Soil Chemistry

Colloids
 Clay minerals and humus and complexes
 The most chemically active part of soil
 Large surface area
 Electrical charge (usually net negative)
 Some +, some –
 Nutrient cations (+ions) and anions (- ions)
are held on colloid surfaces, in reserve for
plants
 Why are colloids negative?
1.Clay:
 Oxygen ions along edges of micelles
2. humus:
H+ ions tend to migrate away from
organic compounds in humus, to soil
solution, leaving net negative charge (OH-)
 Ion Exchange
What is the exchange?

exchange of ions on soil surfaces with ions

in soil solution.

Cations and anions are involved

 Where does exchange take
place?
 Organic colloids (humus) and inorganic
micelles (clays) and complexes of both

 Where do ions in soil come from?

 Release from organic matter
 Rain
 Weathering of parent material
 Leaching

 ions (on soil surfaces) cannot be removed

by leaching.

 ions (in solution)

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

…the ions on soil surfaces STAY ON

adsorption sites

…the soluble ions (in soil solution) precipitate

or crystallize (come out of solution) 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,
available for plants

“outer sphere complex”

Nonexchangeable:
adsorbed by strong
bonds or held in
inaccessible places
 (e.g., the K+ between
layers of illite)

 “inner sphere complex”

 not part of ion

exchange !
 Cation exchange capacity (CEC)

Sum total of exchangeable cations that a

soil can adsorb.

If a soil has a high CEC,

it prevents nutrients from
being leached away from roots
 CEC
Expressed in:

milliequivalents per 100 g (meq/100g)

 Dynamic 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 K fertilizer

K+
Ca+2
K+ Ca+2 Ca+2
+ K+
+
K+ K+
Ca+2 K+ K+
K+
exchangeable
exchangeable
solution 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
 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
The more strongly a cation is attracted to the
exchange surface, the greater the chance
of adsorption.

Depends on:
1. charge
2. hydrated radius
Radius Unit Na+ K+ Mg2+ Ca2+ Al3+
Non-
nm 0.095 0.133 0.066 0.099 0.050
hydrated
Hydrated nm 0.360 0.330 0.430 0.410 0.480

Strong --------------------------------------Weak
Al+3 > Ca+2 > Mg+2 > [K+ = NH4+ ] > Na+ > H+
 The less tightly held (lower energy of
adsorption) ions are the ones furthest from
the soil surfaces and can be leached more
easily and are further down the soil profile.

 The strongly held ones are closer to the

soil particle surfaces and tend to move
more slowly down profile
 How do plants get nutrients?
 Nutrients on the colloids are kept within
root zone of plants.
 H+ from roots exchange with cations on a
charge-by-charge basis
 Two videos:
 CEC  CEC
 Treating a sodic soil
 Sodic: too much sodium (Na)

 Add gypsum (CaSO4) : increases calcium

concentration; Ca is adsorbed at expense
of sodium

Al+3 > Ca+2 > Mg+2 > [K+ = NH4+ ] > Na+ > H+
 Base saturation
% of exchange sites occupied by basic
cations (cations other than H+ and Al3+)

Base saturation
+ H+ / Al ion saturation
should equal 100%
Base saturation and pH
relationship
(for midwest US soils)

Notice neutral pH (7.0)

requires a base sat
of 80%.
Soil pH
 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 Al3+ ions produce acidity

Al3+ produces H+ ions when it reacts with

water.

(when pH below 6: Al3+ 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 Mg2+.
 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 Ca2+ + 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 (Al3+, 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
Dissociation of exchangeable H+ or Al+3

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

equivalent amount of H+ ions.

Al3+ + H2O AlOH2+ + 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
pH dependence of humus