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Soil Colloidal
 Chemistry
        Compiled and Edited by
             Dr. Syed Ismail,
       Marthwada Agril. University
           Parbhani,MS, India
                                 1
The Colloidal Fraction
 Introduction
 What is a colloid?
 Why this is important in understanding
  soils?
 How can we understand this fraction?
 What are the fundamental basics of this
  fraction?
                                            2
Soil Colloids
 The most chemically active fraction of soils.
 They are very small, less than 2 µm in
  diameter
 Shape
 Colloids can be either
    – mineral (clays) or organic (humus)
    – crystalline (definite structure) or amorphous.


                                                       3
Colloids
   Properties imparted to soils
    – Static Vs. dynamic properties
    – Sand and Silt (no colloids)
        Static and occupy space

    – Clay and Humus (colloids)
        Dynamic and very active (charges)




                                             4
Colloids
   Properties imparted to soils by colloids
    – Chemical Vs Physical properties
        Chemical
            –   Sources of ions for plant nutrition
            –   Source of electro-negativity (CEC)
            –   Buffering capacity
            –   Chemical cement agents
          Physical
            – Large surface area per unit of mass (cm2/g)
            – Plasticity


                                                            5
Types of Soil Colloids

 Crystalline silicate clays
 Non-crystalline silicate clays
 Iron and aluminum oxide
 Organic material (Humus)




                                   6
Soil Colloids: Silicate Clays
  Kaolinite      Montmorillonite




                                   7
Crystalline Silicate Clays
 What is it?
 Shape: x, y and z.
 Surface area: 2 sources ***
    – External Vs Internal
   Composition of crystalline structures:
    –   Silicon-Oxygen and Aluminum- Hydroxide … others
    –   Silicon Tetrahedral and Aluminum Octahedral sheets
    –   Si-O Tetrahedral sheet (tetra=four void spaces)
    –   Al-OH Octahedral sheet (0cta=eight void spaces)




                                                             8
Charges
Isomorphous Substitutions
Process in which one element substitutes
  another of comparable size in the crystalline
  structure
Al is slightly larger than Si, consequently Si
  may replace Al!
IF Al+3 and Si+2 then what?

                                              9
10
Charges
   Permanents
    – Isomorphous substitutions
   pH dependant (non-permanents)
    – Broken Edges
    – Al-OH + OH ==H- == Al- O- + H2O
     (no charge)           (- charge)
    – C-OH + OH     ==H- == -C- O- + H20
     (no charge)           (- charge)

                                           11
Structures (2D)
   Si Tetrahedral Sheet



   Al Octahedral Sheet

Al-Si combined

                               12
Example 1:1 type clay

   Sheets              Layer

                         Interlayer
   Sheets              Layer



                                      13
Clay silicate crystals
   1:1 type              KAOLINITE



   2:1 type             SMECTITE
                       VERMICULITE
                     MONTMORILLONITE


                                  14
Clay silicate crystal
   2:1:1 type              CHLORITE




                                   15
Clay silicate crystals
   1:1 type            KAOLINITE
                        4 O and 1 Si
                       6 OH and 1 Al
                        Hydrogen ion
                        STRONG BOND!
                        NO WATER and
                        NO OTHER ION!



                                        16
1:1 type clays
   Stable and non expanding clay
   Low total charges
   Relative low specific surface area
   pH dependant charges
   Good physical properties
   Limiting holding capacity for nutrients
   Good for roads, buildings, ceramic and bricks.
   Hexagonal shape
                                                     17
Clay silicate crystals
   2:1 type           Expanding
                         4 O and 1 Si
Montmorillonite          6 OH and 1 Al
                         4 O and 1 Si
                         O bonding (WEAK)
                             Hydrated
                             exchangeable
                             cations
                             Non Hydrated ions
                                            18
Smectite (includes montmorillonite)




                                      19
kaolinite     illite




              humus
mont-
              (fulvic acid)
morillonite



                    20
Sheets and Layers
1:1 non-expanding   2:1 non-expanding   2:1 expanding




    Al sheet
    Si sheet                            + ++++ + +
    Al sheet
    Si sheet
    Al sheet
    Si sheet
    Al sheet                             ++ + ++ + +
    Si sheet



  kaolinite              illite         smectite and
                                         vermiculite

                                                        21
22
2:1 Clay expanding type
 Expanding clays
 Shrinking and swelling constantly
 Poor physical characteristics
 Abundant charges and surface
 Rich in nutrients
 Good soils for crops if managed properly
 Not affected much by pH
                                             23
Clay silicate crystals
   2:1 type (Fine Mica)     Non expanding
                           Charges: 20% Al octa-
                                   by Si
    tetrahedral
                           Strong bonding forces
                                Large Net Charge
                                Attract ions K+ and NH4+
                                Fits perfectly in hexahedral
                                holes
                                                     24
Hexahedral holes




                   25
26
2:1 Clay non expanding type
 Limited expanding
 Good physical properties
 Medium total charges
 Lower specific surface area than expanding
  2:1 clays
 Good soils for crops
 Challenging management for K+ and NH4+


                                           27
Clay silicate crystal
   2:1:1 type
                           Fe/Mg instead
                          of Al octahedral

                          Mg dominated sheet
CHLORITE                          Hydrogen

                                  STRONG
                                  BOND 28
2:1:1 Clay type
 Non Expanding clays
 Very limited shrinking and swelling
 Good physical characteristics
 Limited charges and surface
 Good soils for crops if managed properly
 Not affected much by pH


                                             29
 Distance between UNITS of crystalline
  structures
 1.41 nm Vermiculite
 1.00 nm Micas
 0.71 Kaolinite




                                          30
31
Non silicate Clays
 Alone or mixed with silicate clays
 Organic colloids – Humus
    – Large molecules (+ and – charges)
   Iron and Aluminum oxides
    – Modified octahedral sheets with substitutions
    – No tetrahedral sheets
          Gibbsite (Al(OH)3) Oxisol and Ultisol
          Goethite (FeOOH) yellow brown color
          Hematite Fe2O3 red color

                                                      32
Clay Minerals Comparison
                      Kaolinite          Illite    Vermiculite       Smectite

Tetrahedral     0                   20% Al3+      10% Al3+        2.5% Al3+

Octahedral      0                   0             15% Mg2+        15% Mg2+

Tetrahedral     ---                 20% Al3+      10% Al3+        2.5% Al3+

CEC   me/100g   3-15 (edges)        30            150             80 - 150

Shrink-swell Low                    None          Mod to High     High

Interlayer      H-bonds             Fixed K+      Exch. cations Exch. cations

                                    Early         Intermediate    Recrystallization
                Recrystallization
                                                                  under moderate
Origin          under intense       alteration of alteration of   neutral to
                acid weathering     micas         micas           alkaline weath.

                                                                              33
Thanks


         34

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Soil colloidal chemistry

  • 1. Soil Colloidal Chemistry Compiled and Edited by Dr. Syed Ismail, Marthwada Agril. University Parbhani,MS, India 1
  • 2. The Colloidal Fraction  Introduction  What is a colloid?  Why this is important in understanding soils?  How can we understand this fraction?  What are the fundamental basics of this fraction? 2
  • 3. Soil Colloids  The most chemically active fraction of soils.  They are very small, less than 2 µm in diameter  Shape  Colloids can be either – mineral (clays) or organic (humus) – crystalline (definite structure) or amorphous. 3
  • 4. Colloids  Properties imparted to soils – Static Vs. dynamic properties – Sand and Silt (no colloids)  Static and occupy space – Clay and Humus (colloids)  Dynamic and very active (charges) 4
  • 5. Colloids  Properties imparted to soils by colloids – Chemical Vs Physical properties  Chemical – Sources of ions for plant nutrition – Source of electro-negativity (CEC) – Buffering capacity – Chemical cement agents  Physical – Large surface area per unit of mass (cm2/g) – Plasticity 5
  • 6. Types of Soil Colloids  Crystalline silicate clays  Non-crystalline silicate clays  Iron and aluminum oxide  Organic material (Humus) 6
  • 7. Soil Colloids: Silicate Clays Kaolinite Montmorillonite 7
  • 8. Crystalline Silicate Clays  What is it?  Shape: x, y and z.  Surface area: 2 sources *** – External Vs Internal  Composition of crystalline structures: – Silicon-Oxygen and Aluminum- Hydroxide … others – Silicon Tetrahedral and Aluminum Octahedral sheets – Si-O Tetrahedral sheet (tetra=four void spaces) – Al-OH Octahedral sheet (0cta=eight void spaces) 8
  • 9. Charges Isomorphous Substitutions Process in which one element substitutes another of comparable size in the crystalline structure Al is slightly larger than Si, consequently Si may replace Al! IF Al+3 and Si+2 then what? 9
  • 10. 10
  • 11. Charges  Permanents – Isomorphous substitutions  pH dependant (non-permanents) – Broken Edges – Al-OH + OH ==H- == Al- O- + H2O (no charge) (- charge) – C-OH + OH ==H- == -C- O- + H20 (no charge) (- charge) 11
  • 12. Structures (2D)  Si Tetrahedral Sheet  Al Octahedral Sheet Al-Si combined 12
  • 13. Example 1:1 type clay  Sheets Layer Interlayer  Sheets Layer 13
  • 14. Clay silicate crystals  1:1 type KAOLINITE  2:1 type SMECTITE VERMICULITE MONTMORILLONITE 14
  • 15. Clay silicate crystal  2:1:1 type CHLORITE 15
  • 16. Clay silicate crystals  1:1 type KAOLINITE 4 O and 1 Si 6 OH and 1 Al Hydrogen ion STRONG BOND! NO WATER and NO OTHER ION! 16
  • 17. 1:1 type clays  Stable and non expanding clay  Low total charges  Relative low specific surface area  pH dependant charges  Good physical properties  Limiting holding capacity for nutrients  Good for roads, buildings, ceramic and bricks.  Hexagonal shape 17
  • 18. Clay silicate crystals  2:1 type Expanding 4 O and 1 Si Montmorillonite 6 OH and 1 Al 4 O and 1 Si O bonding (WEAK) Hydrated exchangeable cations Non Hydrated ions 18
  • 20. kaolinite illite humus mont- (fulvic acid) morillonite 20
  • 21. Sheets and Layers 1:1 non-expanding 2:1 non-expanding 2:1 expanding Al sheet Si sheet + ++++ + + Al sheet Si sheet Al sheet Si sheet Al sheet ++ + ++ + + Si sheet kaolinite illite smectite and vermiculite 21
  • 22. 22
  • 23. 2:1 Clay expanding type  Expanding clays  Shrinking and swelling constantly  Poor physical characteristics  Abundant charges and surface  Rich in nutrients  Good soils for crops if managed properly  Not affected much by pH 23
  • 24. Clay silicate crystals  2:1 type (Fine Mica) Non expanding Charges: 20% Al octa- by Si tetrahedral Strong bonding forces Large Net Charge Attract ions K+ and NH4+ Fits perfectly in hexahedral holes 24
  • 26. 26
  • 27. 2:1 Clay non expanding type  Limited expanding  Good physical properties  Medium total charges  Lower specific surface area than expanding 2:1 clays  Good soils for crops  Challenging management for K+ and NH4+ 27
  • 28. Clay silicate crystal  2:1:1 type Fe/Mg instead of Al octahedral Mg dominated sheet CHLORITE Hydrogen STRONG BOND 28
  • 29. 2:1:1 Clay type  Non Expanding clays  Very limited shrinking and swelling  Good physical characteristics  Limited charges and surface  Good soils for crops if managed properly  Not affected much by pH 29
  • 30.  Distance between UNITS of crystalline structures  1.41 nm Vermiculite  1.00 nm Micas  0.71 Kaolinite 30
  • 31. 31
  • 32. Non silicate Clays  Alone or mixed with silicate clays  Organic colloids – Humus – Large molecules (+ and – charges)  Iron and Aluminum oxides – Modified octahedral sheets with substitutions – No tetrahedral sheets  Gibbsite (Al(OH)3) Oxisol and Ultisol  Goethite (FeOOH) yellow brown color  Hematite Fe2O3 red color 32
  • 33. Clay Minerals Comparison Kaolinite Illite Vermiculite Smectite Tetrahedral 0 20% Al3+ 10% Al3+ 2.5% Al3+ Octahedral 0 0 15% Mg2+ 15% Mg2+ Tetrahedral --- 20% Al3+ 10% Al3+ 2.5% Al3+ CEC me/100g 3-15 (edges) 30 150 80 - 150 Shrink-swell Low None Mod to High High Interlayer H-bonds Fixed K+ Exch. cations Exch. cations Early Intermediate Recrystallization Recrystallization under moderate Origin under intense alteration of alteration of neutral to acid weathering micas micas alkaline weath. 33
  • 34. Thanks 34