Soil Chemistry

Kimia FMIPA Unlam 2019

 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 (pelapukan)
 Ion exchange :
1.Exchangeable cations
2. Soluble cations
 Exchangeable cations (on soil surfaces)
cannot be removed by leaching.

 Soluble cations (in solution)

can be removed by leaching.
 When soil is dried…
 Bagaimana nasib/keadaan kation tertukar
dan kation terlarut?

…exchangeable cations hold to adsorption sites

on soil surfaces.

…soluble cations (and anions) precipitate or

crystallize as salts.
 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)

 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
 Apa yg berperan  Apa yang berperan
meningkatkan meningkatkan
keasaman tanah? kebasaan tanah
 Apa yang dimaksud  Apa yang dimaksud
kation asam? kation basa?
 Apa yang dimaksud  Apa yang dimaksud
KTK tergantung pH kejenuhan basa (base
dan KTK permanen? saturation)
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
+
Na + OH
-
H2O
Na + H
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
 Soil organic matter as a source of CEC

•Temporary (will ultimately decompose)

•Nearly insoluble in water, but soluble in base (high pH)
•Contains 30% each of proteins, lignin, complex sugars
•50% C and O, 5% N
•Very high CEC on a weight basis
•Develops a net negative charge due to the dissociation of H+

from enolic (-OH), carboxyl (-COOH), and phenolic ( -OH)

groups as pH increases (solution H+ concentration decreases):
 Base Saturation

Since we consider only major exchangeable cations,

CEC = Ca2+ +Mg2+ + K+ + Na+ + Al3+ + H+ (in cmolc kg-1)

And therefore:

Ca 2  Mg 2  K   Na 
% BS  2 2   3 
Ca  Mg  K  Na  Al  H
 Ammonium chloride CEC (does not control soil pH)

Step 1: Extract with 1 M NH4Cl Step 2: Extract with 1 M KCl

Extraction funnel

Soil sample

Solution extracted

NH4+ displaces exchangeable K+ displaces exchangeable NH4+ into

Ca2+, Mg2+, K+, Na+, Al3+ into extractant; this gives effective CEC
extractant; this gives sum of (CECeff) which includes
cations CEC (CECsum)
exchangeable H+ at normal soil pH
--- Ca2+ -- NH4+ -- K+
--- Mg2+ -- NH4+ -- K+
--- K+ + NH4+ -- NH4+ + K+ -- K+ Discard
--- Na+ -- NH4+ -- K+ soil sample
--- H+ -- NH4+ -- K+
--- Al3+ -- NH4+ -- K+
 Ammonium acetate CEC (buffers pH to 7.0)

Step 1: Extract with 1 M Ammonium acetate Step 2: Extract with 1 M KCl

Extraction funnel

Soil sample

Solution extracted

NH4+ displaces exchangeable K+ displaces exchangeable NH4+ into

Ca2+, Mg2+, K+, Na+, Al3+ into extractant; this gives effective CEC (CEC eff)
extractant; because of high pH,
which includes exchangeable H+ at pH
Al3+ is precipitated as Al(OH)3
7.0 (which is often greater than soil pH!)
--- Ca2+ -- NH4+ -- K+
--- Mg2+ -- NH4+ -- K+
--- K+ + NH4+ -- NH4+ + K+ -- K+ Discard
--- Na+ -- NH4+ -- K+ soil sample
--- H+ -- NH4+ -- K+
--- Al3+ Al(OH)3 -- NH4+ -- K+
 Three ways to measure (cont.)

3. Ammonium acetate CEC (CECOAc).

• This
includes permanent charge CEC + all pH-dependent
CEC. Is is measured by extracting the soil with either
ammonium acetate (NH4OAc, buffers pH at 7.0). (Figure
2).
• Then the same produre is followed as for the neutral salt

CEC.
• Note: exchangeable Al should be measured separately

with a KCl extract because Al precipitates as Al(OH)3 at

high pH
Figure 3. Types of CEC depend on how it is measured

CECOAc

CECeff

CECsum

Permanent Charge CEC pH-dependent CEC

CECsum: Measured as the sum of Ca + Mg + K + Na + Al extracted with ammonium

chloride in the first extraction in Figure 1

CECeff: Measured with ammonium chloride, neutral salt, after second extraction in Fig 1

CECOAc: Measured with ammonium acetate at pH 7 in Figure 2

 Base Saturation

• Since CEC can be measured in different ways, %BS will vary

with the method used, and must be specified.
• For a soil with a given amount of exchangeable bases, % BS
calculated from CECsum will be greater than that calculated from
CECeff which will be greater than that calculated from CECtot
because more of the potential acidity on the pH-dependen CEC
is counted as CEC (i.e., CECsum < CECeff < CECtot).
• The example in Figure 4 shows how this might occur. In each
case, the base cations are the same (6 cmolc kg-1); only the
measure of CEC (the denominator) changes.
Figure 4. Base saturation value depends on which CEC measure is used

CECOAc= 10 cmolc kg-1

CECeff = 8 cmolc kg-1

CECsum = 7 cmolc kg-1

Base Cations Acid cations

Ca + Mg2+ + K+ + Na+ = 6 cmolc kg-1
2+
Aln+ = 1 cmolc kg-1
H+ = 3 cmolc kg-1

Ca2+ + Mg2+ + K+ + Na +
________________________
%BSsum= X 100
CECsum

Ca 2+
+ Mg2+ + K+ + Na +
__________________________ 6
= X 100 = X 100 = 85%
Ca + Mg + K + Na + Al
2+ 2+ + + n+ 7

Ca2+ + Mg2+ + K+ + Na +
________________________ 6
%BSeff= X 100 = X 100 = 75%
CECrff 8

Ca2+ + Mg2+ + K+ + Na +
________________________ 6
%BSOAc= X 100 = X 100 = 60%
CECOAc 10