 Class evaluations

Soil Chemistry
 Ion Exchange
 Ions adsorbed to soil surfaces can be
exchanged with ions in soil solution.

 Cations and anions

 Ion exchange
 Organic colloids and inorganic micelles
(clays) are sites of ion exchange

 Where do ions in soil come from?

 Release from organic matter
 Rain
 Weathering of parent material
 Ion exchange

 Exchangeable cations (on soil surfaces)

cannot be removed by leaching.

 Soluble cations (in solution)

can be removed by leaching.
 When soil is dried…

…exchangeable cations hold to adsorption sites

on soil surfaces.

…soluble cations (and anions) precipitate or

crystallize as salts.
Examples of soluble cations precipitating
 Ion exchange
Exchangeable ions on soil surface trading
places with ions in solution.
 On soil surfaces, there are:
Exchangeable and Nonexchangeable Ions
:

Exchangeable: weakly held, in contact with soil

solution, ready for quick replacement.
“outer sphere complex”

Nonexchangeable:
“inner sphere complex”
 adsorbed by strong bonds or held in
inaccessible places
 (e.g., the K+ between layers of illite)
 not part of ion exchange !
 Cation exchange capacity (CEC)

Sum total of exchangeable cations that a

soil can adsorb. ( prevents nutrients from
leaching away from roots)
 CEC
Expressed in:

milliequivalents per 100 g (meq/100g)

 Base saturation
% of exchange sites occupied by basic
cations

Basic cations are cations other than H+ and

Al+3
Base saturation
+ H+ ion saturation
should equal 100%
For midwest US soils
Notice neutral pH (7.0)
requires a base sat
of 80%.
(neutral pH is not 50%
because most base
cations have a + charge
of 2)
 equilibrium
Strive for equivalent proportions of solution
and exchangeable ions.

Upset equilibrium by:

removal by plants
leaching Initiate ion exchange

fertilization
weathering
 Ion exchange example:
Add H+ ions to soil :

H+ H+
Ca+ Ca+ Ca+ Ca+
Ca+ H+
Ca+
+ + Ca+ H+
H+
Ca+ soil Ca+ H+ H+
H+ Ca+
Ca+ Ca+ solution Ca+ Ca+
Ca+ Ca+

exchangeable solution exchangeable solution

 Rules of ion exchange
 Process is Reversible

 Charge by charge basis

 Ratio Law:
 ratio of exchangeable cations will be
same as ratio of solution cations
 Add K fertilizer…

K+
Ca+2
K+ Ca+2 Ca+2
+ K+
+
K+ K+
Ca+2 K+ K+
K+

1 Ca : 2 K 1 Ca : 2 K

Same ratio
 Energy of adsorption
Strong --------------------------------------Weak

Al+3 > Ca+2 > Mg+2 > [K+ = NH4+ ] > Na+ > H+

(based on charge and hydrated radius)

 Soil pH importance
 Determines solubility
of nutrients
 Before plants can get
nutrients, they must be
dissolved in soil
solution

 Microbial activity also

depends on pH
 pH
negative log of the hydrogen ion concentration

(also a measure of OH- concentration)

If H+ concentration > OH- : acidic

If OH- > H+ : basic

Soil pH is pH of solution, NOT exchange complex

 General soil pH conditions:
“Slightly acid” “Slightly basic”
6.0 – 6.6 7.4 – 8.0

“Moderately acid” “Moderately basic”

5.0 – 6.0 8.0 – 9.0

“Strongly acid” “Strongly basic”

< 5.0 > 9.0
In soil, both H+ and Al+3 ions produce acidity

Al+3 produces H+ ions when it reacts with

water.

(when pH below 6: Al+3 is the cause of acidity)

Causes of soil basicity

1. Hydrolysis of basic cations

2. Hydrolysis of carbonates
 1. Hydrolysis of basic cations:
(especially Ca+2, Mg+2, K+, NH4+, Na+)

(also called exchangeable bases)

Extent to which exchangeable bases will hydrolyze

depends on ability to compete with H+ ions for
exchange sites.

Na Na Na Na
H2O + + OH-
H Na
Na +
Na Na Na Na
K+ and Na+ are weakly held compared to
Ca+2 and Mg+2.
 Recall energy of adsorption

So, K+ and Na+ are hydrolyzed easily and

yield higher pHs .
 2. Hydrolysis of carbonates
(especially CaCO3, MgCO3, Na2CO3)

• As long as there are carbonates in the soil,

carbonate hydrolysis controls pH.
• Calcareous soils remain alkaline because H+ ions
combine with OH- to form H2O.
• For those soils to become acid, all carbonates
must be leached.
• Basic cations replaced by Al+3 and H+

CaCO3 + H2O Ca+2 + HCO3- + OH-

Na2CO3 + H2O Na + HCO3- + OH- (higher pH because Na more soluble)

 Causes of soil acidity

1. Accumulation of soluble acids

2. Exchangeable acids (Al+3, H+)
 1. Accumulation of soluble acids
at faster rate than they can be neutralized or
removed

a. Carbonic acid
(respiration and atmospheric CO2)

b. Mineralization of organic matter

(produces organic, nitric, sulfuric acids)

Precipitation increases both a and b

 2. Exchangeable acids
Exch. H+ or Al+3 dissociate

Al+3 ties up OH- from water, releases an

equivalent amount of H+ ions.

Al+3 + H2O AlOH+2 + H+

 CEC and pH
Only 2:1 silicate clays do not have pH-dependent CECs.

Others are pH-dependent:

1:1 kaolinite:
low pH: low CEC
high pH: high CEC

Oxidic clays