“Strengthening the Capacities of BSWM and RSLs in the

Operation and Establishment of Soils Laboratories as per

PD 1435”

Soil pH

PD 1435
LABORATORY SERVICES DIVISION
 Scope
• This method presents the common measurement of soil pH in a 1:1 mixture of
soil to deionized water along with modifications with electrolyte solutions
using a pH meter.

• The pH-H2O method measures active acidity and is used for fertilizer
recommendation and for routine analysis.

• The pH in One Molar Potassium Chloride (1 M KCl) is used to measure

reaction in highly weathered tropical soils.

• The pH in One-One Hundredth Molar Calcium Chloride (0.01 M CaCl 2) method

is applied for soil characterization, soil classification and soil taxonomy
purposes. The pH in 0.01 M CaCl2 is somewhat, but not entirely invariable
with naturally changing salt concentration in soils.
 Principle
• A measured quantity of soil is shaken with a convenient volume of water or an
electrolyte solution under consistent conditions. Soil pH is determined with
an H+ ion-selective glass electrode (referenced with a standard calomel
electrode) inserted into a soil mixture that simulates the soil solution. The
difference between the H+ ion activities in the soil solution and the glass
electrode gives rise to an electrometric potential difference that is related to
the soil solution pH, or the active acidity.

• It is determined by the concentration of hydrogen ions [H +]. It is measured

using the formula of negative logarithmic scale of the hydrogen ion
concentration [H+], pH = -log[H+.]. The soil pH value is either an acidic
solution (less than 7) or an alkaline solution (greater than 7). So, as the
hydrogen ion concentration goes up, the pH value goes down, which makes it
more acidic, and vice versa with alkaline solution. [2]
 Principle
• Soil pH is influenced by both acid and base-forming cations (positively charged dissolved
ions) in the soil. Common acid-forming cations are hydrogen (H +), aluminum (Al3+), and
iron (Fe2+ or Fe‑), whereas common base-forming cations include calcium (Ca 2+),
magnesium (Mg‑), potassium (K+) and sodium (Na+). [2]
• The determination of soil pH value is used to characterize and make a rough calculation
about the nutrient availability of the soil because of the H+ ions, which take up the space
on the negative charges along the soil surface. Thus, at higher pH, Potassium, Sulfur,
Calcium and Magnesium are more available while at lower pH, the micronutrients (Zn,
Cu, B, Mn, Fe and Mo, for example) are more available. [2] Using the pH value of the soil, we
can identify the dominant cations on soil cation exchangers at the time of soil sampling
and analysis. If the pH value below 4.0 it is impossible to achieve with Al 3+ saturation so
that acidity 10 to 100 times more intense (pH of 2-3) indicates the presence of free
mineral acid, usually H2SO4. At pH 4-5, the presence of exchangeable Al3+ will be
encountered in mineral soils. In a very acid soils, a suspension of soil made with KCl
solution similar to soil-water mixture releases into the soil solution aluminum and
hydrogen ions present. Whereas the exchangeable Al 3+ will be no longer present if the pH
is 5.5 and above. If the pH values are around 7.6 to 8.3, it can be an indicator of CaCO 3
excess which is found to be calcareous. [1]
 Principle
• In determining the pH value of soils, analysts can identify what affects the plants. All
plants can be affected by the extremes of pH depending in their tolerance of acidity and
alkalinity. Some plants can grow in a wide pH range, while others are very sensitive to
small variation of acidity or alkalinity. Microbial activity in the soil can also have affect by
soil pH. Various species of earthworms and nitrifying bacteria disappear, when there is
an occurrence of extreme of acidity or alkalinity. The changes in the availability of
nutrients can have some effects on plant growth attributed to acid soils. Soil pH affects
the availability of nutrients and how it reacts with each other. At a low pH, beneficial
element such as molybdenum (Mo), phosphorus (P), magnesium (Mg) and Calcium (Ca)
become less available to plants. Other elements like aluminum (Al), Manganese (Mn) and
Iron (Fe) may reach levels that are toxic to plants. Thus, knowledge of the soil pH and
associated aluminum toxicity is vital before planning to sow crops or pastures. Also,
alkaline soils cause zinc and cobalt deficiencies that lead to stunted plants, poor growth
and reduced yields in some crops and pastures. [3]
• The pH of soil changes over time, by monitoring and comparing the past and present soil
test there is a probability to see if the soil acidity is increasing over time. Thus, we can
prevent this trend from continuing. [3]
 Test Precautions
• The pH values are dependent on temperature. It should be measured at
constant temperature. If a precision greater than 0.1 pH unit is desired, the
temperature of the standard solutions, the glass electrode, and the test
solution must be within 2oC of one another. They must be at the temperature
of measurement for at least two hours prior to making the measurement in
order to reduce to a negligible value the effects of thermal or electrical
hysteresis of the electrodes.

• Solutions used in the determination of pH are to be prepared with carbon-

dioxide-free water, i.e. distilled water previously boiled for 15 min and cooled
to room temperature. The final pH of the water should lie between 6.2 and
7.2.

• In soil pH measurement, electrodes may be placed in the clear supernatant

above the soil. Also, be cautious, the electrode must not touch the suspended
soil to avoid error in pH value. The important thing is that the measurement
be carried out in a consistent way.
 Test Precautions
• In water pH determination, values taken in the supernatant generally will be slightly
higher than in the stirred suspension. The determination of soil pH is to measure the
average activity of hydrogen ions in the soil-water system. With a salty pH, the
differences between the three techniques practically disappear.

• Before use, glass electrodes are to be soaked in dilute acid and thereafter should not be
allowed to dry out. When not in use, they should be kept immersed in distilled water.
The presence of water is essential to maintain the pH function of a glass electrode. This
function is being impaired even if the bulb is immersed in a dehydrating fluid such as
ethanol. When not in use, ensure that the reference electrode always contains saturated
potassium chloride in contact with solid potassium chloride crystals.

• Clean the glass electrode periodically if necessary, by soaking it in a solution of a mild

detergent and wiping it with a piece of tissue paper, to remove the film of soil that
adheres to the electrode surface. A film of CaCO 3 that sometimes forms on the surface of
the glass electrode during measurement of pH of calcareous soils may be removed by
dipping the electrode for a few seconds in dilute HCl and rinsing it with water.
 Equipment
1. pH meter equipped with glass and reference electrode, or combination
electrode
2. Balance, precision of at least 0.001g
3. Reciprocating shaker
 Laboratory Ware
1. Pipet or Bottle Top dispenser, 10 mL
2. Beakers, 50 mL or 100 mL beaker
3. Stirring rods
4. Polyethylene container tubes, 50 mL or 100 mL capacity
 Chemicals and Reagents
1. NIST Traceable standard buffer solutions of pH 4.0, pH 7.0, and pH 10.0.
2. Deionized water.
3. Calcium chloride, 0.01 M. Dissolve 1.47 g of CaCl2.2H2O in one liter distilled
water.
4. Calcium chloride, 0.02 M. Dissolve 2.94 g of CaCl2.2H2O in one liter distilled
water.
5. KCl solution, 1 M. Dissolve 74.55 g dry KCl in distilled water and make up to 1
L.
 Health and Safety
• Wear proper personal protective equipment. Use laboratory coat, close
shoes, gas mask or dusk masks and appropriate gloves when performing
chemical analysis to mitigate the harmful effects of exposure on chemicals. [6]

• Observe careful and proper handling of chemicals when using inorganic

salts, strong alkali bases, strong acids and oxidizing agents. Potential direct
body contact (e.g. ingestion, inhalation) may cause severe irritation and
inflammation to the skin, eyes, respiratory and digestive tracts. Severe
exposure to these corrosive substances may cause serious health damage or
death. [7]

• Avoid mixing incompatible chemicals to reduce risks of fire and explosion

inside the laboratory. Keep locked up and away from incompatibles such as
moisture. [6]
 Procedure
Calibration of the pH meter
 
1. Calibrate pH meter with fresh aliquots of three standard pH.
2. These calibration buffers must be within ±0.05 of true value. Slope value
must be at 90-100%.
 Procedure
A. pH in Water (H2O, 1:1) [1]
 
1. Weigh out 10 g of air-dry soil in a 50 or 100 mL container tube.
2. Add 10 mL of deionized water to the soil in the container tube, place a stopper
and shake it in a mechanical shaker for 10 mins. If a mechanical shaker is not
available, shake the container vigorously by hand for 1 minute at least four
times at 30 minutes intervals. A stirring rod or stirring machine can be used
but care should be exercised to minimize contamination. Shake for 10
minutes.
3. Let stand for 10 minutes.
4. Swirl the suspension in the container and insert the electrodes into the
suspension.
5. Read pH and record as pHw.
6. Rinse the electrodes with deionized water between pH readings. Blotting is
not necessary.
 Procedure
B. pH in 0.01 M and 0.02 M CaCl2 [1]
 
If pH determination in water is also required, use 0.02 M CaCl 2 (CaCl2 1:2)
 
1. Add 20 mL of 0.02 M CaCl2.2H2O to the soil suspension used in determining
pH in water.
2. 2. Place a stopper and shake it in a mechanical shaker for 10 mins. If a
mechanical shaker is not available, shake the container vigorously by hand
for 1 minute at least four times at 30 minutes intervals. A stirring rod or
stirring machine can be used but care should be exercised to minimize
contamination. Shake for 10 minutes.
3. Let stand for 10 minutes.
4. Swirl the suspension in the beaker and insert the electrodes into the
suspension.
5. Read pH and record as pHCaCl2.
 Procedure
B. pH in 0.01 M and 0.02 M CaCl2 [1]
 
If only pH determination in CaCl2 is required, use 0.01 M CaCl2 (CaCl21:1)
 
1. Weigh out 10 g of air-dry soil in a 50 or 100 mL container tube.
2. Add 10 mL of 0.01 M CaCl2 to the soil in the container tube, place a stopper
and shake it in a mechanical shaker for 10 mins. If a mechanical shaker is
not available, shake the container vigorously by hand for 1 minute at least
four times at 30 minutes intervals. A stirring rod or stirring machine can be
used but care should be exercised to minimize contamination. Shake for 10
minutes.
3. Let stand for 10 minutes.
4. Swirl the suspension in the beaker and insert the electrodes into the
suspension.
5. Read pH and record as pHCaCl2.
 Procedure
C. pH in 1 M KCl (KCl, 1:1) [1]
 
1. Weigh out 10 g of air-dry soil in a 50 or 100 mL container
2. Add 10 mL of 1 M KCl to the soil in the container tube, place a stopper and
shake it in a mechanical shaker for 10 mins. If a mechanical shaker is not
available, shake the container vigorously by hand for 1 minute at least four
times at 30 minutes intervals. A stirring rod or stirring machine can be used
but care should be exercised to minimize contamination. Shake for 10
minutes.
3. Let stand for 10 minutes.
4. Swirl the suspension in the beaker and insert the electrodes into the
suspension.
5. Read pH and record as pHKCl.
 Quality Assurance Procedure
1. Precision Test – Perform duplicate analysis on one sample for every 10 tests.
The difference of duplicates must be 0.1 pH units or corrective action must be
taken.

2. Accuracy Test – Analyze Certified Reference Material and participate in Inter-

Laboratory Proficiency Test (PT) at least once a year. Result of CRM should fall
within the certified value. The PT z-score should be less than 2. If not, identify
root cause, develop corrective and preventive actions, prepare CAPA Report, and
address the problem.
 
3. Accuracy Test – Perform standardization with fresh buffer solutions. The
acceptable range for the slope value is 90-100%
 
4. Control Chart – Analyze check sample once for every 20 samples or at least
once every day. Plot the result in the control chart. Assess trend for Out of Control
Signals and develop corrective actions; prepare CAPA Report.
 Waste Disposal
• The extracting solutions such as deionized water, Potassium Chloride and
Calcium Chloride and excess soil extracts can be stored in a wide mouth
container (e.g. carboy). The container must be labelled inorganic salt waste.
Upon disposal, Potassium Chloride and Calcium Chloride can be diluted or
neutralized before draining into the sink since the inorganic salts are
considered to be low in toxicity, might as well the water used for extraction. [8]
 References
[1]
Thomas, G.W. (1996). Soil pH and Soil Acidity. In D.L. Sparks (Ed.-in-Chief), Soil Science Society of
America, Book Series 5. Methods of Soil Analysis Part 3, Chemical Methods. Madison, Wisconsin: Soil
Science Society of America, Inc.
[2]
McCauley, A., Jones, Clain, Olson-Rutz, Kathrin (2017). Soil pH and Organic Matter. Nutrient
Management Module No. 8. Retrieved from http://landresources.montana.edu/nm/documents/NM8.pdf
[3]
Lake, B (2000). Understanding Soil pH. Acid Soil Management, Leaflet No.2.
Retrieved from https://www.dpi.nsw.gov.au/__data/assets/pdf_file/0003/167187/soil-ph.pdf
[4]
Malaya (2016, May 30). In DENR Administrative Order 2016-08: Water Quality Guidelines and General
Effluent Standards of 2016. Retrieved from https://server2.denr.gov.ph/uploads/rmdd/dao-2016-08.pdf
[5]
Updated Manual for Soil, Water, Plant Tissue and Fertilizer Analysis. Bureau of Soils and Water
Management – Laboratory Services Division. 2014.
[6]
Safety Manual. Bureau of Soils and Water Management – Laboratory Services Division. 2018. (1 st. ed.,
pp. 8-13)
[7]
Safety Data Sheet. Bureau of Soils and Water Management – Laboratory Services Division.
[8]
Montana State University. Lab waste drain disposal. Retrieved from
http://web.mit.edu/cohengroup/safety/drain%20disposal120810.pdf