SOIL PHYSICS

The Solid Phase: Nature and Behavior of Clay

Clay Minerals

Clay minerals by definition consist of particles less than 2m in equivalent diameter. Clay minerals are built up of silica and alumina sheets and classified into types:
2:1 clays with 2 tetrahedral and 1 octahedral sheets 1:1 clays with 1 tetrahedral and 1 octahedral sheets

The silicon tetrahedron: Si surrounded by 4 O atoms. The aluminum octahedron: Al surrounded by 6 OH- .

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals Tetrahedral

Al3+
Si4+ O1:1 Clay 2:1 Clay

Octahedral

Tetrahedral

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals

1:1 Clay

2:1 Clay

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals

Examples of clay minerals are kaolinite, micas, illite, chlorite, vermiculite, and montmorillonite. Most significant is montmorillonite due to its high degree of shrinkage and swelling. Clays are also characterized by high specific surface ranging from 5-100 m2 kg-1 for kaolinite to 700-800-to m2 kg-1 for montmorillonite. The negative charge of clays arises from isomorphous substitution.

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals Isomorphous substitution

Refers to the substitution of an ion by another of similar size:

Al3+ for Si4+ in the tetrahedral sheet Mg2+ or Fe2+ for Al3+ in the octahedral sheet

Isomorphous substitution is the main cause of the negative charge in clays.

Another source of negative charge is the broken edges.

The unbalanced charge must be compensated externally by the adsorption of ions (mostly cations) from surrounding solution.

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals Coulomb's Law
F k q1 q2 d2

F = force of attraction; q1 and q2 = the quantity of charge on two objects (Coulombs); d = the distance of separation between the two objects (m); k is Coulomb's constant.

Clay minerals with negative charge at the tetrahedral layer have higher attraction. This affects the hardness, ease of fracture of the minerals, swelling, crystal growth and mineral internal surface area.

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals Swelling and Shrinkage of Clay Minerals

The amount of swelling is related to the strength of interlayer bond:

if strong, you have non-expanding clay minerals if weak, you have swelling clay minerals
+++++++++ H2O Interlayer spacing

Clay dispersion occur when particles are separated to the extent that the attractive forces are no longer able to pull them together.

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals Kaolinite

It is a 1:1 clay mineral

Has very little or no isomorphic substitution

Has very little layer charge Very few counterions (low CEC: 3-15 meq/100 g clay) Layers are held together by H-bonding External surface area only 25 m2/g of clay

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals Montmorillonite

It is a 2:1 clay mineral

Fair amount of isomorphic substitution in octahedral sheet

High CEC: 80-120 meq/100 g clay Layers are held electrostatically by the covalent ions. The bond is relatively weak because of the distance. Large specific surface: 700-800 m2/g of clay

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals Illite

It is a 2:1 clay mineral Has isomorphic substitution in tetrahedral sheet Force of attraction is strong so that K+ is fixed
K+ K+ K+ K+

Water molecules do no enter in interlayer space The CEC is relatively low (20-40 meq/100 g clay)

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay Clay Minerals
Chlorite

It is a 2:1:1 clay mineral Has isomorphous substitution in tetrahedral sheet Brucite-like layer (with some Al) is sandwiched between tetrahedral layers [Mg AlSi O (OH) ]-1
3 3 10 2

brucite

[Mg2Al(OH)6]+1

Like illite, water molecules do no enter in interlayer space The CEC is relatively low (20-40 meq/100 g clay)

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals The Diffuse Electrical Double Layer

Since overall electrical neutrality is always maintained in nature, the net negative charge of the clay platelet is compensated by an equivalent positive charge of cations. Since the cations counteract the negative charge of the clay platelet, they are called counterions. Counterions include Na+, K+, H+, Mg2+, and Ca2+, and are either adsorbed at the surface or swarm in the surrounding solution.

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals The Diffuse Electrical Double Layer

Looking at the principle of minimum energy, cations try to be as close as possible to clay surface. Condition of minimum energy. But due to their thermal motion (kinetic energy), the cations will tend to diffuse away from the clay surface and maintain same concentration everywhere. This represent a condition of maximum entropy. The net result of these opposed forces is the condition of minimum free energy.

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals The Diffuse Electrical Double Layer
Minimum Energy - + - + - + - + - + - + - + - + - + - + - + - + - + - + - + - + Maximum Entropy + + + - + + + + - + + + + - + + + + - + Minimum Free Energy - + - + + - + + + + + - + + + + - + + + - + -

Distance from clay particle

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals
The Diffuse Electrical Double Layer

Ion concentration

c+

A-

Distance from clay particle

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals
The Diffuse Electrical Double Layer
Effect of changing ion concentration
Ion concentration

n2 > n1 n2 n1
Distance from clay particle

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals The Diffuse Electrical Double Layer
Divalent (Ca2+) vs monovalent (Na+) cations
Ion concentration

Na+ Ca2+

Distance from clay particle

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals
The Diffuse Electrical Double Layer
Effect of drying: Soil A is drier than soil B
Ion concentration

A B
Distance from clay particle

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals Ion Exchange

The cations in the double layer can be replaced or exchanged by other cations introduced into the solution.

This exchange is considered to be an intrinsic property of the soil, called cation exchange capacity (CEC).
Cation exchange depends on both clay content and clay type.

Cation exchange affects retention of ions in the soil but also affects transport of pollutants.
Flocculation-dispersion processes of the soil colloids are affected by the cation exchange.

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals Hydration and Swelling

Water is attached to clay surfaces by several mechanisms:

Electrostatic attraction Hydrogen bonding Adsorbed cations

When a confined body of clay sorbs water, swelling occurs. Swelling is greatest for monovalent cations. High salinity of the soil solution will suppress swelling.

Swelling lowers soil permeability as larger pores get clogged.

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay
Clay Minerals: Hydration and Swelling

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay Clay Minerals Flocculation and Dispersion

As clay particles interact with one another , we have:

Repulsive forces Attractive forces

When repulsive forces are dominant =dispersion. When attractive forces dominate = flocculation. Plate condensation flocculation (tactoid) Card-house structure flocculation

SOIL PHYSICS
The Solid Phase: Nature and Behavior of Clay Clay Minerals
Flocculation and Dispersion