Soil Chemistry / Soil pH

• Soil pH is the single most important chemical property

of the soil (like soil texture is to the physical
properties)
• Knowing the pH of the soil will quickly allow you to
determine if the soil is suitable for plant growth and
what nutrients will be most limiting.
• "Life is a struggle, not against sin, not against the
Money Power, not against malicious animal magnetism,
but against hydrogen ions.“--H.L. MENCKEN
• Strictly speaking, hydrogen ions are protons and do not
exist in the naked state in fluids; instead they react
with water (H20) to form hydronium ions, such as H3O+
• For most purposes H+ can be used to represent these
hydrated protons.
 Acid Base Chemistry
• Acid-base chemistry is an important part
of everyday life. The excess hydronium
(H3O+) ions in acids give them interesting
properties.
• Acids can react with metals and other
materials. The strong acid HCl is produced
in your stomach to help digest food. In H3O+ depends on the
dilute concentrations, acids are Strength of acid and
responsible for the sour taste of lemons, Initial concentration
limes, vinegar and other substances.
Of acid
• Bases are also very reactive. The strong
base NaOH is used in many household
cleaning agents such as oven cleaner and
drain clog-remover.
• How do we measure the concentration of
an acid or base?
 Measuring Acidity
• The acidity (or basicity) of a solution is measured
using the pH scale. (this scale is used because of
the very small concentrations that are being
measured)
• The pH scale corresponds to the concentration of
hydronium ions in a solution.
• If you take the exponent of the H3O+
concentration and remove the negative sign, you
have the pH of a solution.
• For example, in pure water the concentration of
hydronium ions is 1 x 10-7 M.
• Thus, the pH of a solution of pure water is 7.
• The pH scale ranges from 0 to 14, where 7 is
considered neutral ([H3O+ ] = [OH-]),
 pH
Hydronium ions
 Acid solutions are when pH is < 7.0 Hydroxide ions
Water
 Alkaline solutions are when pH > 7.0
 An acid can be defined as a proton
donor, a chemical that increases the
concentration of hydronium ions in
solution.
 Conversely, a base is a proton
acceptor, a chemical that reduces
the concentration of hydronium ions Neutral Solution
in solution (and increases the
concentration of hydroxide ions).

Slightly Acidic
Solution
 Soil pH
* pH - the negative log of the hydrogen ion(H+)
concentration in the soil water solution.
pH = - log [ H+]
* the pH scale is how we measure acidity and
alkalinity of solutions.
at neutral (pH =7) the number of H+ = OH-
Remember –
at pH of 6 there are 10x more H+ ions than at a pH 7
and there are 100x more H+ ions between pH 7 & 5
 Soil Cation Exchange
• Cation Exchange - the
ability of the soil to
hold onto nutrients and
prevent them from
leaching beyond the
roots.
• Cations are “+ “charged
ions = Ca++, Mg++, K+,
NH4+,
• The more cation
exchange a soil has the
more likely the soil will
have a higher fertility
level.
 Cation Exchange
• The interchange between a cation in
solution and another cation on the
surface of any negatively charged
material such as clay or organic
matter
H+
soil Ca++ +2H+ + Ca++
H+
colloid soil solution soil
colloid solution
 Cation exchange influenced by:

1) Strength of adsorption:
Al+3 > Ca2+ > Mg2+ > K+ =NH4+ > Na+ >H+
held tight --------------------------> easily replaced
2) the relative concentration of the cations in the
Soil Solution
 Cation Exchange Capacity
1) the number of cation adsorption
sites per unit weight of soil or
2) the sum total of exchangeable
cations that a soil can adsorb.
* CEC is expressed in milliequivalents
(meq) per 100 g of oven dry soil.
Equivalent weight = molecular or atomic wt (g)
valence or charges per formula
 Milliequivalent (MEQ)

1 meq wt. of CEC has 6.02 x 10 20

adsorption sites
MEQ of Common Cations
Element Na+ K+ Ca++ Mg++
Valence 1 1 2 2
Eq. Wt 23/1=23 39/1=39 40/2=20 24/2 = 12
MEQ wt .023 .039 .02 .012
 Back to Soil pH
Active Acidity - due to the H+ ion
activity in the soil solution at any given
time
Reserve Acidity - represented by the H+
and Al3+ that are easily exchanged by other
cations (positively charged ion)
HHHH H+ H+
H Ca++ H+
soil Mg Mg++ H+
Ca Ca++ H+ H+
H H H Na
Reserve Acidity Active Acidity -Soil solution
 Sources of acidity in Soil

* Hydrogen and Aluminum cations are

responsible for soil acidity
* Exchangeable Hydrogen is the main source of H+
at pH 6 and above. Below pH 6 Aluminum is the
main source of H+ due to dissociation of Al from
clay minerals. Aluminum becomes more soluble at
lower pH’s
Al3+ + H20 ----> Al(OH)++ + H+
Al(OH)++ + H2O ---> Al(OH)2+ + H+
Al(OH)2+ + H20 ---> Al(OH)3 + H+
 Sources of
acidity in Soil

1. Nitrification: Ammonium to Nitrate

(oxidation of NH4+)
NH4+ + 2O2 ---> NO3- + H2O + 2 H+
2. O.M. decomposition
organic acids ionized :
R-COOH---> R-COO- + H+
respiration: CO2 + H2O ---->
H2CO3 = H+ HCO3-
 3. Acid rain
 Acid rain is caused by the
burning of fossil fuels.
 Burning oil, gas and coal in
power stations releases
Sulfuric Dioxide (SO2) into
the atmosphere.
 Burning oil and gasoline in
motor vehicles puts nitrogen
oxides (NOX) into the
atmosphere.
 These gases mix with water
droplets in the atmosphere
creating weak solutions of
nitric and sulfuric acids.
 When precipitation occurs
these solutions fall as acid
rain.
 Acid Rain in USA
3. Acid Rain
SO2 +OH --> H2SO4 --> SO4- + 2 H+
NO2 + OH --> HNO3--> NO3- + H+
 Dyad
• Have you experienced acid rain? If so
where.
• If not, where might you experience the
results of this environmental problem.
 Sources of acidity in Soil
• 4. Uptake of basic
cations by plants.
Basic cations are
sources of OH- to the
soil solution.
• Ca++, Mg++, K+, =
• Basic cations that are
taken up by plants no
longer contribute OH-
to the soil solution.
• H+ ions are released to
the soil solution.
 Leaching
5. Leaching of basic cations -
as basic cations are removed
from the soil solution by
leaching they no longer
contribute the OH- ions to
neutralize the ever increasing
amounts of H+
Ca++ + 2 H20 ---> Ca(OH)2 + 2H+
-----> Ca++ + 2OH-
 Soil Acidity and Plant Growth
• Soil acidity is a major
environmental stress factor which
limits the growth of most crops.
• Acid soils are widely dispersed and
comprise approximately 40% of the
arable land in the world.
• In addition, acid rain also
accelerates the acidification of
soils.
• Aluminum (Al) ion is solubilized
from soils at low pH. This is a
major toxic factor for plant growth
for low pH soils. Acid soil (Yunnan Province,
People's Republic of China).
 Soil Acidity in Australia
• Soil acidification is a natural process
that is part of all landscapes.
• Land clearing of native vegetation and
their replacement with productive
crops and pastures has accelerated
acidification over the past 200 years.
• In the past 50 years a significant
lowering in soil pH due to greater use
of fertilizers, increased production, a
greater use of legumes and an
increase in irrigated agriculture.
• An effective option
in some cases is a
matter of applying
lime…. however
• The land use should
be matched to the
capability of the
land and soil,
available rainfall,
and rate of
acidification.
 Acid Sulfate Soils
• Acid sulfate soils form The red color of the
when pyritic* (mineral water is caused by
of FeS2) estuarine oxidized iron
sediments in the
subsoil are exposed to
air, oxidizing to form
sulfuric acid.
• A variety of soil
minerals react with
the acid and release
free aluminum, toxic
to crops and marine
life.
*Pyrite is the most common iron disulphide mineral in rock. It is found most often
in metamorphic and sedimentary rocks where it occurs as either a primary mineral
or a fine, widespread impregnation of subsequent origin. Pyrite is frequently found
in association with coal and shale deposits.
• Acid sulfate soils are
extremely acidic (at
times less than 3.0)
soil horizons resulting
from the aeration of
soil materials that are
rich in iron sulfides,
(FeS)
• Acid sulfate soils are
unique in that the
impacts can be so
severe that they can
affect engineering
works, agricultural
productivity, and
water quality of Acid soils have cost Australia $10
estuarine systems billion in environmental damage as
a result of coastal development.
• Iron staining is often a good
indicator of disturbed acid
sulfate soils.
• When acid sulfate soils are
disturbed and undergo oxidation,
the sulfuric acid produced
mobilizes iron, aluminum and
heavy metals present in the soil.
• Toxic amounts of dissolved iron
can then be washed into
waterways.
• This iron can precipitate when in
contact with less acid water,
such as rainwater or seawater.
• This results in a rust-colored
iron oxide scum or ‘floc’ which
can smother vegetation and stain
concrete and soil.
• From: 'QASSIT, Qld
Department of Natural
Resources and Mines'
Green acid water leached from Acid Sulfate
Soils pours into a river