Chapter 7

Soil chemical properties

AGR521_Norazlina AS

Soil colloids
Soil colloids are the most
chemically ac:ve frac:on of soils
with very small size, less than 2 m
in diameter.
Because of their small size, all soil
colloids expose a large external
surface area per unit mass.
Soil colloids can aFract and hold
posi:vely charged ions due to their
large surface area and nega:ve
charges.
This characteris:c is important
because many posi:vely charged
ions are plant nutrients.

Soil colloids

Crystalline
silicate clay

Iron and
aluminum oxide
(Sesquioxides)

Types of
soil colloids

Non-crystalline
silicate clay

Organic
(Humus)

Silicate clay (crystalline and non-crystalline)

Silicate clay consists mainly of :ghtly
bonded, silicon and oxygen atoms.
The dierences between crystalline and
non-crystalline silicate clay is the
arrangement of sheet:
Crystalline silicate clay; their
crystalline structure is layered like
pages in book (Figure a).
Non-crystalline silicate clay; do not
exhibit ordered, crystalline sheet
(Figure b).

Kaolite (crystalline)
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Imogolite (non-crystalline)

Basic units of silicate clay

Silicate clay mineral composed of two kinds of ahorizontal sheet:

Silicon Tetrahedral
(1 Si, 4 O)

Aluminium-magnesium
Octahedral(1 Al/Mg, 6 O/OH)

Basic units of silicate clay: Sheets

The basic molecular and structural component of silicate clay. (a) A single tetrahedron,
composed of a Si ion surrounded by four O2 atom; and a single octahedron, in which an Al (or
Mg) ion is surrounded by six hydroxy groups or O2 atoms. (b) In clay crystals thousands of these
teterahedral and octahedral are connected to give planes of Si and Al (Mg ions).

Basic units of silicate clay: Combined sheets

1:1
Type of
silicate clay

Non-
expanding

Expanding

Kaolinite, halloysite
SmecHte
(Monmorillonite)
Vermiculite

2:1
Non-
expanding

Fine-grained mica/
Illite
Chlorite

Basic units of silicate clay: Combined sheets

Schema:c drawing illustra:ng the organiza:on of tetrahedral and octahedral sheets

in one 1:1-type mineral (kaolinite) and four 2:1-type minerals.

Charges of colloids
Permanent charges
Through isomorphous subs:tu:on
Mostly in 2:1 silicate clays
Temporary charges
Through pH dependent
Depend on soil pH
In 1:1 clays (kaolinite), humus, allophane and Fe/Al
oxides
Charge related to OH- group.

Isomorphous substitution
Isomorphous subsHtuHon: the replacement of one atom by another
without of similar size in a crystal la\ce without disrup:ng or changing the
crystal structure of the mineral (ca:on replacement in minerals).
Known as permanent charge and unaected by solu:on pH.
Major source of ve charge: replacement of tetrahedral Si+4 and octahedral
Al+3 ca:ons with ca:ons of lower charge.
Substitution of
Al3+ with Mg2+
formed one net
ve charge at
exchange sites.

Predominately in the 2:1 minerals.
Occur during the forma:on of these minerals and unaected by present
environmental condi:ons.

pH dependent
Second source of charges is associated with edge charge of the clay
minerals.
The quan:ty of ve and +ve charge on the edges depends on soil
solu:on pH.
Termed as variable or pH-dependent.
Under low pH, the edge is +ve because of the excess H+ ions associated
with the exposed Si-OH and Al-OH groups.
As soil solu:on pH increases, some of the H+ is neutralized and the (-ve)
edge charge increases.
Increasing the pH above 7.0, complete removal of H+ ions on the Si-OH
and Al-OH groups, which is maximizes the (-ve) edge charge.
Soil OM is source of pH dependent charge with the dissocia:on of H+
from carboxylic acids and phenolic acids groups. As pH increases, some
of these ion H+ neutralize and increasing the (-ve) surface charge.

1:1-type silicate clay

Adjoining sheet

1:1, indicate; 1 Silicon tetrahedral and 1 aluminium octahedral sheet

(for each layer).
Example: Kaolinite, halloysite, nacrite and dickite.
The two types of sheet are :ghtly held together because the apical O
atom in each tetrahedron also forms the boFom corner of one or
more octahedrons in the adjoining sheet.

1:1-type silicate clay

Layer 1

Hydroxyl plane is exposed:

removal/addi:onal of H+ can produce +
or charges depending on the soil pH.
Also binds with anions.

When the sheets are stacked on top of

one another, the adjacent layers are
bound together by hydrogen bonding.
Strong hydrogen bonding results no
swelling in kaolinites (non-expanding
Layer 2
Hydrogen bonding
adjacent layer).
Kaolinite exhibit less plas:city, s:ckiness,
cohesion, shrinkage, swelling and hold
The OH- of the octahedral sheets in
less water than other clays.
layer 2 are adjacent to the basal O- of
the tetrahedral sheet of layer 1, which 1:1 clays are easy to cul:vate for
form hydrogen bonding between these
agriculture and suitable for roadbed and
two layers (at interlayer).
building founda:ons.

2:1-type silicate clay (expanding)

Interlayer

Each layer contains 1 octahedral sheet

sandwiched between 2 tetrahedral sheets

2:1-type silicate clay (expanding: Smectite group )

Smec:tes hve a 2:1 structure that exposes a
layer of O atoms at both the top and boFom
plane that contributes to the loosely bound at
interlayer (very weak O:O and O:ca:on linkage
between 2 layers).
Common smec:te: Montmorillonite.
Interlayer expansion occurs as H2O lls spaces
between layer in dry clay.
Have a high amount of nega:ve charge due to
isomorphous subsHtuHon:
Mg2+ oien replaces Al3+ in the octahedral
sheet (refer to the next gure)
Al3+ some:mes replaces Si4+ in the
tetrahedral sheet

Mg2+
Al3+

Al3+ in the octahedral sheet

Mg2+
Al3+

Al3+ come out from colloid,

3 ve charge at exchange site

Mg2+

Al3+

1 ve charge is not occupied

2:1-type silicate clay (expanding: Vermiculite group )

Very high nega:ve charge, due to frequent
subs:tu:on of Si4+ ions with Al3+ in the
tetrahedral sheets (isomorphous
subsHtuHon).
CEC is higher in vermicullites than in any
other clay.
Swelling occurs, but less than in smec:tes
due to strongly adsorbed H2O molecules,
Al-hydroxyl ions and ca:ons, which act
more as bridges than wedges.

Al3+
Si4+

Si4+ in the tetrahedral sheet

--

Al3+
Si4+

Si4+ come out from colloid,

4 ve charge at exchange site

Al3+

Si4+

1 ve charge is not occupied

2:1-type silicate clay (non-expanding)

2:1-type silicate clay group

Mica / Illite

Chlorites

Structure

Tetrahedral
Octahedral
Tetrahedral

Tetrahedral
Octahedral
Tetrahedral

Tetrahedral
Octahedral
Tetrahedral

K+

Hydroxide
Tetrahedral
Octahedral
Tetrahedral

Source of charge

Subs:tu:on of Si4+ with Al3+

in tetrahedral sheets

Subs:tu:on of Si4+ with Al3+

in tetrahedral sheets

CaHon in octahedral sheets

Al

Fe and Mg

Interlayer sheet

The size of K+ can t in

between layers

Mg-octahedral hydroxide
sheets is sandwiched in
between adjacent 2:1 layers.

The adjacent sheet binding

between layers

Strong

Strong with H:O binding

2:1-type silicate clay (non-expanding: Mica group)

Interlayer

Each layer contains 1 octahedral sheet

sandwiched between 2 tetrahedral sheets

K+ ions are :ghtly held between layers, that prevent the movement of
water and ca:ons into the space between layers.

Nonsilicate colloids (Iron and Aluminium Oxides)

Octahedral sheets: Fe2+ or Al3+ in
the cation positions.
No tetrahedral sheets and no Si.
Lack of isomorphous
substitution (little ve charge)
Small charge (+ or -) due to
removal or addition of H+ from
surface hydroxyl groups.
Non-expansive and relatively
little stickness, plasticity and
cation absorption.
E.g: gibbsite, goethite,
ferrihydrite and hematite.

Structure of gibbsite, an aluminum

oxide. Consists of dioctahedral
sheets (two octahedral) that are
H-H bonded.

Humus (organic matter)

Non-crytalline organic substance.
Consists of very large organic
molecules with general chemical
composi:on: 40-60% C, 30-50% O,
3-7% H and 1-5% N.
Actual structure of humus colloids is
very dicult.
-ve or +ve charges (large ve sites) is
develop as H+ ion are either lost or
gained from:
Carboxyl group COOH
Phenolic hydroxyl group
Alcoholic hydroxyl group
Humus can adsorb large amounts of
water due to its great surface area and A possible structure of humic acid, primary
many hydrophilic (water-loving) group. cons:tuent of colloidal humus in soils

Cation exchange capacity (CEC)

CEC is the interchange between a ca:on in solu:on and another
ca:on on the surface of any nega:vely charged material such as
clay or organic maFer.
It measure the ability of the soil to hold onto nutrients and prevent
them from leaching beyond the roots.
The more ca:on exchange capacity a soil has, the more likely the
soil will have a higher fer:lity level.
The ca:on exchange capacity of a soil is simply a measure of the
quan:ty of sites on soil surfaces that can retain posi:vely charged
ions by electrosta:c forces.
Ca:ons retained electrosta:cally are easily exchangeable with
other ca:ons in the soil solu:on and are thus readily available for
plant uptake.

Quantifying CEC and AEC

Soil CEC represents the total quan:ty of (-) surface charge on the
minerals and OM available to aFract ca:ons in solu:on.
CEC is expressed as miliequivalents of (-) charge per 100 g of oven dried
soil (meq/100 g) or cmolc/kg.
1 mole = 6 x 1023 atoms, molecules, ions or compounds
Equivalent weight /(eq.) wt : mass (grams) of a substance (ca:on, anion
or compound) that will react with 1 g of H+ or 1 mole (6 x 1023) of
charges (g/eq).

Atomic weight = g/ 6 x 1023 ions or molecules

Equivalent weight = g/ 6 x 1023 (-) or (+) charges
= g/mole charge
= g/eq

 1 mole K+ ions = 6 x 1023 K+ ions

= 6 x 1023 or 1 mole (+) charges
atomic weight of K+ = 39 g/mole K+ ions
equivalent(eq) weight of K+ = 39 g/mole (+) charges or 39 g/eq

1 mole Ca2+ ions

atomic weight of Ca2+
eq. weight of Ca2+

= 6 x 1023 Ca2+ ions

=2 x (6 x 1023) (+) charges
= 2 mole (+) charges
= 40 g/mole Ca2+ions
= 40 g/2 mole (+) charges
= 20 g/1 mole (+) charge
= 20 g/eq
What is eq. wt of
Al3+ (27 g/mole)?

 The soil CEC is strongly aected by the nature and amount of

clay minerals and OM present in soil:
2:1 minerals >1:1 minerals
High sand and OM soils > sandy and low OM soils
* > indicate content more CEC

Typical CEC values for dierent soil textures:
Soil texture

Meq/100 g

Sands (light colored)

3-5

Sands (dark colored)

10-20

Loams

10-15

Silt loams

15-25

Clay and clay loams

20-50

Organic soils

50-100

 Principal/predominant ca:ons of:

Acidic soil: Al+3, H+, Ca+2, Mg+2 and K+
Neutral or basic soils: Ca+2, Mg+2, K+ and Na+
The strength of ca:on adsorp:on (lyotropic series) is depends on:
Ca:on charge ( charge, adsorp:on strength)
If similar charge, determined by the size or radii of hydrated
ca:ons ( size/radii, adsorp:on strength)

Al+3 > *H+ > Ca+2 > Mg+2 > K+ = NH4+ > Na+

*H+ is unique because of its very small size and high charge
density, thus, its adsorp:on strength between Al+3 and Ca+2.

Determination of CEC

1N NH4OAc

Base ca:on at the

exchangeable sites
Leachate containing
base satura:on

A conven:onal method to
determine CEC value: NH4OAc
(ammonium acetate) method
buered at pH 7.0 by leaching
method.
When soil sample is extracted
with 1 N NH4OAc, the
exchangeable ca:ons are
replaced by NH4+ and CEC
become saturated with NH4+.
Then, dierent salt (eg; K2SO4)
is needed to replace NH4+. The
leachate containing the NH4+ is
a measure of the CEC.

Determination of CEC

Saturated the
soil with NH4+

Measure
exchangeable
cations in leachate

Leach NH4+
with K+

Measure
CEC (NH4+)
in leachate

Base saturation (BS)

Base satura:on (%BS): the percentage of total CEC occupied by
Ca2+, Mg2+, K+ and Na+.
Base satura:on: (total bases/CEC) x 100
%BS, the availability of Ca2+, Mg2+ and K+ to plant.
soil pH, %BS,

Anion exchange (AEC)

Anion exchange: anions in soil solu:ons that adsorbed to (+) charge
sites on clay mineral surfaces and OM.
The (+) charges are on the mineral edges and OM.
Anion exchange also occur with OH group on the hydroxyl surface of
kaolinite.
Displacement of OH ions on hydrous Fe and Al oxides par:cularly in
highly weathered soils of the tropics and subtropics.
AEC , as soil pH .
AEC in acid soils high in 1:1 clay > 2:1 clay

H2PO4- > SO42- > NO3- > Cl-

Acid and base concept

Acid: A molecule that donates H+ to some other molecule in water.
Base: A molecule that accepts H+ in water.

H2O D H+ + OH-

(weak acid, donate H+)

AFaches to another H2O molecule

H2O + H+ D H3O+ (weak base, accept H+)

Strong acid: 100% of dissocia:on of acid when added to water.
Weak acid: 1% or slight dissocia:on of acid when added to water.
HCl D H+ + Cl- (Strong acid, 100% dissociation)
CH3COOH D CH3COO- (Weak acid, 1% dissociation)

Soil pH
Soil pH: determina:on of ion hydrogen (H+) concentra:on/ac:vity in

soil system
It is nega:ve logarithm of the ac:ve H+ in solu:on.

pH = - log [H+]
= log 1/[H+]

pH of pure water:

pH

= -log [H+]
= - log [1 x 10-7]
= - (-7) log [1 x 10]
= 7 log 10
= 7 x 1
= 7

[H++] of pure
[H ] of pure
water =
water =
0.0000001

1 x 10-7 -7
@ 1 x 10

= log [1/[H+]
= log [1/[1 x 10-7]
= log 107
= 7 log 10
= 7 x 1
= 7

Soil pH
The pH scales ranges from 0 to 14 with 7 as
the neutral point:

[H+] x [OH-] = 1 x 10-14

At pH 7, the H+ concentra:on is equal to OH- :


[H+] = [OH-] = 1 x 10-7

The H+ concentra:on has a tenfold change
between each whole pH number, thus a soil
of pH 5 has 100 :mes more H+ in solu:on
than a soil with a pH of 7.

Classification of soil acidity

The sources of Hydrogen ion/acidic in the tropic soil

Atmosphere/precipita:on
Leaching
Oxida:on of pyrite
Oxida:on of commercial fer:lizers
Oxida:on in chemicals (Sulphur)
Uptake of nutrients by plants
Exchange of nutrients during nutrients uptake (H+ ions)
Decomposi:on of OM
Decomposi:on of OM and root respira:on (CO2)

Influence of pH on nutrient availability and microbial activity

Soil pH has signicant eect on
soil chemical proper:es and
biological ac:vi:es.

In acidic soil (low soil pH):
v macronutrients (N, P, K, Ca,
Mg and S).
v micronutrients ( Fe, Mn, Zn,
Cu and Co)
In slightly to moderately
alkaline:
v macronutrients (except P)
and Mo.
v micronutrients (Fe, Mn, Zn,
Cu and Co)
Bacteria and ac:nomycetes
func:on well at intermediate
and high pH levels.

Soil pH

Buffering capacity (BC)

Buering capacity: is the ability or capacity of soil to resupply an ion
to the soil solu:on.
It measure the capacity of soil to maintain the concentra:on of
nutrients in soil.
For example: When plant root absorbs nutrients such as K+ from the
soil solu:on, the K+ in the soil solu:on will decreased. The mineral
soils resupply the K+ to the soil solu:on from the exchangeable to
maintain the K+ concentra:on in soil solu:on.

CEC, OM, and other solid cons:tuents, BC.
As CEC increases with increasing clay content, therefore, BC in ne-
textured soil > BC in coarsed-texture soil.
BC is very important soil proper:es that strongly inuences nutrient
availability.

Buffering capacity (BC)

Important of buering capacity:
To ensure reasonable stability in the soil pH
Prevent dras:c changes of soil pH which have signicant
eect to higher plants and soil organisms
Example: acid rain

Inuences the amounts of amendments (lime or sulphur
required to eect the desired change in soil pH)
PBS at around 50% is considered good for most soils.

Determination of soil pH: Dye method

Determination of soil pH: Electrometric method

Methods of increasing or decreasing soil acidity

Increasing soil acidity:
Acid OM
Inorganic chemical (e.g.; Ferrous sulphate)
Decreasing soil acidity:
Liming materials such as:
Carbonate forms (e.g.; limestone that contain calcite (CaCO3) and dolomite
[CaMg(CO3)2])
Oxide and hydroxide forms:
i. Calcium oxide (CaO)
Known as quicklime/burned lime
Produce by hea:ng limestone (calcite or dolomite) at 850oC and
released CO2

ii. Calcium hydroxide [Ca(OH)2]

Known as hydrated lime
Produced by adding hot water

Lime requirement
Liming material is added to soil in order to decrease the soil acidity.

Liming is a process of altering soil pH to levels that are suitable for
plants.

Eect of lime on soil properHes:
Ca2+ and Mg2+
Na+
i. Physical
Improve soil aggregates

Na+ at soil exchange sites

Ca2+ and Mg2+

from liming
materials

Ca2+ and Mg2+ from lime

replaced the Na+ at exchange
site and aFract soil par:cles
:ghtly due to its ++ than Na (+)

Lime requirement
ii. Chemical
Increase soil pH
reduce Al and Mn toxicity
Increase the nutrients
availability
iii. Biological
Most soil organisms are
more ac:ve with
increase soil pH

Lime requirement

Macronutrients
Non-mineral

Primary

Mostly from air

and water

Secondary

Micronutrients

Mostly from soil

Iron (Fe)
(Fe2+, Fe3+)

Carbon (C)
(CO2)

Nitrogen (N)
(NH4+, NO3-)

Hydrogen (H) Phosphorus (P)

(H+, OH-, H2O) (H2PO4-, HPO42-)

Oxygen (O)
(O2)

Potassium (K)
(K+)

(*) indicate forms adsorbed by plant

Calcium (Ca)
(Ca2+)

Manganese (Mn)
(Mn2+, Mn4+)
Boron (B)
(H3BO3, BO3-, B4O72-)

Magnesium
(Mg)
(Mg2+)
Sulphur (S)
(SO42-)

Zinc (Zn)
(Zn2+)
Copper (Cu)
(Cu2+)
Molybdenum (Mo)
(MoO42-)
Chlorine (Cl)
(Cl-)
Nickle (Ni)
(Ni2+)

Movement of ions from soils to roots

1
2

Root interception
Root intercep:on: exchange of ions through physical contact
between the root and mineral surfaces.

Ions on the root surface (e.g. H+) D Ions on clays and OM surface.

ions adsorbed or the surface of root cells and clay par:cles are not
held :ghtly but oscillate within small volume of space.

If the roots and clay par:cles are in close contact with each other,
the oscilla:on volume of ions adsorbed on root surface may over by
the oscilla:on volume of ions adsorbed on clay par:cles, and the
ions adsorbed on clay par:cle may be exchanged with the ions
adsorbed on root surface directly without rst being dissolved in
soil solu:on.

H+

K+

Clay

Oscilla:on
volume

Root

Root interception

K+

H+

Clay

Root

The ions held by electrosta:c forces at these

sites oscillate within a certain volume.

When the oscilla:on volumes of two ions

(H+ and K+) overlap, ion exchange occur.
K+ adsorbed by root and u:lized by plant.

Root interception
Root interception can be enhanced by mycorrhiza which
colonization is favor under conditions of slightly acidic soil pH,
low P, adequate N and low temperature.
Without mycorrhiza

With mycorrhiza

Mass flow
Soil Fertility and Fertilizers

John L. Havlin

Mass ow: Moving of dissolved nutrients in

owing soil solu:on towards the roots
It occurs when ions in soil solu:on are
transported to the root as a result of:
water uptake (transpira:on) by the plant
Water evapora:on at the soil surface
Percola:on in the soil prole
The quan:ty of nutrients reaching roots by
mass ow is determined by:
The rate of water ow or
The water consump:on of plants
Average nutrients concentra:on in the
soil water.
Mass ow decreased when:
soil moisture
Low temperature
evapora:on

Ca2+
NO3NO3Ca2+

2014 by Pearson Higher Education, In

Upper Saddle River, New Jersey 07458 All Rights Reserve

Diffusion nutrients move from higher concentration

in the bulk soil solution to lower concentration at the root

Diffusion
Diusion occurs when an ion
move from an area of high
concentra:on to low
concentra:on area.
The nutrients concentra:on at
the root surface decreased
compare to the bulk soil solu:on
concentra:on.
Therefore, ion diuse from soil
solu:on (high concentra:on)
towards the root (low
concentra:on).
Most of P and K move to the
root by diusion.

NO3-

John L. Havlin

High concentra:on

NO3NO3

Soil Fertility and Fertilizers

Low concentra:on

NO3-

NO3-

NO3-

2014 by Pearson Higher Education, In

Upper Saddle River, New Jersey 07458 All Rights Reserve