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Tablets of Soil Science - Soil Chemistry

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Chapter 3 : Soil Chemistry 85

Chapter 3

Soil Chemistry

 Soil chemistry is the study of the chemical characteristics of

the soil. Soil chemistry is affected by mineral composition,
organic matter and environmental factors.
 Soil Colloid – The colloidal state refers to a two-phase system
in which one material (or materials) in a very finely divided
state is dispersed through a second.
 In general, the range of true colloids is from 2 nm to 200 nm.
 The scattering of light by colloids is called Tyndall scattering
or simply “Tyndall effect”.
 Due to unbalanced impact of solvent molecules on colloid
particles, these particles move in a zig-zag way in the soil
solution which is called “Brownian movement”.
 A typical value of CEC of humic colloids (which is pH
dependent) 200 - 250 c. mol (p+) kg-1 or even higher.
 The tetrahedral unit is SiO4-4 in which the silicon ion is
equidistant from the 4 oxygen ions.
86 Tablets of Soil Science

 The octahedral unit consists of an Al, Fe or Mg ion, surrounded

by equidistantly spaced 6 oxygen or hydroxyl ions in the form
of an octahedron.
 When Al is present, say in gibbsite structure, Al2 (OH)6, two
thirds of the ionic positions are filled to become the unit is
called “Dioctahedral structure”. With divalent cations, as in
brucite Mg3 (OH)6, all the octahedral positions are filled to
give a “Trioctahedral structure”.
 1:1 minerals – Dimorphic minerals.
 2:1 minerals – Trimorphic minerals.
 2:2 minerals – Tetramorphic minerals.
 The 1:1 types of clays are include kaolinite, halloysite,
anauxite, nacrite and dickite. To illustrate the properties of 1:1
silicate clays we will focus on kaolinite, which is by far the
most common in soils.
 Kaolinite – The most widely occurring clay mineral in soils is
kaolinite, which is the simplest mineral among all the clay
minerals. This is the dominant type of clay mineral in red and
laterite soils. In this mineral units are held together very rigidly
by hydrogen bonding. Basal spacing of kaolinite is 7.2 A0 (0.72
nm). On the other hand kaolinite mineral can have an anion
exchange capacity as high 43 me/100 g at an acidic equilibrium
pH of 4.7
 Montmorillonite – Montmorillonite is best example for 2:1
type expanding clay mineral. A Montmorillonite crystal unit
consists of a single gibbsite octahedral sheet sandwiched
between two silicon tetrahedral sheets. The crystal units are
held together by very weak oxygen-oxygen linkages.
 Vermiculite has high CEC on volume base and high surface
area among all clay minerals.
 Layer charge highest for Mica and Chlorite.
Chapter 3 : Soil Chemistry 87

 AEC highest in Kaolinite.

 Illite is non expanding 2:1 clay mineral and which is also
called hydrous mica.
 Montmorillonite is 2:1 type expanding clay mineral.
 Vermiculite is slightly expanding 2:1 clay mineral.
 Chlorite (had brucite sheet) is example for 2:2 or 2:1:1 mineral.
 CEC on weight base highest in humus.
 A number of techniques have been developed to identify clay
minerals such as X-ray diffraction analysis (XRD technique),
Electron diffraction analysis, Differential thermal analysis,
Electron micrograph, Surface area determination, Cation
exchange capacity determination, Elemental chemical analysis
and Y-index.
 Ethylene glycol (EG) or ethylene glycol monoethyl ether
(EGME) adsorption is recommended to determine total,
internal and external surface areas of clay minerals.
 Molecular ratio of silica/sesquioxide (SiO2/ R2O3) where R2O3
stands for Fe2O3 and Al2O3 was used extensively to ascertain
whether the soil clay was dominantly kaolinitic or
montmorillonitic. In the former, the ratio is less than 2 (for
kaolinite) where as in the latter ratio is higher than 2 (for
montmorillonite).
 The content of K2O in illite varies from 6 - 10 %.
 The Y-Index was proposed by “Martin and Russell”.
 Y-Index has proved to be useful to assess the dominating type
of clay mineral in soil.
 The laws governing structural characteristics of the
phyllosilicates are known as Goldschmidt’s Laws – Law I and
Law II.
88 Tablets of Soil Science

 Goldschmidt’s Law I - In an ionic crystalline compound,

Isomorphous replacement of one cation by another, without
incurring any change in the order of the crystal pattern, is
permitted provided that the radii of the cation replaced and the
cation substituting it agree with in 15 %.
 Goldschmidt’s Law II - This law also called “Radius Ratio
Law”. When the number of anions surrounded a central cation
such that they satisfy the charge completely, the number of
anions that can be so accommodated around the cation depends
on the radius of the central cation to that the surrounding
anions. Thus, this ratio of ionic radii governs is known as
“Coordination number”.
 Isomorphous Substitution – Negative charge developed in
layer silicate clay minerals by Isomorphous substitution.
Isomorphous substitution is the substitution of one ion with
another ion in a mineral without a significant change in the
crystal structure.
 Generally Exposed edges, Isomorphous substitution and Anion
exchange are important sources for negative charge in silicate
clays.
 The pH at which net surface charge of the soil colloids is zero
is called zero point charge or ZPC (here positive charge is
equal to total negative charge, resulting in the zero net charge).
 Among the functional groups, carboxylic groups are acidic
groups with higher dissociation constant than other organic as
well as inorganic S-OH groups. The carboxylic groups
dissociate at the lower pH giving rise to the development of the
negative charges. Phenolic and enolic groups dissociate at the
higher pH to produce negative charges. Unlike inorganic S-OH
groups, organic COOH and OH groups do not associate with
H+ at lower pH, meaning there by that net positive charge does
Chapter 3 : Soil Chemistry 89

not develop on the organic colloids. Thus soils rich in organic

matter may not have a zero point charge.
 The thickness of diffuse double layer decreases as the
electrolyte concentration in the water increases at equal
equivalent concentrations of electrolyte.
 Divalent cations decrease the thickness of double layer more
strongly than that of monovalent cations, and trivalent more
strongly than divalent.
 The double layer is thicker if the exchangeable ions are sodium
(Na+) and potassium (K+) than calcium and magnesium.
 DDL thickness will be more due to presence of sodium than
potassium (That is why soils containing more sodium show
high pH resulting from more thicker diffuse double layer).
 “With increasing the electrolytic concentration four times,
DDL thickness reduces to half”.
 The potential difference between the fixed layer and freely
mobile portion of DDL (Diffuse Double Layer) is known as
“Zeta potential”.
 Due to decrease in pH the zeta potential can be reduced
resulting from the reduction of negative charge on the clay
micelle and also from the replacement of sodium or other
monovalent cations with hydrogen (H+) ion.
 Ion exchange in soil system refers to exchange of equivalent
amounts of ions between two phases in equilibrium in contact
in a reversible process.
 The experimental evidence of cation exchange was provided
around 1850 by Thompson, followed by J. Thomas Way.
 Colloidal material of the soil with effective particle diameters
of less than 20 microns being the most important site for
causing the ion exchange phenomena.
90 Tablets of Soil Science

 Inverse Ratio Law was given by Matson.

 Adsorption is defined as a phenomenon by which an increase
in concentration or an accumulation of an ion species on a solid
occurs due to ion exchange or other reactions. Desorption is a
phenomenon by which the replacement or release of an
adsorbed ion occurs.
 The weight of one hectare furrow slice (depth of 0-15 cm
layer) is 2.2 × 106 kilograms.
 Famous Physical Chemist C. E. Marshall had emphasized that
the CEC is the second most important in nature, surpassed in
fundamental importance only by the photosynthetic process of
green (CEC is next to photosynthesis).
 ECEC (Effective Cation Exchange Capacity) – It is the sum
of exchangeable bases (Ca+2, Mg+2, K+ and Na+) as extracted
by 1 M NH4OAc (one molar ammonium acetate at 7 pH) and 1
M KCl extractable Al+3.
 In most soil laboratories, CEC of a soil is determined by
extraction with 1 N neutral ammonium acetate (1N NH4OAc).
 Surface Charge Density = CEC/Specific Surface Area.
 On the basis of experimental data, the preference of different
anions for the positive sites has been found to follow the order
- SiO4-4 > PO4-3 > SO4-2 > NO3- = Cl-.
 Kaolinite mineral can have an anion exchange capacity as high
43 me/100 g at an acidic equilibrium pH of 4.7.
 The repulsion of anions by the negatively charged sites leads to
a local deficit of anions near a clay particle in comparison with
the equilibrium solution. The deficit has been termed as
“Negative adsorption”.
 Negative adsorption also called “Anion exclusion”.
Chapter 3 : Soil Chemistry 91

 Langmuir Adsorption Theory is the basic theory of adsorption

of gases on solids.
 Freundlich Isotherm is one of the most widely used adsorption
equations to describe the experimental data on adsorption of
ionic or molecular species in soil.
 The theory of Brunauer, Emmet and Teller (BET) extends
Langmuir derivation to obtain an equation for “Multilayer
adsorption”.
 Ratio between the cations on soil surface and CEC is termed as
the relative base saturation and when expressed on percentage
basis, it is termed as the percent base saturation or base
saturation percentage (BSP)
 At pH 7.0 percent base saturation is about 80 and each unit
decrease in pH, base saturation decreases by about 20 %.
 If base saturation percentage is more than 80 which indicates
highly fertile soil, while if it is between 50 - 80 % which
indicates medium fertile soil and if it is less than 50 % less
fertile soil.
 The sequence of tenacity with which ions will be adsorbed is
called “Hofmeister series or lyotropic series”. For the alkali
ions, the selectivity has been often found to increase in the
same order of lyotropic series namely Li+ < Na+ < K+ < Rb+ <
Cs+ and alkaline earth ions it follows the sequence Mg+2 < Ca+2
< Sr+2 < Ba+2. Lyotropic series in respect of adsorbability is
given as Al+3 > Ca+2 > Mg+2 > K+ = NH4+ > Na+.
 Activity Coefficient – It is the ratio between the activity
(chemical) and the concentration of a substance in solution.
When concentration is corrected by a factor which is always
less than 1 and that factor is called activity coefficient. This can
be expressed by a = f x c.
92 Tablets of Soil Science

 Activity in the soil solution phase can be calculated easily by

Debye-Huckel equation
 Concept of Root CEC was given by Devaux.
 The cation exchange capacity of roots of different plant species
ranges from less than 10 to almost 100 me/100 g of soil. The
exchange properties of roots appear to be attributable mainly to
carboxyl groups (-COOH) present in pectic substances.
 Complementary ion effect is defined as the influence of one
adsorbed ion on the release of another ion from the surface of a
colloid.
 Gapon constant values commonly range from 0.010 - 0.015.
 For heterovalent exchange, the equations proposed by
Vanselow and Gapon are widely used and both are based on
“law of mass action”.
 Krishnamoorthy, Davis and Overstreet (KDO) proposed
“Nearest Neighbour Model” and Jenny proposed “Oscillation
volume”.
 F. G. Donnan in 1911. Donnan membrane equilibrium belongs
to mass action equations.
 Jarusov’s Rule (Complementary ion principle) – The
exchangeability of a given ion was not a constant, but was a
function of its amount in relation to the amount and kind of
other cations present.
 Electrons, small negatively charged components of atoms of all
substances.
 Protons, positively charged particles of much greater mass than
electrons.
 The unit of mass in the International System of Units (SI) is the
kilogram (kg).
 Gram atomic weight = atomic weight in grams.
Chapter 3 : Soil Chemistry 93

 The number of atoms in 1 gram atomic weight of any element

is as 6 × 1023. This number is known as Avogadro’s number
and is used for a number of calculations, such as calculating the
weight of one atom.
 Normality - The number of equivalent weights of a substance
dissolved in 1 litre (L) of a solution determines the normality
(N) of the solution- in other words, “Normality” is the strength
of the solution. If one equivalent is dissolved in 1 L of a
solution, the solution has a strength of 1 N (one normal). If two
equivalents are present in 1 L of solution, the solution is 2 N.
The symbol N is usually italicized, or when a capital letter is
used underscored or underlined (N), to distinguish it from the
symbol N, the nitrogen element.
 Molarity (M) is defined as the number of moles of a substance
per litre of solution. Molality (m), on the other hand, is the
number of moles per kilogram (kg) of water, and formality (f)
is the number of moles of a substance per kg of solution.
 Another chemical unit, which is sometimes used in soil
chemistry, is the mole fraction. The latter is defined as the ratio
of the number of moles of a given substance to the total
number of moles of all constituents in solution, including the
number of moles of water if it is an aqueous solution.
 Radioactivity, discovered for the first time in 1896 by Henri
Becquerel, involves a spontaneous disintegration of certain
types of elements or atoms to form other elements or atoms.
 Half-life is a measure of the rate of decay of radioactive
material. It is the length of time during which the material loses
one-half of its radioactivity, or the time required for
decomposition of one-half of the atom. In the latter sense, the
term half-life has now been adopted for measuring the
persistence of pollutants in soils.
94 Tablets of Soil Science

 Half-life of 14C is only 5370 years.

 The Nernst equation was formulated by Walther Hermann
Nernst (1864 – 1941), a German physical chemist (Wahl,
2005). Known also for his Nernst–Thompson rule, explaining
the ionization process, and for the Heat Theorem as reflected in
the Third Law of Thermodynamics, for these and many other
contributions Nernst was awarded the Nobel Prize for
electrochemistry in 1920. This provides a means for the
determination of the redox potential of a half-cell reaction and
can also be used to calculate the electromotive force of the
whole electrochemical cell.
 Henry’s rule indicates that the solubility of a gas in a liquid is
proportional to the partial pressure of the gas in contact with
the liquid.
 When compounds dissolve, the energy is released, a
phenomenon called heat of solution. The ions are then hydrated
and the corresponding release of energy is called heat of
hydration. In thermodynamic language, it is the increase in
enthalpy due to formation of a hydrate. In contrast, when clay
particles are hydrated, the energy released is called heat of
wetting.
 Biological oxygen demand (BOD) -This is defined as the
amount of oxygen consumed by microorganisms in the process
of decomposition of organic matter during a 5 - day incubation
period. The test was developed in England, where it was
believed that dissolved organic matter not decomposed within
5 days would be transported into the sea.
 Chemical oxygen demand (COD) -This is defined as the
amount of oxygen consumed in the chemical oxidation of
organic matter by potassium dichromate in the presence of
sulphuric acid. The analysis for oxidation of organic C is
known today as the Walkley – Black method.
Chapter 3 : Soil Chemistry 95

 Total oxygen demand (TOD) - This is the amount of oxygen

consumed in the catalytic oxidation of carbon. The amount of
CO2 produced in the reaction is measured.
 The attraction of soil solids (matrix) for water provides a
matrix force, and that part of the water potential attributed to
the matrix force is called matric potential. Taylor and Ashcroft
(1972) reported that the matric potential is similar to the
capillary potential and replaces terms such as soil moisture
tension, soil moisture suction, or matric suction.
 The Debye - Huckel theory, developed by Peter Debye and
Eric Huckel in 1923, is simply a concept conveying the
behaviour of ionic solutions, in which electrical potential
fluctuations due to ions are practically very small.
 The term ionic strength is used as a measure of the strength of
ionic concentrations in the solution. The concept was
introduced by Lewis and Randall (1921) to assess the
combined effect of the activities of several electrolytes in
solution on a given electrolyte.
 Lignin is considered, second to cellulose, the most abundant
biopolymer in nature.
 Cyclosilicates - Tourmaline, benitoite.
 Inosilicates - Amphibole, pyroxene, hornblende.
 Nesosilicates - Garnet, olivine, zircon, topaz.
 Phyllosilicates - Chlorite, vermiculite, illite, kaolinite, smectite.
 Sorosilicates – Epidote.
 Tectosilicates - Feldspars, quartz, Zeolite.
 Members of the kaolinite group are kaolinite, dickite, nackrite,
and halloysite. Except for halloysite, the other minerals are
nonexpandable in water. Upon heating, it is irreversibly
dehydrated, and the mineral is then called metahalloysite.
96 Tablets of Soil Science

 The illite minerals are micaceous types of clay. However, in

contrast with the true micas, which are primary minerals or
primary formation, illites are of secondary origin. They are also
known under the names “hydrous mica” or “soil mica”. The
term illite is suggested for the fine-grained minerals in this
group, whereas the coarser particles are frequently called
hydrous mica.
 Vermiculite name is derived from vermiculare or vermicularis
(Latin: “wormlike,” or “to breed worms”), because upon
heating, the mineral becomes elongated, twisted, and curled.
After heating, it usually expands to 20 to 30 times its original
size.
 The Fe-rich chlorite is called chamosite, and Mg-rich chlorite
is known as clinochlore.
 Several of the different types of clay minerals may be stacked
together as a packet. This process is called interstratifications
and such clays are referred to as interstratified clays or mixed-
layer clays.
 In general, solubility of silica minerals is related to the packing
density of the silica tetrahedra. The solubility increases in the
following order: Quartz < crystobalite < opal < amorphous
silica.
 The x-ray diffraction (XRD) method is perhaps the most
widely used technique in the identification of clays.
 Isomorphous substitution is believed to be a major source of
negative charges in 2:1 layer clays.
 The negative charge of the clay surface is thus screened by an
equivalent swarm of counter ions that are positive. The
negative charge on the clay surface and the swarm of positive
counter ions are called the electric double layer.
Chapter 3 : Soil Chemistry 97

 When a colloidal suspension is placed in an electrical field, the

colloidal particles move in one direction (toward the positive
pole). The counter ions move in another direction (toward the
negative pole). The electric potential developed at the solid–
liquid interface is called the zeta potential.
 Adsorption is defined as the concentration of constituents at the
colloidal surfaces. The curve relating the concentrations of
adsorbed materials at a fixed temperature is called the
adsorption isotherm.
 If the soil–water potential decreases, soil–water content also
decreases. The latter may cause water to move out of the cell,
ultimately producing a phenomenon called cytoplasmolysis.
 The cation exchange capacity of sesquioxides is 2 - 4 meq /
100 g of soil.
 Under certain conditions, the adsorbed cations are held so
strongly by clays that they cannot be recovered by exchange
reactions. These cations are called fixed cations.
 The repulsion of anions from colloidal surfaces possessing
negative charges is called negative adsorption.
 Bolt (1976) reported a decreasing order of preferential
adsorption among the different anions –
SiO44 – > PO43– >> SO42– > NO3– = Cl–.
 Phosphate anions can be attracted to soil constituents with such
a bond that they become insoluble and difficult to obtain by
plants. This process is called phosphate retention and
phosphate fixation, which can occur biologically or chemically.
Some call it chemical fixation of phosphate.
 The term phosphate potential is introduced by Schofield (1955)
to be used as an index for availability of soil phosphorus.
Similarly, as with the definition of soil water potential, the
phosphate potential is defined as the amount of work that must
98 Tablets of Soil Science

be conducted to move reversibly and isothermally an

infinitesimally small amount of a phosphate ion from a pool of
phosphates at a specified location at atmospheric pressure to
the point under consideration.
 Bronsted and Lowry defined independently, in 1923, that an
acid is a compound capable of donating a proton (proton
donor). On the other hand, any compound capable of accepting
a proton is considered a base (proton acceptor). This acid-base
concept is also known as the proton concept.
 Lewis Concept - According to this theory, an acid is a
compound that can accept an electron pair (electron-pair
acceptor). A base is a compound that can donate an electron
pair (electron-pair donor). Hence, any substance that has an
unshared pair of electrons is a base, and any compound that can
react with that pair of electrons is an acid. This is also called
the electron concept.
 When a liquid is dispersed in a gas medium, it also forms an
aerosol, like spray and fog, but when it is dispersed in a liquid
it is called an emulsion.
 Hymatomelanic acid soluble in alkali and alcohol mediums but
insoluble in acid mediums.
 Humic acid and humin both are insoluble in alcohol medium.
Chapter 3 : Soil Chemistry 99

Table–1 CEC (C. mol. P+ kg-1 (or) meq / 100 g of soil)

1 Sesquioxides 2–4
2 Kaolinite 3 – 15
3 Montmorillonite 80 – 100
4 Illite 15 – 40
5 Vermiculite 80 – 150
6 Humus 150 – 300

Table - 2 [C –AXIS SPACING (AO)]

S. No Name of the mineral Spacing
1 Kaolinite 7.2
2 Montmorillonite 14
3 Halloysite 10.25
4 Illite (or) Mica 10
5 Vermiculite 10 - 15
6 Chlorite 14
NOTE: 1 nm = 10 Aº
 100 Tablets of Soil Science

Table - 3 HUMIC COMPOUNDS

S. No Fraction Molecular Soluble medium
name weight
1 Fulvic acid Low Soluble both in alkali and
acid medium
2 Humic acid Medium Soluble in alkali medium
only
3 Humin High Insoluble in both acid and
alkaline mediums

Table – 4 Y - INDEX
[Link] Name of the mineral Y-index value
1 Kaolinite 0-5
2 Illite 5 - 25
3 Montmorillonite > 25



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