SURFACE CHEMISTRY

Interaction of Water and Clay Minerals

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A. Origins of Charge Deficiencies
Permanent
(due to isomorphous substitution)

pH-dependent

(variable, due to edges)

 A. Origins of Charge Deficiencies
1. Imperfections in the crystal lattice
-Isomorphous substitution.
• The cations in the octahedral or tetrahedral sheet can be replaced by
different kinds of cations without change in crystal structure (similar
physical size of cations).
For example,
Al3+ in place of Si4+ (Tetrahedral sheet)
Mg2+ instead of Al3+(Octahedral sheet)
unbalanced charges (charge deficiencies)

• This is the main source of charge deficiencies for montmorillonite.

• Only minor isomorphous substitution takes place in kaolinite.

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 A. Origins of Charge Deficiencies

Octahedral sheet neutral Net negative charge

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B. Origins of Charge Deficiencies (Cont.)
2. Imperfections in the crystal lattice
- The broken edge

The broken edge can be

positively or negatively
charged.

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 B. Origins of Charge Deficiencies (Cont.)

3. Proton equilibria (pH-dependent charges)

M  OH  H   M  OH 2 (Pr otonation )
M  OH  OH   M  O   H 2 O (Deprotonation )

H Kaolinite particles are positively

M O + charged on their edges when in a
H
low pH environment, but negatively
M O H charged in a high pH (basic)
M: metal
environment.
M O-

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 B. Origins of Charge Deficiencies (Cont.)
3. Proton equilibria (pH-dependent charges)

H+ bound tightly, so
the lower the pH, the
less exchange there is
(i.e., lower nutrient
availability)

Especially important in kaolinite, humus, where no

internal charge imbalance
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 B. Origins of Charge Deficiencies (Cont.)
• 4. Adsorbed ion charge (inner sphere complex
charge and outer sphere complex charge)

Ions of outer sphere complexes do not lose their hydration spheres. The
inner complexes have direct electrostatic bonding between the central
atoms.
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 C. “Charged” Clay Particles
- or +
• External or interlayer surfaces are
negatively charged in general.
• The edges can be positively or
negatively charged.
• Different cations balance charge
deficiencies.

Cation

- or +
Kaolinite and negative gold sol Dry condition
(van Olphen, 1991)
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 D. Polar Water Molecules
Structure Polar molecule O(-)

H(+) H(+)
Hydrogen bond Salts in aqueous solution

hydration
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 E. Clay-Water Interaction
1. Hydrogen bond
Kaolinite

H
O O
H H

Clay Surfaces
Adsorbed layers Free water
3 monolayers Bulk water

Oxygen Hydroxyl
O OH
The water molecule “locked” in the adsorbed
layers has different properties compared to
that of the bulk water due to the strong
attraction from the surface.
H
O 11
H
 E. Clay-Water Interaction (Cont.)
Na+ crystal radius: 0.095 nm
2. Ion hydration radius of hydrated ion: 0.358 nm

cation

Clay
layers

The cations are fully hydrated,

Dry condition The water molecules which results in repulsive forces
(Interlayer) wedge into the interlayer and expanding clay layers
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after adding water (hydration energy).
E. Clay-Water Interaction (Cont.)
3. Osmotic pressure

A B

From Oxtoby et al.,

1994

The concentration of cations is higher in the interlayers (A) compared with that
in the solution (B) due to negatively charged surfaces. Because of this
concentration difference, water molecules tend to diffuse toward the interlayer
in an attempt to equalize concentration. 13
 E. Clay-Water Interaction (Cont.)

Relative sizes of adsorbed water layers on sodium montmorillonite and

sodium kaolinite

Holtz and Kovacs, 1981

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Thanks