Soil Chemistry

The Colloidal Fraction:

Kaolinite Mica

Montmorillonite Fulvic acid

Figure 8.1
 What is a colloid?
• either organic or inorganic with very small
particle size (< 0.001 mm or 1 µm)
• large surface area
• presence of electrical charges (+/-)
 Types of Soil Colloids

1.) Organic Colloids – Humus

2.) Inorganic Colloids – Clay Colloids
a.) Layer Silicate Clays/Phyllosilicates
Kaolinite
Illite
Montmorillonite
Vermiculite
Smectite
b.) Oxide Clays - Iron and Aluminum Oxides (Goethite,
Hematite, Gibbsite)
c.) Amorphous Clays – Allophane and Imogolite
Figure 8.4
Basic Phyllosilicate

Tetrahedr Octahedr
al Sheet al Sheet
 Important Clays Minerals
• Kaolinite – Most common in soils
• Smectite – Shrink-Swell Clays
– Montmorillonite
• Vermiculite
• Micas – Fine-grained micas
– Illite
• Chlorite
• Humus – Humic acid and organic matter
 Types of Silicate Clay Minerals:
A.) 1:1 Type Silicate Clay Minerals - KAOLINITE

• Consist of one layer of silica tetrahedron

and one layer of Alumina Octahedron
• The layers are held together tightly by H-
bond to restricts the expansion and limits
the reactive area to external surface
• Two sheets are held together by O atoms
that are mutually shared by Si and Al
A.) 1:1 Type Silicate Clay Minerals - KAOLINITE

• Has little isomorphous substitution

• Low colloidal property
• Highly impermeable – water cannot permeate
the layers to cause expansion or contraction
with wetting and drying
• Low CEC (6 – 15 meq/100 g soils)
 Kaolinite micelle

Gibbsite
layer

Silicat
e
layer
 Kaolinite clay mineral

…consists of stacks of micelles

Usually hydrogen bonds micelles

together:
 a strong bond
 stable clay mineral
Kaolinite

Hydrogen
bonding
Kaolinite
 B. 2:1 (Expanding Type) – MONTMORILLONTE
and VERMICULITE
• Consist of one layer of aluminium octahedral
sheet sandwiched in between by two silica
tetrahedral sheets
• Layers are held loosely by weak O to O bond and
cation – O linkages
• Exchangeable cations and water molecules are
attracted between layers causing the expansion of
the layers or lattice when they are wet
• Flake-like crystals and much smaller than kaolinite
 B. 2:1 (Expanding Type) – MONTMORILLONTE
and VERMICULITE
• Has larger specific surface area due to contribution
of internal surfaces
• Soils with high montmorillonite cracked markedly
upon drying and tend to be impermeable when wet
• Montmorrilonite can hold more water than its
volume
• It has more negative charges
• Montmorillonite derives its negative charges from
the isomorphous substitution of Mg2+ for Al3+ in
the octahedral sheet
 B. 2:1 (Expanding Type) – MONTMORILLONTE
and VERMICULITE
• Vermiculite derives its negative charges from
the isomorphous substitution of Al3+ for Si4+
in the tetrahedral sheet
• Water molecules along with other ions act as
bridges holding the unit together rather than
apart
• Vermiculite swells less than montmorillonite
– High CEC (80-100 meq/100 g soils)
Smectite (includes montmorillonite)
2:1 Expanding Type
C. 2:1 (Non - Expanding Type) – ILLITE
• Crystals occur as irregular flakes
• Unit layers are held together by K ions, O-K-
O bond is created hence no expansion upon
wetting
• If all or most of K is removed, illite becomes
vermiculite
 Illite

magnified
about
15,000
times
 2:1:1 or 2:2 (Non - Expanding Type) –
CHLORITE

• 2:1 layers alternate with a hydroxide sheet

commonly dominated by a magnesium
• No water adsorption between the unit layers
hence it does not expand in nature
Figure 8.14
 OXIDE CLAYS
• mainly Iron and Aluminum Oxides
• Common in highly weathered soils (Ultisol and
Oxisol)
• Oxides of Iron includes Goethite, Limonite, Hematite
and Magnetite
• Oxides of Aluminum includes Gibbsite, Boehmite and
Alumina
• Has low CEC and pH dependent
• High phosphate fixing capacity
• Has stable aggregates and exhibit low plasticity
• Infiltration of water is rapid
 AMORPHOUS CLAYS
• Allophane and Imogolite
• Common in soils developed from volcanic ash
(Andisol)
Important Characteristics of Soil Colloids
Related to Chemical Reactivity:

• Fineness and large

specific surface area

• Presence of electric
charges
 Source of negative (-) charge
• Isomorphous substitution (IS)
- substitution of one ion for another of similar size within a
crystal lattice
 major source of negative charge in 2:1 layer
silicates
are:
- Al3+ for Si4+ in the tetrahedral sheet
- Mg2+, Fe2+ for Al3+ in the octahedral sheet
• Exposed –OH at broken edges of crystals
- at high pH, the hydrogen of these exposed hydroxyls,
dissociates and rge surface of the clay is left with the (-)
charge of the oxygen ions
- This type of (-) charge is called variable or pH-dependent
charge
 Source of negative (-) charge
• Functional groups of organic colloids (carboxyl group,

phenolic –ON, alcoholic –OH)

 Source of positive (+) charge

• Protonation of exposed hydroxyl groups and NH2

groups in the case of organic colloids
Al-OH + H+ = AlOH2+
• Agriculturally important soils generally possess net
negative charge adsorbed on the surface
In humid regions : (H+,Al3+)>Ca2+>Mg2+>K+>Na+
In arid regions : Ca2+,Mg2+, Na+,K+,H+
• In general, the order of adsorbability or replacing
power of cations commonly found in soils is:
(H+,Al3+)>Ca2+>Mg2+>K+=NH4> Na+
Factors affecting strength of adsorption

• Charge (valence) : The higher the valence,

the stronger the adsorption
• Ionic sizes (radius): The smaller the size,
the stronger the adsorption
• Hydration of ion: The smaller the hydrated
size, the stronger the adsorption
• Concentration of solution: The higher the
concentration, the stronger the adsorption
 Remarks:
• Generally, agriculturally important soils possess net
negative charge
• Negatively charged colloids attract cations which
becomes adsorbed on the surface
• In humid regions, (H+, Al3+) > Ca2+ > Mg2+ > K+ >
Na+
• In arid regions, Ca2+, Mg2+ > Na+ , K+ > H+
• In general, the order of adsorbability or replacing
power of cations commonly found in soils is:
• (H+, Al3+) > Ca2+ > Mg2+ > K+ = NH4+ > Na+
 ION EXCHANGE
Two Types of Ion Exchange:
 Cation Exchange
 Anion Exchange
CATION EXCHANGE - The attraction of cations
(positively charged ions) on the surface of colloids and
exchanged for ions in the soil solution (NH4+,
Ca2+,Mg2+, Na­­+, H+, K+)
ANION EXCHANGE - The attraction of anions
(negatively charged ions) on the surface of colloids
and exchanged for ions in the soil solution (NO3-,
PO4-, SO4-)
 Ion Exchange Reaction is :

• Instantaneous
• Reversible
• Stoichiometric
( 1 milliequivalent (meq) of one cation is
replaced by 1 meq of another cation)
Principles Governing Cation Exchange Reactions

• Reversibility – A cationis usually replaced by a hydrogen

ion and this reaction is reversible
Micelle*Na+ + H+ = Micelle*H+ + Na+
• Charge Equivalence – Exchanges take place on a
charge-by-charge basis
Micelle*Ca2+ + 2H+ = Micelle*2H+ + Ca2+
• Ratio Law – The amount of exchangeable cation in the soil
solution will affect the ion’s equilibrium
Principles Governing Cation Exchange Reactions

• Mass Action – If a product precipitates, volatilizes, or

strongly associates with an anion, the reaction is not
reversible.
• Cation Selectivity – Higher charge and hydrated radius
affect the exchangeability of cations
Al3+ > Ca2+ > Mg2+ > K+ = NH4+ > Na+
 Cation Exchange Capacity
The capacity of a soil to
adsorb and exchange
cations and it is the
sum of all exchangeable
cations adsorb in a soil
expressed in meq/100 g
soil or in centimole/kg
soil (cmol/kg)

CEC indicates the fertility of the soil as it reflects the capacity of the
soil to retain nutrients
 Factors Affecting CEC:

 Soil Texture : the finer the texture, the higher the

CEC
 Amount and type of clay:
 Higher amount of clay, higher CEC
 More montmorillonitic type, higher CEC
 Amount of OM: the higher the OM, the higher the
CEC
 Soil pH: higher pH, higher CEC
• A high CEC value (>25) is
a good indicator that a
soil has a high clay
and/organic matter
content and can hold a
lot of cations.
• Soil with a low CEC value
(<5) is a good indication
that a soil is sandy with
little or no organic
matter that cannot hold
many cations.
http://www.spectrumanalytic.com/support/library/ff/CEC_BpH_and_percent_sat.htm
 CEC Determination: Ammonium Acetate
(NH4OAc) Method

The amount of NH4+ is

a measure of the CEC.
CEC and pH in Soil Orders
 CEC of Clay Minerals

• soil colloids Cation Exchange Capacity

(meq/100 g soil)
Humus 100 – 300
Vermiculite 80 – 150
Montmorillonite 60 – 100 Hydrous
Mica 25 – 40
Kaolinite 3 – 15
Figure 8.23
Relation of CEC to pH
 SOIL pH or SOIL REACTION (potential of
Hydrogen/potential H+)
• Refers to the acidity or alkalinity of the soil due to the relative
concentration of H+ and OH- ions
• One of the most important chemical properties of the soil
• Affects the availability of nutrient elements in the soil as well
as the microbial activities associated with soil fertility
• It is the negative logarithm of the hydrogen ion concentration
in the soil
• Defined by the equation:
Soil pH = - log [ H+] , where
[H+] = concentration of H+ in moles/liter
 Soil pH
– pH scale covers a range from 0-14,
– pH value of 7.0 is neutral (pure water)
– Values below 7.0 are acid and above 7.0 are basic.
– Each unit change in pH is associated with tenfold
change in the H+ concentration
– As pH increases, the H+ concentration decreases
 Category of Soil pH
pH Category pH value
Acidity Extremely Acid < 4.5
Very strongly Acid 4.5 – 5.0
Strongly Acid 5.1 – 5.5
Moderately Acid 5.6 - 6.0
Slightly Acid 6.1 – 6.5
Neutrality NEUTRAL 6.6 – 7.3
Alkalinity Mildly alkaline 7.4 – 7.8
Moderately alkaline 7.9 – 8.4
Strongly alkaline 8.5 – 9.0
Very strongly alkaline > 9.1
1 Strict neutrality is pH 7.0 but in field work, soils having soil pH value between 6.6 and 7.3 are called neutral. In rare cases, the
terms very slightly acid and very mildly alkaline may be used for soils of pH 6.6 to 6.9 and 7.1 to 7.3, respectively.
 Soil Chemistry / Soil pH

• Soil pH is the single most

important chemical property of
the soil (like soil texture is to
the physical properties)
• Knowing the pH of the soil will
quickly allow you to determine if
the soil is suitable for plant
growth and what nutrients will be
most limiting.
 Acid Base Chemistry
• Acid-base chemistry is an important part
of everyday life. The excess hydronium
(H3O+) ions in acids give them interesting
properties.
• Acids can react with metals and other
materials. The strong acid HCl is
produced in your stomach to help digest H3O+ depends on the
food. In dilute concentrations, acids are Strength of acid and
responsible for the sour taste of lemons, Initial concentration
limes, vinegar and other substances. Of acid
• Bases are also very reactive. The strong
base NaOH is used in many household
cleaning agents such as oven cleaner and
drain clog-remover.
• How do we measure the concentration of
an acid or base?
 pH
Hydronium ions
 Acid solutions are when pH is < 7.0 Hydroxide ions
Water
 Alkaline solutions are when pH > 7.0
 An acid can be defined as a proton
donor, a chemical that increases the
concentration of hydronium ions in
solution.
 Conversely, a base is a proton
acceptor, a chemical that reduces
the concentration of hydronium ions
Neutral Solution
in solution (and increases the
concentration of hydroxide ions).

Slightly Acidic
Solution
Soil pH- Measure H+ in the Soil Solution

* pH - the negative log of the hydrogen ion(H+)

concentration in the soil water solution.
pH = - log [ H+]
* the pH scale is how we measure acidity and
alkalinity of solutions.
at neutral (pH =7) the number of H+ = OH-
Remember –
at pH of 6 there are 10x more H+ ions than at a pH 7

and there are 100x more H+ ions between pH 7 & 5

 Soil Cation Exchange
• Cation Exchange - the
ability of the soil to
hold onto nutrients and
prevent them from
leaching beyond the
roots.
• Cations are “+ “charged
ions = Ca++, Mg++, K+,
NH4+,
• The more cation
exchange a soil has the
more likely the soil will
have a higher fertility
level.
 Cation
Cation Exchange
Exchange
• The interchange between a cation in
solution and another cation on the
surface of any negatively charged
material such as clay or organic
matter
H+
soil
Ca++ +2H+ + Ca++
H+
colloid soil solution soil
colloid solution
 Cation exchange influenced by:

1) Strength of adsorption:
Al+3 > Ca2+ > Mg2+ > K+ =NH4+ > Na+ >H+
held tight --------------------------> easily replaced
2) the relative concentration of the cations in the
Soil Solution
 Cation Exchange Capacity
1) the number of cation adsorption sites
per unit weight of soil or
2) the sum total of exchangeable
cations that a soil can adsorb.
* CEC is expressed in milliequivalents
(meq) per 100 g of oven dry soil.
Equivalent weight = molecular or atomic wt (g)
valence or charges per formula
 Back to Soil pH
Active Acidity - due to the H+ ion activity
in the soil solution at any given time
Reserve Acidity (on sites)- represented by
the H+ and Al3+ that are easily exchanged by
other cations (positively charged ion)
HHHH H+ H+
H Ca++ H+
Mg Mg++ H+
Ca Ca++ H+ H+
soil
H H H Na

Reserve Acidity Active Acidity -Soil solution

 Sources of acidity in Soil

* Hydrogen and Aluminum cations are responsible

for soil acidity
* Exchangeable Hydrogen is the main source of H+ at
pH 6 and above. Below pH 6 Aluminum is the main
source of H+ due to dissociation of Al from clay
minerals. Aluminum becomes more soluble at lower
pH’s
Al3+ + H20 ----> Al(OH)++ + H+
Al(OH)++ + H2O ---> Al(OH)2+ + H+
Al(OH)2+ + H20 ---> Al(OH)3 + H+
 Sources of
acidity in Soil

1. Nitrification: Ammonium to Nitrate

(oxidation of NH4+)
NH4+ + 2O2 ---> NO3- + H2O + 2 H+
2. O.M. decomposition
organic acids ionized :
R-COOH---> R-COO- + H+
respiration: CO2 + H2O ---->
H2CO3 = H+ HCO3-
 3. Acid rain
 Acid rain is caused by the
burning of fossil fuels.
 Burning oil, gas and coal in
power stations releases
Sulfuric Dioxide (SO2) into
the atmosphere.
 Burning oil and gasoline in
motor vehicles puts nitrogen
oxides (NOX) into the
atmosphere.
 These gases mix with water
droplets in the atmosphere
creating weak solutions of
nitric and sulfuric acids.
 When precipitation occurs
these solutions fall as acid
rain.
3. Acid Rain
SO2 +OH --> H2SO4 --> SO4- + 2 H+
NO2 + OH --> HNO3--> NO3- + H+
 Sources of acidity in Soil (cont.)
• 4. Uptake of basic
cations by plants.
Basic cations are
sources of OH- to the
soil solution.
• Ca++, Mg++, K+, =
• Basic cations that are
taken up by plants no
longer contribute OH-
to the soil solution.
• H+ ions are released
to the soil solution.
 Leaching
5. Leaching of basic cations -

as basic cations are

removed from the soil solution
by leaching they no longer
contribute the OH- ions to
neutralize the ever increasing
amounts of H+
Ca++ + 2 H20 ---> Ca(OH)2 + 2H+
-----> Ca++ + 2OH-
 Soil Acidity and Plant Growth
• Soil acidity is a major
environmental stress factor which
limits the growth of most crops.
• Acid soils are widely dispersed and
comprise approximately 40% of the
arable land in the world.
• In addition, acid rain also
accelerates the acidification of
soils.
• Aluminum (Al) ion is solubilized
from soils at low pH. This is a
major toxic factor for plant growth
for low pH soils. Acid soil (Yunnan Province,
People's Republic of China).
 Soil Acidity
• Soil acidification is a natural process
that is part of all landscapes.
• Land clearing of native vegetation and
their replacement with productive
crops and pastures has accelerated
acidification over the past 200 years.
• In the past 50 years a significant
lowering in soil pH due to greater
use of fertilizers, increased
production, a greater use of legumes
and an increase in irrigated
agriculture.
• An effective option
in some cases is a
matter of applying
lime…. however
• The land use should
be matched to the
capability of the
land and soil,
available rainfall,
and rate of
acidification.
 Acid Sulfate Soils
• Acid sulfate soils form
The red color of the
when pyritic* (mineral water is caused by
of FeS2) estuarine oxidized iron
sediments in the
subsoil are exposed to
air, oxidizing to form
sulfuric acid.
• A variety of soil
minerals react with
the acid and release
free aluminum, toxic
to crops and marine
life.
*Pyrite is the most common iron disulphide mineral in rock. It is found most often
in metamorphic and sedimentary rocks where it occurs as either a primary mineral
or a fine, widespread impregnation of subsequent origin. Pyrite is frequently found
in association with coal and shale deposits.
• Acid sulfate soils are
extremely acidic (at
times less than 3.0)
soil horizons resulting
from the aeration of
soil materials that are
rich in iron sulfides,
(FeS)
• Acid sulfate soils are
unique in that the
impacts can be so
severe that they can
affect engineering
works, agricultural
productivity, and
water quality of
estuarine systems
Acid soils have cost Australia $10
billion in environmental damage as
a result of coastal development.
• Iron staining is often a good
indicator of disturbed acid
sulfate soils.
• When acid sulfate soils are
disturbed and undergo oxidation,
the sulfuric acid produced
mobilizes iron, aluminum and
heavy metals present in the soil.
• Toxic amounts of dissolved iron
can then be washed into
waterways.
• This iron can precipitate when in
contact with less acid water,
such as rainwater or seawater.
• This results in a rust-colored
iron oxide scum or ‘floc’ which
can smother vegetation and stain
concrete and soil.
• From: 'QASSIT, Qld Department of
Natural Resources and Mines'

Green acid water leached from Acid Sulfate

Soils pours into a river