin (at low pH of 4, 5,
6).
Humus Humus
COOH COOˉ+ H+
2. Dissociation of phenolic hydroxyl groups (OHˉ) in lignin,
amino acids & humus (at high pH)
Humus Humus
OH Oˉ+H+

3. Dissociation of heterocyclic nitrogen/amino group (-NH2)

group present in nucleic acid at independent pH values.

Humus Humus
NH2 NHˉ+H+

Charges due to broken edges:

In clay minerals, both cation & anion charges are equal in
neutral condition. When the clay minerals are broken down physically,
unequal charges (positive or negative) are developed/ produced. If the cation
charges are more than that of anion, the clay minerals (gibbsite, goethite)
show the positive charge & vice-versa.
Anion exchange:
The anion & molecular retention capacity of most
agricultural soils is much smaller than the cation retention capacity.
Numerous anionic and non-ionic species are important to today’s
agriculture, and their reactions in soils can not be ignored.
Common soil anions include Clˉ, HCO3,
CO3²ˉNo3ˉ,SO4²ˉ, HPO4²ˉ, H2PO4ˉ, OHˉ and Fˉ. In addition some
micronutrients exist as anions, such as H2BO3ˉ and MoO4²ˉ, as do some
heavy metals, e.g. CrO4²ˉ and HAsO4²ˉ and also as molecular form such as
some pesticides in undissociated form ( DDT; 2, 4, 5-T and 2, 4-D). In
humus there is NH2ˉ group.
Many anions and all molecular species are related by
more complex mechanisms than the single electrostatic attractions involved
in most cation adsorption reactions. Anion may be retained by soils through
a number of reactions. Some of these are purely electrostatic and are referred
to as nonspecific. A variety of non-electrostatic reactions are also possible.
These are collectively known as specific adsorption, or chemi-sorption
 22

reactions. That is, there are two steps of mechanisms for anion retention in
soils:
1. Nonspecific Anion Reactions; and
2. Specific Anion Reactions.
Nonspecific Anion Reactions:
In this case, adsorption (or retention) is not specific for
any anion. An anion, which is more powerful, takes the place first.
An anion (approaching a charged surface/ soil solid) is
subjected to
i. attraction by positively charged sites on the
surface, or
ii. Repulsion by negative charges.
Anion repulsion (negative adsorption):
Layer silicates in the clay fraction of soils are
normally negatively charged; so, anions tend to repel from the mineral
surfaces.
Factors affecting anion repulsion include:
a. Anion charge & concentration;
b. Species of exchangeable cation;
c. pH;
d. Presence of other anions; and
e. Nature & charge of the colloidal surface.
Ions commonly exhibiting anion repulsion include Clˉ, NO3ˉ and
SO4²ˉ.
Anion repulsion expressed in units of milliequivalents repelled per
square centimeter of solid surface (me/cm²), increases with anion charge
(valence).
If the negative charge on a soil colloidal surface remains constant,
anions of higher charge are repelled more than anions of lower charge. For
example, Mattson found anion repulsion in a Na- montmorillonite
suspension to increase in the order: Cl~ NO3ˉ< SO4²ˉ<Fe (CN)64ˉ.
Similarly, increasing of the anion concentration increases anion
repulsion.
In soils with pH dependent charge, lowering the pH decreases the
net negative charge of the system. Anion repulsion thus decreases as the soil
pH decreases.
Anion repulsion decreases when anions are adsorbed by positively
charged sites on soil colloids.
 23

Permanent of the colloids with highly charged and tightly adsorbed

anions, such as phosphate, can effectively mask such positive charges. These
adsorbed anions present a negative face to anions added subsequently.
Anion repulsion is then greater than in the absence of the tightly
adsorbed anions.
Colloid type, or more correctly, the negative charge on various
solids of the soil matrix, has an obvious effect on anion repulsion.
The greater the negative charge of the soil solids, the greater the
anion repulsion.
Montmorillonite soils thus exhibit greater anion repulsion than do
kaolinite soils at all pH values. This is especially true at low pH values
where kaolinite may develop positive charge.
Importance:
Anion repulsion has important consequences during solute
transport through soils. Since anions are excluded from some of the volume
surrounding soil particles, these ions can travel through a soil faster than the
water in which the salt was originally dissolved.
Electrostatic attraction of anions:
Anions approaching possibility charged sites on layer silicate or
hydrous oxide minerals are attracted electro statically in the same manner as
cations are attracted to negatively charged soil colloids.
Anions whose retention in soils can be described by
electrostatic considerations alone are said to be non- specifically adsorbed.

OHˉ½ OHˉ½ (a)

+ H+ +Clˉ =
OHˉ½ OH+½……………Cl

OHˉ½ OH (b)
+NO3ˉ =
OH+½….Cl OH+½…………..NO3 + Clˉ

Fig: Non-specific anion reactions at a solid/solution interface: a. adsorption

 24

b. anion exchange (after Hingston et al; 1967).

The figure (a) diagrammatically shows the non-specific
adsorption of Clˉ. The dotted line represents electrostatic attraction of a
positively charged mineral surface site for the anion. Here, the positive
charge which retains Clˉon the mineral surface is the result of protonation of
the surface.
The figure (b) represents the exchange of one non-specifically
adsorbed anion (NO3ˉ) for another Clˉ.
The anions Clˉ, NO3ˉ and SO4²ˉare generally considered to be
non-specifically adsorbed. The capacity of soils to adsorb anions increases
with increasing acidity and is much greater in the kaolinite soil, which has
significant pH-dependent charge.
At all pH values, the divalent SO4²ˉion is adsorbed to a greater
extent than the monovalent Clˉion. The attraction of anion to positively
charged colloids depends on the charge strength of the anion:
SiO44ˉ>PO4³ˉ>>SO4²ˉ>NO3ˉ≈Clˉ
Importance:
Chloride, nitrate and sulfate are common and important anions
in moist soils and have been studied extensively. Chloride, in particular, is
often used as an indicator of NO3ˉmobility in soils, since Clˉ is not subject to
the complicating biological reactions characteristic of NO3ˉ. In most other
respects, Clˉbehaves in a manner similar to NO3ˉ.
Specific anion reactions:
A hydrous oxide system is amphoretic, having a negative or
positive charge and therefore, either cation or anion exchange capacities,
depending upon the pH. These solids (oxides) possess the ability to
specifically interact with various anions. This characteristic gives Fe or Al
oxide-dominated soils an adsorption capacity for some anions. Infact, ion
oxides and other oxides can scavenge arsenate, phosphate, molybdate and
similar anions from solutions with high efficiency.

OH2+0.5 +1 Fˉ0.5 0

…Clˉ+NaF + NaCl +H2O

OH2+0.5 OH2+0.5
(a)
PO4Hˉ1.5 ˉ²
OHˉ0.5 ˉ1
….Na+ + NaH2PO4²ˉ ..2Na++ H2O
OHˉ0.5 OHˉ0.5
 25

Figure: Specific anion reactions at a solid/solution surface: (a)

neutralization of positive charge, and (b) ionization of a proton of an
adsorbed acid anion (after Hingston et al, 1968).
Phosphorus is an essential plant nutrient and is probably the
most important example of specifically adsorbed anions. Many soils fix
large quantities of phosphorus by converting readily soluble phosphorus to
forms less available plants. In terms of ligand exchange or anion penetration
theory, phosphorus adsorption on oxide surface can be explained by the
following figure:
Fe Fe OH

O OH O O P O
OH
Fe + 2H2PO4ˉ Fe +2OH
OH
O OH O O P O
OH
Fe Fe

Figure: Representation of H2PO4ˉpenetration into and Fe oxide surface.

The figure illustrates that-
1. Anion exchange:
One anion (H2PO4ˉ) is replacing the other one (OHˉ)
2. Ligand exchange:
A group (OHˉ) is replaced by another one (H2PO4ˉ).
3. Mechanism of phosphate fixation.
4. Source of OHˉion in soil solution.
Molecular retention:
A species need not be initially charged to be retained by
soils. Molecules in the soil solution may be concentrated to charged species
and then adsorbed as cations or anions, or may remain non-ionic and be
adsorbed as a consequence of polarity that produces localized charge within
the molecule.
Certain non-ionic species protonate in acidic solution and
become cations subject to adsorption on negatively charged soil solids.
B+ H+ BH+
BH+ + M soil BH soil + M+
Where, B is a weakly basic molecule, BH+ is a
protonated weakly basic molecule and M+ is a cation.
 26

Bailey and white suggested several possibilities for bonding of

non-ionic polar molecules to the oxygens of layer silicate surfaces. These
include molecular characteristics such as:
1. Chemical character, shape and configuration
2. acidity or basicity
3. water solubility
4. charge distribution
5. polarity
6. size; and
7. polarizability
all influence the adsorption of nonionic compounds by soil

R-N-H………..O

R-C-H…………O

Layer silicate
O

R-C-OH………O

R-C-O………..O