n HOnC Naira #

i coiioidal state rofers to a [W0-phase svstem

: us Fou 0F ci0r5 il
q Dispersion of clay in wawr) and Liqu
p::cles less than 0.6 !
ispherc). he clr racion of the soiB contu!S
olnda! propertics ad etC Ah\n
size. Particles less than 0.00T mm size possess
Clay aeln (oeD2mmm
M coleoids.
soil colloisle
Saller n
Ihe inorganic and organic colloids are extremely sai size -
m2iOiclers in dianeiCr. TheSC Darticies canol be >,)0SMg an rdB! : h

!NOSCone but can he SCCN On ith an clectron MCrUSNODe.

'cUseof their smalisve. al soil collcits havc alarzr external r T

.t!mass. The external surtace area of 1gof'colloid'uy is G)i s
of coarse sand. Certain silieae elays have CNiensie i.emai srlhs t h t : .

the esiernal surtace arca. Ih lotal surface area oi s; coloids rlges

1g for clays with only extenal surlaces to merr th:n 800 n chn
evienNeinternal surfaces. Tie colloid surface area ir. ir: nper !5 em of,ss. tge
f a y soilcouid be as hiy}: an 700,000 kn' g'.

Both exicrnal and internal surtaces of soil colids cN negatie

3:e
chres, Most of he oraNiC . norganic soil co cT

ih wigrate to anode. the posiive ce rode indicatii at t cr uive

 hnilude of the ge
tHd ;uision of
the tr.
chare nluence

tulci iun.Hds cuch oiher. there

i Ionizabie hvdrogen i0ns

isomorphous substitution.
i;s<ovdoHiOns ta clan
These re hvdroen irn
un
Ihe -Al-OH or -Si-OH portion of the clar io/ehe iandi C )
st:rluces.
(-A0 eor - S he CVic Oi i 0 !
ncuraiZed negative charge on thc oXVeen
hcgative charges r pi
h drogen depends on soBution pH and hence thes.
dependeni churges. Morc ionization occurs in alkalihsic) soUONS.
This is duc to the suhv.HORt aON O

ictee with another cation of iower vaicnce but sh, i.r si/e it ihvl crysta!
iUCrc. 0n cla VStals some i0ns it exactt into a! ulic Si: tiiN

her ovenient size and charge. Dominantiy. c.r Si trahcirai sis

in octahcdral sites. Other ions presnl H irg ailois deiig cin
slallization can replace some of the A!
tötiutions ure the Si replaced by A.nd repknt o A by ! .
tr Zn As the total ncgative charge on i rL?} nHN v s
unchanged, the lower positive chrgc ol he subsutl! d cl:)ts Csuli eICNS
igtive charges on clay cry stais.
As sod colloids possess cihwue i i dilaet and
dich e ions of positive chargc on the colloidal surits !h
aat ca$ ie
ii.A.Ca and Mg.This gives rise to an ionie dexhie er
The Isomorphous substitution in the
coilotiliR: i

t c anions, wihich torm the inier laver cf the

i y . ie oUer i , r i

for
hut lorn fesife yalena
ner
lu chay
 (adsorbed)calion: ltracicd io the negatisei
looseh held
}hde u) of a suam of
vhrgd surtaces. with
number of water moecules are ass0Ciated
trtinn oi er A large cations
ddsorbcd
Some water molcculesare atlracted to the
0lcoiloidal particles. th
hvdrated state. Others water molccules are hcld in
and the cation is said to be in molecuBes play a
clay particles. These water
incmal surfaces of the colloidal soil!.
in determining both the phvsical and chenical properties ol
criticalrole (ohesion
(Attractive force between sinmilar molvcules or materials).
( sstacvaon
stick together. This tendency is duc to
indicates the tendency of clay particles to
water molecules held betwcen them. When
the attraction of clay particles for
adheres to individual clay particles and
colloidai substances are wetted, water first
more adjacent colloidal particles.
then brings about cohesion bet1ween two or
moiecules or malriaBs). Adheso)
1 , H. (Atractive force between different
the surtace of anv oher bod, or
refers to the attraction of colloidal materials to
substance wih which it comes in contact.
grvup
! 9d shrinkuge. Some soil clay collods belonging to sncclite
dry
likc Montmorillonite swell when wet and shrink when dry. Afir aprolongd
show crises-Cross
speli. soils high in smectite clav (c.g. Black soil -Vertisois) oflen
wide and deep cracks. These cracks first allow rain to penetrate rapidly. Iuer.
Icause of swelling. the cracks will close and bccome impervious. But soi!s
dominated bv kaolinite, chlorite. or fine grained micas do0 not swell or shrink.
Vermiculite is intermediate in itsswelling and shrinkingcharacteristics.
i9rtyion and floccuBation. As long as the colloidal particles emain
tigalively chargrd, they repel cach other and the suspension remains stabie. If on
ny aecount they koose their charge. or if the nagnilude of the charge is teduvd.
the particles coalesce. form flock or loose aggregales. and seule down. ihis
phenomenon of coalescence and formation of locks is known as tloccuiation. he
 individualpaiiey
into
brcakineup of tlocks
process of the
Unhed
de-locculation or dispersiOD. colloidal partiles s
of
eHen When a suspension duC to the
1ro#a 0scillate. The osCillauo}}
to
the particles seem
under a microscope
with those of the iiquid nv hich ther
or molecules
collision of colloidal particles of walcr in hich lhu
are
collojdal particles with those
are suspendcd. Soil pariciC. the
a constant state of motion. The smaller he
siISpended are always in
more rapidisits movement.
uiable t0 pass
i. permeaiiit Colloids. as opposcd to crvsta!loids. are
colloidal paricls ar
through a semi-pcrmeable membrane. Even though the
n wtcr.
exreMely small. thev are bigger than molecules of crystalloid dissoBvcd
"he membrane allows the passage of water and of the dissolved substance iiough
its pores. butretains the colloidal particles

lhercare four nmaor ivpes of colloids present in soil

1. aver silicate ciays
2. lTon and aluminum oxide clays (sesquioxide clavs)
3. Allophane andassocialed amorphousciays
4. Ilumus

Laver silicate clavs. iron and aluminum Oxide clays.

allophane and ted
amorphous clays are inorganic colloids while humus is an organic coll0id

These innportant silicate clays are also knoIvn as phyilosiicates (P}io:

hecause of their caf-like or plate like structure. These are made up
of lo inds o!
hori/onla! sheets. One dominaed by silicon and oher by
amun or
 for the silica-dominated sheet nd
The basic building block
surrounded by lour oxygnaOms. It s callcd
silicon atom
unit composcdof onc configuration. An interlock ing arras
because of its four-sided
the silica terahedron horizontally b slharcd onen
terahcdra ticd together
0r a series of thcse silica
sheçt.
inionsgives a tetrahedral
are the kev calions
Aluminium and/or magnesium ions

six Oxygen atoms or hydroxvl group giving an eight sided huitdin!

srounded by
octahedron. Numcrous octahedra linkcd together hori/ontaliy
block Lermed
comprise the octahedral shect.
known as a di-octahedral shect, whereas
An alunminum-dominated sheet is
distinction is duc
dominated by magncsium is called a tri-octahcdral sheet. The
one
in a di-0clahedral sheel satisf the suhle
to the fact that [vo aluminum ions
hydroxyls as thre magnesium ions
ncgative charge from surrounding oxygen and
in atri-0ctahedral sheet.
fundamental siructura! nits o
The tetrahedral and octahedral sheets are the
crystals bv sharcd oxvgen
silicate clavs. ThCse shects arc bound together within the
combination of sheets n these
atoms into different lavers, The specific nature and
the phvsiçal and chemical
layers vary from onc type of clav to another and control
properties of cach clav.
i#ir claVs (sesqukkitie ca Under COnities of
ion md ai
of minerats in
extensive leaching bv rainfall and long time intensive wcathecring
prnmary mineraBs are
humid warm climates, most of the silica and alumina in
have tover
dissolved and slows leached awav. The remnant materials. which
niNures of
solubility are called sesquioxides. Sesquioxides (metal oxides) are
aluminumhvdroxide. Al (OD, and iron oxide, Fe,(0,, or iron hvdrovile. FeO!):
The Lain word sesqui means one and one-half timcs. NCanine one nd one-hal!
times more oxygen than Al and Fe. These clavs can grade irom amorphous to
 ODNO) nsoils
alu)inUDOXIdes
of ironnd known about these clavs an
(es0H,0). Less is
geothite and have high
(ALO.3LO) and
not swell. not sickv
layer silicates. These clavs do
about the
phosphorus adsorption capacity. miNUrs
These silicale clays are
EvCn mixture of othr
are amorphous in naure.
of silica and alumina. They
of the mixtuic. Iypically. hcse ckars
be a part
iNeathered oxides (iron oxid) ay are conWon
veathcred products existcd. Thesc clavs
OCCur where large amount of
from volcanic ash (c.Q.. Allophane). Thcsc clavs have high anio!
In soils forming
capacity. Almost all of their
CXChangc capacity or even high cation exchange
charge is from accessible hvdroxvi ions (0!H), which can attract a p0sitIVe ion or
lose the Hattached. These clavs have a variabie charge that depends on |
solution (the soi! aciditv ).

Humus is amorphous, dark brown lo black. ncrtv insoluble in waci. bu

)osth soluble in dilute alkal' (NaOH or KoD soluions. It is a
tuporar
intermediate product left after considerable decomposiiion of pl:unt_ani nul
remains. They are temporary ntermediate hecause the
organic substances remain
continue to deconpose slowly. The humus is ollen refecrcdto as
an organic collod
and consists of various chans and
Boops of lnked carbon atoms. The
Collojds are not crystalline. They are unus
Composed hasicalB of cartbon. hvdroy nd
0XYgen rather than of silicOn, aluminum. iron.
Oxygen, and hvdroxyi grouns
The organic colloidal
particles vary n SZe. but they may be at least
as the silicate clav as smal!
particles. The negative Charges o} humus are
ialy dissociated enolic (-0}). carhoxyI(-(0OH). and associated u ih
groups nturn are associated with central units of phenolic groupx thee
varying size and
complexiiv.
 Made up ofCUO Made u of SiAi)
CompleN amorphoUs organic Inorganic nd eryslallm
colod
More dynamic.formd and Clarsae stabk reluiiei
destroved more rapidly
Chns have deinite nd nei
Complex stncurc no c} known sruCure
known

are ofien transported via coloidal

Th organic and inorganic contaminats
particles.
resides in the less
Majoritv of surface arca and clectrostatic charge in a soi!
belwCen 20 nd l000 mm
ihan | um size Iraction. with particles with radn
of the surtace area
COnsiluting the major par of sol surlace area. Since major part
conroBld proesses
is in the colloidai traction of the soil. almost all surtace
cooids n
including adsorption reactions. nuclcation and precipitation invo!e
thus !
addition io these chemical processes. colloids are obile in sols. and
bul also a
not onk the chemical transport of otherwise immotbile chenmicals.
sirong ifluence on soil hydrauhcpropertics.
 Negatve charge
Variable%
Constant%
Total
90
10
200
Organic
5%
95
Montmorilionite 100
20
30 80
Ilfite
95 2
5
Keolinite
100
Gibbsite 4

4 100
Geothite

LECTURE 25

ION EXCHANGE IN SOILS

ion exchenge is defined as a reversible process b' hich cations and anions are
exchanged between solid and liquid phases and hctween solid s, if in ci:se contact with
each uther

Adsorption is defined as a phenomenon by which a rease in concentration or an

accumulation of an ion on a solid occurs due to ion exchange ..: o ' rreactions.
Desorption is a
phenomenon by which the replacement or reiease of an adsoried ion species
occurs.
ion exchange_property is almost entirely to the clay
a:nd silt fractions and the organic
matter. The soil particles are amphoteric in nature ard
soil particl: ave the power to hold both
cations and anions. The charge density and
potential are high 3 edges and corners anJ in
furrows and cavities as compared to flat
(plane) surfaces and consequently in
phenomena probably concentrated more in those sites.
are exchange
The
exchangeable ions are helu to the surface by cUil.b forces and
forces. n most of van der-waal's
the soi!s the exchangeable cations are
Ca, , H, K, Na and NH. of
which Ca is the dominant
exchangeable ion. in strong aciri s.iOH), may act as a dominant
exchangeable ion. In alkali soil Na becomes domin2rt and the r:ost common anion So
HCO; etc c and

106
 Catior Exchange cations
exchange compiex by other
replacement of cations adsorbed on
The orocess of the inter
cation exchange takes place rapidiy and
exchange. The reaction of
S caie cation the coil takes place
between.
chemcally equivalent The exchange of cations in
change iS
soil (clay crystal and
solution and those on the exchange compiexes of
Cations in the sO
humus)
soil.
those on the exchange complexes of
Cations released by plant roots and
or a clay and
on the surface of either two clay crystais, twc crsanic colloids;
Cation
humus particde.
tenacity, and the exchange complex does not
All the cations are na adsorbed with equal
higher
al! points. The cation with iess size and
possess same strength of negative charge at
cation.
charge per unit size are held more strongly than other
H=AP'>Ca>Mg">K*= NH> Na
Power or repiacement of cation;

Cation Exchange capacity of soiis (Thomas Way, 1850)

soit can sbsorb is known as "Cation
The sum totai of the exchangeable cations that a
per unit weight of dry
Exchange Capacity" of that soil. it is the amount of exchangeable cations
of soil (Recentlycmol (p) kg ')
soil. It i measured in mil! equivalents of cations per 100 grams
sites in a given
The mil! equivalent is used because the number of negative charge
adsorbed to those sites at one
sampie does not change, but the weightS of cations, that may be
time do changc bccIUSc thcy have different weights.

termed base
Base Saturation: The percentage of total CEC satisfied with basic cations is
with
saturation. It is defined as the extent to which the exchange comnlex of a soil is saturated
exchangeable cations other than hydrogen arnd aluminum andi: is expressed as a percentage of

the total cation exchange capacity.

meq.0f basic catio:s per 100 g soil

xl00
%Base Saturation = Total CEC in n.eg. per 100 g soil

The degree of base saturation is an important property of oil which usually reflects the

extent ef leeching and weathering of soils. It is an indicatien of soil fertility. The ease with which
adsorbed cations are released to plants depends cn the degree uf base saturation.

07
 Highly fertile soils
>80%
Medium fertile
50-80%

Low fertile
<50%
increased. As
common means by which the percent base saturation of soils is
Liming is the
cultivated soils is higher for arid than
general rule, the degree of base saturation of normal
formed from lime stones or basic
humid region soils. Also, the degree of base saturation of soils
acid igneous rocks.
igneous rocks is greater than that of soiis formed from sand stones or
Soils with larger amounts of organic colloids or 1:1 type clay colloids can supply the

nutrient catio ns to plants at a much lower degree of tbase saturation than soils high in 2:1 type
clay colloids.

The percent base saturation does provida numerical values of the amount of
exchangeable hydrogen and aluminum ion species and this helps in predicting the amount of
lime needed to neutralize soil activity.

Kind of adsorbed cations also affects the soil pH. With

same base saturation percentage,
the soil dominated by Na cation presents higher pH
vaBues than the soil dominated by Ca and
Mg" cations.

Factors affecting CEC

More fine the soil more is the CEC
Testy
More humus content more is the CEC

3 2:1 clay minerals have more

bm.
CEC than 1:1 type minerals
4 Inalkaline p range,CECwould be more
5 Liming & Fertilization increases the CEC
Importance of CEC
6 The most important
reaction in nature after
7 It is an
photosynthesis.
important reaction in correcting soil acidity and
basicity
It alters soil phyaical
properties
Through cation exchange
will be purified or
mechanism (large cation exchanger), the
altered (Ground water pollution is checked) percolating waters
108
 tct thetween he OOt hairs
or
exchangeable aions by interchange
0 ants absorD
and cottoidaB complex
related to the
the soilsoiution are intimately
of cations in
! The amounts
exchangeable cations.

to soils.
12 offers buffering capacity
ANION EXCHANGE
edges of layer silicate
occurs on positively charged sites exist on the
Anion exchange area), mainty
surfaces of oxides (with iow specific surface
(1:1 type in particular) and
minerals
under acidic conditions.
soil, is termed as its
amount of exchangeable anions held by a urit mass of
The total
anion exchange capacity.
acidity
generally low and increases as the pH decreases or
Anion exchange capacities are
increases.
of anions
silicate mineral incease, the adsorption
As the ratio of CEC/A EC of a layer
and Koolinite 0.5).
decreases. (Monmorillonite 6.7, llite 2.3
and Fe
regions containirg iydrous oxides of Al
Acid soils in tropical and sub tropical
regions.
calcareous young scis cf arid and semiarid
exhibit much higher AEC than alkaline and

Preference of anions for the positive sites

Sio,> PO,>> So,> NO, =Cl

= Al-0H + H,PO, = =A-HP0, +OH

provide
largely determines the ability of soils to
Like cation exchange, anion exchange
nutrient anions to plants properly.

Acidity
Calculation of Base Exchange Capacity and Exchangeable
estimated amount of Ca is 0.160g/100g: Mg
Problem: The CEC of a soil is 20m.eq./100g soil!. The
0.117g/1O0g soil. Calculate the percent base
is 0.048g/100g; Na is 0.046g/100g and K is
acidity.
saturation and base unsaturation or exchangeable

0.160
Exchangeable Calcium 20 8.0 m.eq. / 1008

109
 210
TrXIROOK OF SoL SctNCE
Table i42. Cationexchange capacity of important clay minerals
MINERAL. CE.C. cmolikg Contribution
cach pcr cent
made by
of clay
Montmorillonite 100 0.6 - L.0
Vermiculite 150 0.8 - I 4
Ilite
30 0.1 -0.4
Chloritc 30
Kaolinite 0.1 -04
8
Fe, Al oxides 0.02 -- 0.10
4
0.05

important clay minerals and contribution made by

given in TabBe 14.2. each percentage of clay is
Soil reaction: in general,
only permancnt charges CEC increases with
of clays and organic increasing pH. At low pH,
increases, hydrogen held by clay and organic colloids hold ions. As the pH
replaceable. colloid
Secondly, aluminium hydrogcn ions which becomes
are released forming ionized and is
are adsorbcd at low pH,
colloids. This rcsults inAl(OH),, thereby
an increase in releasing additional exchange sites on the
As much as
20--40% the CEC may be from
of negativd charge andan increase in the
rises, CEC
pH-dependent
(Fig 14.I). CEC also pH-dependent
increases. Most CECfrom humus is sites. As the pH
Nature of cations and their
clayor humus with power of pH-dependent
different degree
power of cations increases replucement:
of tenacity. It has Cations are adsorbed on
been shown that
is a with the atomic
powerful
byclay than replacer than sodium ion weight Thus potassium ion replacing
cations on thesodium.
clay andDivalent cations are(at.wt.23) Potassium is readily (at.wt.39)
difficulty in humus complexes, thus they willstrongly than adsorbed
adsorbed more
monovalent
conparison
ions are adsorbed to
monovalent ions. is
be
more strongly than any Hydrogen an exchanged with more
Hydrogen clays prepared by
of monovalent other exception. Hydrogen
or divalent
exchangeable H* ions and exchange
small reactions initially contain ions.
concentration exchangeable
of
ions cause a partial A* ions amounts of AI ions.
builds up rapidly. The
large
However,
amountsthe
exchangeable. decomposition,
In gencral, the
The solubility of each power exchangeable
and A" released
of from the clay
is, H> Ca > Mg >becomes
H+
cation exchange replacement
cation is regulated by its K> Na.
exchangeable population,
andsodËum ions.
thus
calcium to CEC ASsume contribution
that
relative
calcium solubility is to the total
a soil has regulated by the ratio of
adsorbs more strongly Calcium will tend to take over the equal number of calcium
Size of ion: The on the micelle. Sodiun will tend other exchange sites
sodium and relative abundance of calcium andto leach out of thebecause solution.
it
in
preferencepotassium. Generally,
(Table 14.3) ions with smallcr magnesium is more than
The following hydrated sizes are adsorbed
inonovalent
is the cations by clays has been order of preference
smallest in size. thus its rate of reported: Cs> Rh >K> for adsorption of
of lithium
increases the distance fromadsorption Na> Li.
is highest. A
ion to the clay thick hydrationCesium
cel!
surface.
 209
les ExcHANGE PENOMENA

NH, CH,C00
o CH,COONH, NH,-soil +CH,CO0X
X-soil + NH, + CH,CO0 ’
MgO + H,0’ Mg(OH), ’ Mg?* + 2 (0H) soil + 2 H,0
O Mg+2(OH) ’ 2NH, + Mg- replacement
o 2 NH, -soil + sodium acetate solution (pH 8.2) forwashed down
leached with a are
The soil is Na ions. The excess of salts
cations by
of exchangeable
adsorbed Na ions are replaced by NH," ions, using N
by alcoholand the solution. The Na' ions so released from the exchange
CH,COONH,(pH7) measure of total
measured flame photometrically andserve as the
spoisare equations:
be illustrated by following
exchange capacity ofthesoil. Thiscan
O CH,COONa CH,CO0 +Na'
o X-soil + Na* + CH,CO0 # Na-soil + CH,COOX
CH,COONH, CH,CO0 +NH,
Na-soil+ NH, NH,-soil + Na
EXCHANGE CAPACITY
FACTORS AFFECTING,CATION
soil pH, humus and clay contents
Cation exchange capacity is affected by
values are known.
and can be predicted approximately if their of particles of any specified
Soil texture: The charge at the surface
exposed, which in turn increases
composition will increase with the surface area
Thus, other factors being equal,
with adecrease in the mean particle diameter.
greater the cation exchange
smaller the particles. greater the surface area andgrains is o great relevance to
capacity. The particle size distribution of mineral
capacity incrcases with fineness
its cation exchange properties. Cation exchange (Table 14.). This is because
of soilparticles i.e. with increasing percentage of clay
calions.
negatively charged clay micelle attracts positively chargedincreases with organic
Organic matter: In general, cation exchange capacity capable of
charged and is
matter content of soil. Humus micelle is negatively (-OH) and carboxylic acid
holding nutrient ions. The dissociation of phenolic
pH- dependent, thus cation
(-COOH) groups on soilorganic matter is strongly negative charge on a
exchange capacity varies with pH in many soils. Hence
more H* ions dissociate
humus micelle depends on pH. When the pH increases,
on the humus micelle
from the groups. Consequently, the negativé charge
increases.
mineral varies. Soils
Nature of cluy: Cation exchange capacity of ciay exchange
dominated by vermiculite and montimorillonite clays have greater cation C.E.C.of
chlorite .:crals.
capacity than those dominated by kaolinite, illite or
texture classes
Table 14.1. Cation exchange capacity of different

Soil textural class

CEC(Cnol /kg)
U-5
Sand
5-!0
Fine sandy loam
5-15
Loam, silt loam
15-30
Clay loam >30
Clay
 (CottOH), enolic (OH) arnd
phenpic
(COOH)
ap
(atboxylic
groups
ipotant furxltonal
The
inide (-NH)ete
inorganic colloids
between organicand INORGANIC COLLOIDS
Differenes
ORGANIC COLLOIDS

PROPERTY Weathering of rocks and minerals

Decomposition of o.ganic
Origin
matter
OH
Si, Al, Fe, Mg, O,
C, H,O(N, P, S)
Composition
Crystalline except allophone and
Annorphous
Shape sesquioxide clays

Unstable in nature table

Stability

pH dependant Mostly due to isomorphous substitution

Origin of charge
nd partly by soil reaction
-1
CEC 150-400 cmol kg 3-150 cmol kg

Water and nutrient holding High

capacity
Piasticity Low
"igh
Surface area m/g Around 900
Variable (10 to >700)

LECTURE 24

ORIGIN OFCHARGE ON SOIL COLLOIDS

The two
properties that most ly acCount tor the
irface charge. Surface area is the direct reacli, oi soils are surface area and
result of particle size &nd
in soils is intimately associated with clay sized particles and humus chape. Charge development
Two types of charge arises on
inorganic cOlloids .e., ¢rmanent
charge, temporary charge or variable charge. charge or constant
Permanent charge

Isomorphous substitution and charge

comparable size (within 15 % )
another ion of
Substitution of one ion with
crystal lattice.
without disturbing the
variation of one unit of comparable
size
rocks and minerals pernits cations
wide variety of tetrahedrai and
The weathering of ions in the respective
alluminum and magnesium
substitute for silicon, silicon (0.042 nm).
to
only slightly lzrger than
octahedral shccts. Aluminum (0.051 nm) is place of the silicon
in to the cer1tre of the tetrTh:cron in the
Consequently the aluminum can fit called "Isomorphous
basic structure of the crystal. This pro CSS is
without changing the in the nature of silicate
accounts for the wide variability
substitution", which is common and
both negative and positive
vital importance because it is the primary source of
clays. It is of
charges of silicate clays.
and
octahedral sheet. Iron (Fe* 0.064 nm)
isomorphous substitution also occurs in the
magnesium (0.06),
to the position of either aluminum or
zinc (0.074 nm (Fe*0.070 nm)can fit in
sheet.
as a central ion in the octahedral
developraent of permanent charge on
Isomorphous substitution is responsible for
past
substitutions have taken place slowly through
inorgaric colloids. The isomorphous
modification. Consequently, these charges are
weathering cycles, and are not subject to easy
they are related to the chemical composition of
termed constant or permanent charges, because
silicate clays.
may have a greater, equal or lower
In the process of substitution, the ubstituting ion
The difference in dimensions of substituted
charge and size than the ion for which it substitutes.
difference between the substituting
ions was reported to be no more than 15% and the valency
ions should not be more than one unit (Paton, 1978).
Tetrahedral sheet Al subsituted for Si

SiO. SiAIO4

Octahedral sheet Mg substiruted for Al

Al,0, (OH), MgAIC;{0)

No substitution sybstitution resu'ted in negative charge

103
 Isomorphous substitution can also be a source of p0sitive charge. If A* ion substitutes

Such positive'charges are characteristic of the

charge results
for Mg on, a net positive
vermiculites and chlorites.
trioctahedral sheet in some
Mg,Al0,(OH),
Mg:0, (OH),
because
Trioctahedral sheet net positive charge

AI substituted for Mg
and negative charges on
Though there is a scope for development of both positive
substitutions lead to the
silicate clays, the net charge is always negative because most of the
development of negative charges, which far outweigh the positive charges.

TEMPORARY CHARGE ON COLLOIDS

It, is the second source of charge on some silicate clays (kaolinite) and on humus.
allophone and Fe, Al hydroxides. Because these charges are "pH dependant", they are termed
"variable, temporary and pH dependant" charges.
The positive charge developed at low pH and the excess
negative charge developed at
high pH, are collectively known as pH dependant
charges. The soil's total charge is the algebraic
sum of its positive and negative charges.

The zero point charge (ZPC) has

been used as on index of the
charges on soil colloids. The ZPC is the pB at positive and negative
which negative and positive charges of a
equal. colloid are
The contribution of edge
OH groups on cryatal
rise to charge on certain edges or on exposed planes
colloids.. At high pH, hydrogen of OH on gives
combines with hydroxyl ions to form water crystal lattice dissociates and
molecules. This leaves
protonation of exposed hydroxyl groupsnegative charge
surface. At low pH on colloidal
development. dependant charge is related both to the results in positive charge
of the edge
surface. In 2:1 type minerals, edge acidity of the edge groups and to the area
Vaolinites tend to stack in surface is small relative to the
Cdimension, increasing the relative area of basa! plane.
plane area. For these reasons, pH edges in relation to basal
dependency of charge is more
smectites or vermiculite. important for kaolinite tha nfor
2:1 type minerals
5-10% pH dependant charge
1:1type mineral
SO%
= A|-OH OH
Al0 H,o

104
 edges:
egative charges on crystal
Development of pos1tive and

Fe or A!

OH, h+

+H

+OH
OH /2+ 14
Jlacidic pH))

- H,0
Fe or Al

(alkaline pH)
OH;

OH 1/2.

Fe or Al
OH/2.

be the gain
Organic colloids: The primary source of charge on organic colloids is considered to
groups include
or loss of H' from functional groups on the surface of colioids. The functional
hydroxyl (-OH), carboxyl (CO0H), phenolic (-CH.OH) and amine (-NHz). The charge that
develops from such groups depends largely on the pH of the ambient solution, which regulates
the degree of protonation or deprotonation of the group.

CO-OH OH -Co-0 + H,0

Nocharge -ve charge

The soil colloids that are capable of developing pH dependant charge include layer silicates,
oxides and hydroxídes of Fe and Al and organic matter.

i05
 CEC& AEC - factors iniiecng
on echange
1isorpiion of io!s
exchange- Sigaificamee.

Adsorplion ol iois
exchange are porlant prOCCSSES (hat tak..
subscquent
lon adsorption and
particles.(clays, organic 1aller. seSqulONles, and
place betiveen soil colloidal
various ions.Soil colloids kerve verv much as a mode
amorphous minerals) and
of SsCntual plant nurients are
bank. They arc the siles within the soil where ions
Subsequently, the nutricntscan
held and protccted fiom excessive loss by leaching.
turn.
be "withdrawn" from the collodal "bank" sites and lakeiup by plant ro0ts. 0n
these elements can be "deposited" or returned to the colloids through the addition
of commercial fertilizers. lime. manures, and plant resicucs.
The charges associated with soil particles attract ions (simple and coplex)
of opposite charge. n temperale region soils. igative charges generally
prcdominale on the soil paricies (colloids). hence ad::Cations are present in
larger quantities than anions. In more highly weathercd soils (e.g. in tropics) here
1: type clays and Fe:Al oxides arc the most domi!N IVpe of
coilods, aunion
adsorption andexchange is relaiively mOre prominent.

The lon Exchange phenomcn0n was hrst

identified by Fiarry Stephenlhompson in
England during 1850. When soil was eached
(washed) with ammoniunm suinhate.
calcium sulphate was detected in hc lcachatc. The
ammonium ion in he soui0n
replaccd caleiunm in the soil.
 The procCSs hy which ions are exchanged betwcen solid and hquid phase'S
and or bctween solid phaSes if in close contact wi!h cach oher is called ion

exchange.

The common exchangeable cations are Ca mg H K. NH, and Na.

The common anions are So, CI Po, and NO;.

The ion exchange in soil is due to the presence of residual positive and
negative charges on the soil colloids. These residual charges result due to the
process of isomorphous substitution and ionisation of hydrogen and hydroxide
functional groups. The negative charges attract positively charged ions and thc
positive charges attract negatively charged ions from soil solutions coming in
contact with colloids. The ions thus attracted are reversibie and are on equivalent
proportions.

Exchange of cation is called cationexchange and exchange of anion is called

anion exchangc. The cation exchange phenomenon was first discovered by
Thomasway (1850) lon exchange is the second most important reaction is nature.
The first onc is photosynthesis by green plants.
The capacity of the soil to hold cation is called cation exchange capacity.
The unit is C mol (P)/kg. The capacity to hold anion is called Anion exchange
capacity (AEC). The unit of expression is C mol(e') / kg
Mechanism of cation exchange.

Clay colloids have negative charges. Cations are attracted to the clay
particles. These cations are held on the held on the clay surfaces electro
statistically. They are heid by small particles of clay and organic matter. These
smallparticles are called Micelle(Micro cell). The cations that can be replaced on
 cations are called cxchangeable cations: hes arcuet
changtC site bv other
solution. They can be exchanoed
held and thev are in direct contact vith the soil
Jons that are held very ightly with the colloid may be
trapcd between
fairly casily.
They are
lavers of clav micelle. They do not pass to the soil solution very casily.
called non cxchangcable cations. When any caticn is added to the soil such ac
Ca". K*or NH, through fertilizers and soil amendments they are exchanged with
those ions held on the colloid. When calcium is added to an acid soil the following
reaction takes place.

nniceile (a 2H
H

Similarly when H is added to the soil solution through the decomposition of

organic matter or through acidic matcrials Ca is replaced from the
complex by H. exchange

ExampBe: Ca exchange displaces exehangeable Na

.Nat
[Ca>)
Na*
[Na*]
Dissolved in soil solution INa}

Negatively-charged clay
 XCa+2Na'

X= exchangeable
< ation exchage capacitv (CO

The sum total of the exchangeable cations that a soil can adsorb is called as
cation exchange capacity.
It is also defined as "the amount of cationic species bound atp" 7.0.

Some authors consider p"4.0as the appropriate point.

Principles governing cation exchange reaction

Reversibility

|Micelle Na" + H* Micelle|H* + Nat

(soil colloid) (soil (soilcolloid) (soil
solution) solution)

Charge equivalence

Micelle Ca" + 2H® |Micele + Ca'+

(soil colloid) (soil solution) (sol colloid) (soil solution)

Ratio law when eled

elementb

Micelle 20 Ca'+5 Mp? Micelte 16 Ca +! Mg' + 4 Ca Ratio: 4Ca IMg

4 Mg'*
icoid (ot solution) icollnd) (sod soiutnn,
 MicelleCa'* +H,0 + co,
+CacO,
MicelleH' (addef)
LWaler

(afion selectii
Nat
A13+ >Ca?- > Mg+ > Kt = NH,>
(0mplementar ion eifect

Root
withexuding
cations Hiooqns to cXChSng
Jecol oid
Micelk Micelle

Looscty ield imptemeotary ns lightiy eld copkenentary ins

wih r ge oscilatíon zoes with sinatl osciltation zones

(ECof different texur!aSses.

Sand 0-5 C mol (P)/Kg.
Sandy loam 5-10
Loam 10-15
Clay loam 15-30
Clay 30.0
(EC of important clay niHerals
Kaolinite
7-10C mol (P')/Kg
Montmorillonite 80-100
Vermiculite 100-150
lite 25-30
Chloritc D5-30
 l'e& Aloxides
lumus 200-40)

rectors inuencing C

(HCincrcases vith fincness of thc soil particles. This mcans

increasing clay content willincrcase thc CEC. As the particle size decreases
the surface arca increases per unit volume. This naturally incrcases the nct
charge and the CEC.
In general CEC increases with increase in organic matter
content. The p" dependent charges in the organic mattcr cause variation in
CEC. When p of the soil solution increases the CEC will also increase.
CEC of clay minerals vary soil dominaled with
montmorillonite and verniculite have higher CEC than those dominated
with kaolinite, chlorite or illitc.
In general CEC increases with increase in soil p". As the p'"
increases the p" dependent charge increases. In Humus most CEC is p"
dependent.
Replacing power of ions:

Replacing power of ions increases with atomic weight. Divalent cations have

more replacing poIver than monovalent ions. Hydrogen is an exemption. H ions

are adsorbed more strongly than other monovalent or divalent ions. The replacing
power of cations varies with the type of ion, size, degree of hydration, valence.
concentration and he kind of clay mineral involved. As it is controlled by
number of factors no single order of replacement can be given. All other factors
being equal the replacing power of monovalent cations increases in the folkowing
order: Li< Na <K < Rb <Cs < Hand for divalent cations: Mg <Ca< Sr< Ba. In
case of mixture of monovalent and divalent cations as they exist in normal soils the
 NH, Me (a
tollowing order: Na<K< H
incrcascs in the
replacing powcr than K and K more casily han NË,
casilv replaced
This means Na is more
replacement is
In general the pÍwer of

Rase safaration

cations is called
The pcrccntage of CICthat is satisticd by the base forming
base saturation percentage.

Bave saturatt:

Aluminium and hvdrogen are considered as acid forming i0ns: Calcium.

Magnesiu. Potassium and Sodium are considered as base forming iOns. Base
forming substances are called as besoids and acid forming substances are
calcd as
acidoids. The
percentage of sodiunn in the total CEC is callcd Exchangcable
sodium percentage (ESP) {Na/CEC) 1001. 1hese
parameters are considercd
while deriving fertilizer prescription and
amendments for problem soils A
knowledge of base saturatiOn percentage is useful in many
ways.
1. It helps in determining the
quantity of lime required to raise the p" of acid
soils.
2. It indicates the
proportOn of planl nutrients in CEC. It is an index of soil
fertility.
3. Degree of saturation ot a particuBar
cation in CCindicates the
case vith
which the cation can be releascd tor
plant nutrition. For
example if caleium
 saturati0n is more (a can be very casilk replaccd from the cxchange
complex.
4. Fór a fertile soil it is considered that the base saturation percentage should be
morc than 80.
Anion exchange

Replacement of one anion by another anion on the positively charged

colloids is called anion exchange, positive charges are due to OH of iron and
aluminium. 1:1 clays and allophone (a morphous clays).
Anion exchange is p dependent. Lowver the p" greater is the anion
exchange. Soils with Kaolinite dominant clay have higher anion cxchange capacity
than montmorillonite or illite.

The relative order of anion exchangc is

inportance of anion exchange:

1. The phenomenon of anionexchange is important for the releasec of fixedP in

the soil.

In acid soils the phosphorus is fixed as insoluble Al-Phosphate. Liming the

acid soils release fixed P. Here the OH ion replaces H, PO, from Al(OH))
H,PO4.

2. Similarly the availabilitv of other nutrients like NO3. SO, and Cæ are
influenced by anion exchange.