Cation Exchange Sites

Cations attached to clay particles/OM or free

Charge Development
A. pH dependent charge Deprotonation of surface functional groups (organic matter) COOH + OH- = COO- + H2O 'Broken-edge charges': These occur at the broken edges of clay mineral crystal sheets----- (Edges of layer silicates; oxides of Fe and Al) ------the hydrogen of hydroxyl groups dissociates slightly and the broken edge is left with a negative charge carried by the oxygen. pH dependent charge as pH

Charge Development
B. Isomorphic substitution replacement of one atom by another of similar size in a crystal lattice without disrupting or changing the crystal structure of the mineral

Isomorphic substitution of Mg2+ for Al3+ in the octahedral layer of a 2:1 clay mineral

Al2O2OH2 (no charge) Al has a +3 charge, O has a -2 charge AlMgO2OH2 (minus 1 charge) Mg has a +2 charge http://www.soils1.cses.vt.edu/MJE/shockwav e/cec_demo/version1.1/cec.shtml

CATION EXCHANGE
Plant roots Vs Surface of Clay and Humus

Between Two Clay Particle Two Humus particles Clay and Humus particle

CATION EXCHANGE
The exchange reaction is rapid The exchange reaction is diffusion controlled The exchange reaction is reversible The exchange reaction is stoichiometric

stoichiometric CATION EXCHANGE

1. Soil solution Vs Surface of Clay or Humus

Selectivity of one ion over another

Some cations have a preference over others for the negative surface charge of a soil colloid. In general this is related to the charge of the cation and its hydrated radii. Higher the charge, more strong is the adsorption (exchangeable cation of aluminum, calcium or magnesium stays close to the clay particle and initiate soil aggregation) When the valence of the cations are equal, the cation with the smallest hydrated radius is more strongly adsorbed.

Radius Hydrated

Unit nm

Na+ 0.360

K+ 0.330

Mg2+ 0.430

Ca2+ 0.410

Al3+ 0.480

Order of preference for cations with a different valence (mixed series): Al3+ > Ca2+ > Mg2+ > K+ = NH4+ > Na+ > H +

Cation Concentration
Concentration of cations in the soil solution: If the concentration of a cation in soil solution is high, there is an increased chance or tendency for that cation to be adsorbed.

Cation Exchange Capacity

-vly charged sites: cation exchange sites. Total number of sites = CEC
No. of cation adsorption sites/unit weight of soil or Sum total of exchangeable cations that a soil can adsorb

Cation Exchange Capacity

-* Unit: milliequivalents (meq) per 100 g of oven dry soil

K+, AW: 39; eq wt=39 Ca++, AW: 40; eq wt =20 PO4-3 , AW: 95; eq wt =31.6 1 meq = 10-3 eq

Predicting CEC
1) sum of cations : remove all cations and total the amount 2) NH4+ saturation: soil saturated with NH4+ NH4+ replaced by Ca++ Measure NH4+ removed 3) CEC varies with texture:
Sandy = 0-3 meq/100 g Loamy = 10 15, Clay Loam = 10-30 Clayey = > 30 (depends on kind of clay; 60-100) Humus=400 meq/100 g

 High CEC value (>25) soil rich in clay and/OM

Soil Clay (%) CEC (meq./100 gm soil)
45% 39.5

Low CEC value (<5) : soil sandy with little or no organic matter

Humid Black soil, Maharashtra Arid (Ajmer)

4.4%

4.3

% Base Saturation
Base Cations Calcium Magnesium Potassium Sodium Acid Cations Aluminum Hydrogen

(meq Ca+2 + meq Mg+2 + meq K+ + meq Na+)/CEC x 100