Ion Exchange Process

Cation Exchange Process

Increase in Wetness Water in pores

Dry Saturated
 Cation Exchange Process
Used by plants/microbes or leached
Diffuse Double Layer

Exchange of ions between the

Inner Sphere Bulk Solution
bulk solution and swarm is:
Complex 1. Rapid
Outer Sphere complex 2. Reversible
(swarm/exchange site) 3. Stoichiometric
 Cation Exchange Process

- exchange of cations in solution with

cations sorbed on soil
surfaces/exchange site
Cation Exchange Process – Plant Nutrients

Fertilizer (NH4+) and

lime (Ca2+) and
K+

K+

K+

K+

Inner Sphere Bulk Solution

Complex

Outer Sphere complex

(swarm/exchange site)
Cation Exchange Process – Plant Nutrients
NH4+
Ca2+
NH4+
Ca2+ 2+
Ca

NH4+

K+

K+

K+

K+
Cation Exchange Process – Plant Nutrients
NH4+
Ca2+
NH4+
Ca2+ 2+
Ca

NH4+

K+

K+

K+

K+
Cation Exchange Process – Plant Nutrients

K+ NH4+
Ca2+
K+ NH4+
Ca2+ 2+ All available
Ca
K+ for plant use
NH4+
K+
Cation Exchange Process – Contaminants

Fertilizer with
Chromium (Cr3+)
K+
K+
K+
K+
K+
K+
K+

Inner Sphere Bulk Solution

Complex

Outer Sphere complex

(swarm/exchange site)
Cation Exchange Process – Contaminants

Cr3+
Cr3+
Cr3+

K+
K+
K+
K+
K+
K+
K+
Cation Exchange Process – Contaminants

Cr3+
Cr3+
Cr3+

K+
K+
K+
K+
K+
K+
K+
Cation Exchange Process – Contaminants

Not available for

transport in soil
(immobile)

K+
K+ Cr3+
K+
K+ Cr3+
K+
K+
Cr3+
K+
 Cation Exchange Process
Due to this exchange process:
1) Nutrients that are temporarily stored are made
available for plant use
2) Nutrients in solution may be sorbed temporarily in
the soil and prevented from being lost via leaching
3) Contaminants are sorbed and retained in the soil
 Cation Exchange Process

Degree of sorption depends on:

1. Valences
2. Hydrated Radius

When the hydrated radius is shorter and the

valence of the cation greater… what happens to
the degree of sorption?
 Adsorption Preference

Al3+>Ca2+>Mg2+>NH4+=K+>Na+>Li+

Hydrated radium, nm
Lithium Li+ 103
Sodium Na+ 79
Ammonium NH4+ 54
Potassium K+ 53
Magnesium Mg 2+ 108
Calcium Ca 2+ 96
Aluminum Al 3+
Cation Exchange Capacity (CEC)

- the ability or capacity of a soil colloid to

“sorb” cations that can be exchanged
with cations in solution.

 Determined by the quantity of negative

charges (how negatively charged the soil
particles are)
 Sorption is a surface phenomenon so CEC is
directly related with amount of surface
exposed
Smectite vs Kaolinite
What affects CEC?
Factors Affecting CEC

1. Amount of clay– influences surface area

exposed
2. Type of clay – influences charge
3. Organic matter content
4. Fe and Al oxides
5. pH
Factors Affecting CEC

1. Amount of Clay
– influences surface area exposed

What’s the relationship between

particle size and surface area
exposure?
Factors Affecting CEC
2. type of clay
Type Mineral CEC Comment Specific
(cmol(c)/ surface
kg (m2/g)
1:1 Kaolinite 2-15 Low layer charge; 7-30
low CEC

2:1 Mica (illite) 10-40 High layer charge; 40-100

low CEC due to
fixed K+

Vermiculite 100-200 CEC proportional 600-800

to layer charge

Montmorillonite 70-120 CEC proportional 600-800

to layer charge

2:1:1 Chlorite 10-40 CEC less due to 25-150

interlayer filling
Factors Affecting CEC
2. type of clay

Figure 8.28
Factors Affecting CEC
3. Organic matter content.
- Negative charges from exposed
functional groups (-COOH)
4. Fe and Al Oxides
- Negative charges from exposed
functional group
5. pH
- Influences possibility of
protonation/deprotonation of functional
groups
Factors Affecting CEC - pH
Soil Solution
in pores
OH-

HOOC COOH
Organic
OH- Matter

COOH COOH

OH- OH-

If there is an increase in pH in the soil solution…

Factors Affecting CEC - pH
Soil Solution
in pores
OH-

COOH+

|
+
HOOC
|

Organic
OH- Matter

COOH+

|
COO H+
|

OH- OH-

If there is an increase in pH in the soil solution…

the soil becomes more negatively charged.
What happens to CEC?
Factors Affecting CEC

At any pH, organic matter

contributes to CEC

CEC increases with pH due

to pH-depended charge
contributions of the organic
and mineral fractions

Figure 8.25
Cation Exchange Capacity

CEC can be viewed as the amount of cations

a soil can hold

Units – centimoles of positive charge per kg

soil
- cmol (c)/ kg
Concept of a MOLE
1 mole H+ - how many H+ ions?
Avogadro’s number = 6.022 x 1023
H+ ions or positive charges

1 cmole H+ - how many positive charges?

1/100 × Avogadro’s number

10 cmole H+ - how many positive charges?

1/10 × Avogadro’s number
Stoichiometric Property of Cation Exchange
What does a CEC of 10 cmol/kg mean?
Means – 1 kg soil is capable of sorbing 10 cmol
of monovalent cations (e.g. K+ or Na+)

Means – 1 kg soil is capable of sorbing 5 cmol of

divalent (e.g. Ca2+, Mg2+)

Means – 1 kg soil is capable of sorbing 2 cmol of

ion with trivalents (Al3+), 1 cmol of divalent and 2
cmol of monovalents?
Stoichiometric Property of Cation Exchange

Reemphasize…
Cation are adsorbed and exchanged on
a chemically equivalent basis.

1 mole of negative charge can sorb:

• 1 mole of K+ or Na+
• ½ mole of Ca2+ or Mg 2+
• 1/3 mole of Al3+
Stoichiometric Property of Cation Exchange

Keeping this equivalency concept in

mind….

H+ + 1 Na+ 1Na+ + H+
or

H+ + 1/2 Ca2+ 1/2 Ca2+ + H+

Is a high CEC Good or Bad?
CEC –Implications

What does a high CEC mean?

Soil can sorb/retain large

amount of cations

You may have to

apply more nutrient Effective in fixing
elements (cationic) contaminants
Effective in
retaining nutrients
that can eventually
be supplied to
plants
Cations Sorbed in Exchange Sites
Two groups of adsorbed ions:
1. Acidic Cations
2. Basic Cations
Acidic cations
1. H+ - contributes directly to acidity
• Includes H+ that is measured
by the pH meter
2. Al3+ - contributes indirectly to
acidity via hydrolysis reactions
Cations Sorbed in Exchange Sites
Most of the other cations sorbed are “exchangeable
bases”

Ca 2+
Mg 2+ Technically, these are non-acid
K+ cations and not “bases”
Na +
When sorbed in colloids in place of H+,
they reduce acidity and increase the pH --
- Hence they are referred to as “bases”.
Base Saturation Percentage (BSP)

Ca 2+ The cations that neutralize soil

Mg 2+
K+
acidity and dominate in neutral
Na + and alkaline soils.

BSP
= Proportion of the cation exchange capacity
occupied by these bases.

= [exchangeable bases (cmol/kg)]/ [CEC

(cmol/kg)]
What does a high BSP value
mean?
BSP -Implications

1. Bases dominate the exchange site

2. Soil is not acidic.
3. Soil has high buffering capacity (against
a drop in pH)
How about the ANIONS? What
happens to them?
Anion Exchange
- happens if the net charge emanating from the soil
surfaces is positive.

Net
Charge
cmolc/kg
Gibbsite +10 to -5
Goethite +20 to -5
Allophane
& Imogolite +20 to -150

- Anions such as HCO3-, Cl- and NO3- can be sorbed

and can actively be exchanged with anions in solution.
Anion Exchange Capacity (AEC)

- the capacity of a soil colloid to “sorb” anions

that can be exchanged with anions in solution
- Just like with cation exchange, anion
exchange is rapid, reversible and
stoichiometric

NO3- + 1 Cl- 1Cl- + NO3-

Point of Zero Charge
• pH affects the charge of soil particles
• Decrease in pH (higher H+ concentration)tends to
protonate exposed functional groups leading to a
more positive charge
• Increase in pH (higher OH- concentration)tends to
de-protonate exposed functional groups leading to
a more negative charge

There is a pH wherein the quantity

of + and – charges in the soil are
equal such that the net charge is
zero - Point of Zero Charge (PZC)
Point of Zero Charge
There is no net cation
exchange process at
this pH.

• Applied nutrients
are not retained
• Contaminants are
not sorbed
Review

1. What is cation exchange capacity of CEC?

2. What are the characteristics of the cation
exchange process?
3. What are the factors that influence CEC?
4. What does a high % base saturation mean?
5. What is the generalized relationship between
CEC and fertility?
6. What is AEC and under what conditions does it
predominate in the soil?
7. What is point of zero charge or PZC? What is
happens when pH of the soil is at PZC?