Less effective

cation exchange

More effective
cation exchange

CATION EXCHANGE CAPACITY

Cation Exchange Capacity
 CEC is operationally defined – determine the amount of
a cation that can be removed by a specific substance
once the material and solution have come to equil.
 Generally reported as milliequivalents per 100 grams of
sold (meq/100 g).
Clay Mineral
Organic Matter
Octahedral sheet neutral Net negative charge
Creation of Clay Colloid Charge

pH-dependent charge: on edges

H+ bound tightly, so
the lower the pH, the
less exchange there is
(i.e., lower nutrient
availability)

Especially important in kaolinite, humus, where no

internal charge imbalance
 CEC VS Grain Composition

From Horowitz, 1991

CEC VS Grain Size
Competing Cations
 When one or more cations are present in the solution, the
different cations compete for the anion adsorption sites on the
mineral surface;

In general, as concentration of a cation in solution goes up, the amount of

it exchanged and sorbed to the surface of the mineral goes up

However, even when the concentrations of the ions are the same, some
cations have a stronger affinity for the mineral surface.
Influences on Cation Affinities
 Charge on cation – more highly charged solution species are
preferentially adsorbed.

 Al3+ >Ca2+ >Mg2+ > K+ > Na+

 Also means that affinity is dependent on valence

 Me3+ > Me2+ > Me+

Competing Cations
 Increased Affinity with decrease in diameter of hydrated ion

 Cs+ > Rb+ > K+ > Na+ > Li+

 Selectivity Series for divalent cations (Deutsch, 1997)

 Pb2+ > Ba2+ = Sr2+ > Cd2+ = Zn2+ = Ca2+ > Mg2+ = Mg2+ = Ni2+ =
Cu2+ > Mn2+ > Fe2+ = Co2+
NUTRIENTS REPLACE CATIONS
 Cation exchange- the interchange between a cation in solution and
another cation on a soil surface
 Cation exchange capacity (CEC)- the total sum of exchangeable cations
that a soil can adsorb.
Importance of CEC
 Chemical behavior in soils
 Fertility
 Liming rates
Buffering capacity
 Pesticides
 Contaminants
 Non-acid cation (Base) Saturation
Ion exchange
 Sources of charge:
In 2:1 clays, charge created mostly by isomorphous
substitution.
– Not very pH dependent
Hydroxyls (OH-) and other functional groups on the
surfaces of colloidal particles that cause positive or
negative charges based on releasing or accepting H+ ions.

– pH dependent
– Common source of charge on humus, Fe and Al oxides, 1:1 type
clays, and non-crystalline silicates
 OF GREAT IMPORTANCE:
The influence of clay type on CEC
 Model pertukaran kation.
1. Kation mempunyai energi panas sehingga terdapat seperti hemisphere of
motion disekitar permukaan koloid
 Pertukaran kation terjadi apabila ion yang berada dalam larutan tanah
bergerak ke hemisphere motion (hemisphere motion dihasilkan oleh kation
yang terikat oleh koloid) suatu kation bertepatan dengan kation tersebut
jaraknya jauh dari permukaan koloid. Akhirnya ion tadi tertangkap oleh
muatan negatif sedang kation akan bergerak ke larutan tanah
 Faktor yang berpengaruh terhadap distribusi kation antara larutan tanah
dengan permukaan koloid adalah
(1) konsentrasi kation dalam larutan tanah,
(2) valensi dari kation yang tertukar,
(3) hydrated-size dari kation,
(4) kepadatan muatan pada permukaan koloid
Model 2 : Mass-Action Model
 Misal, 2Na-clay + Ca2+ (aq)  Ca-clay + 2 Na+ (aq)
 Apabila konsentrasi Ca2+ (aq) pada larutan tanah
meningkat maka reaksi bergerak ke kanan, sehingga
konsentrasi Ca pada clay meningkat sambil
melepaskan ion Na ke larutan tanah.
 Jika konsetrasi ion Ca menurun, maka reaksi
bergerak ke kiri sehingga ion Ca terlepas ke larutan
tanah
Typical
CEC
Values

Figure 8.13  Ranges in the cation exchange

capacities (at pH 7) that are typical of a variety
of soils and soil materials. The high CEC of
humus shows why this colloid plays such a
prominent role in most soils, and especially
those high in kaolinite and Fe, Al oxides, clays
that have low CECs.
Principles of Ionic Exchange
Reversible Reactions
Charge Balance
Ratio Law
Mass Action
Ion Selectivity
Complementary Cations
 Reversible Reactions
Can go forwards or backwards

Example:

H + K+
micelle
micelle + 2K+ + 2H+

H + K+
 Balanced by Charge
Charge for Charge…..
NOT ion for ion

Ca ++ K+
micelle
micelle + Ca++
+ 2K+
K+
 The Ratio of Ions on Exchange
Site is Equal to the Ratio of Ions
in the Soil Solution

6 H : 3 Na 4 H : 2 Na 2H : 1Na

before After on colloid After in soln.

H+ H+ Na+
H +

H + Na+
micelle + Na+ and 2H+
micelle + 3Na+

H +
H +
H + H+
H+
H+
 Mass Action
H+
micelle micelle + H2O + CO2
+ CaCO3

H+ Ca++

CO2 is a gas and escapes

from the soil easily….

This drives the reaction to

the right.
Ion Selectivity
Al+3 > Ca+2 > Mg+2 > K+ = NH4+ > Na+

Held tightly ---------------------------------- Held loosely

Based on Valence Charge and Hydrated Ionic Radius

Charge of ion
Selectivity =
Size
Penentuan Kapasitas Tukar Kation (KTK)

KTK di laboratorium ditentukan berdasarkan pH larutan yang

di buffer (karena adanya muatan tergantung pH), yaitu larutan :
 NH4OAc pada pH 7,
 KCl 1 N pada pH Lapang (tanpa buffer),
 BaCl2 + TEA (Trietanolamin) pH 8,2
Sumber Kemasaman Tanah

Sumber kemasaman tanah :

 ion H,
 Ion Al yang dalam reaksinya akan menyumbangkan ion H.

Al+3 + H2O  Al(OH)+2 + H+

Al(OH)+2 + H2O  Al(OH)2+ + H+

Al(OH)+ + H2O  Al(OH)3 + H+

Gibsit