This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

Designation: D4972 − 19

Standard Test Methods for

pH of Soils1
This standard is issued under the fixed designation D4972; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope*
1.1 These test methods cover the measurement of the pH of
soils that will pass the 2.00 mm (No. 10) sieve. Such
measurements are used in the agricultural, environmental,
geotechnical, and natural resources fields. This measurement
determines the degree of acidity or alkalinity in soil materials
suspended in water and a 0.01 M calcium chloride solution.
Measurements in both liquids are necessary to fully define the
soil’s pH. This variable is useful in determining the solubility
of soil minerals and the mobility of ions in the soil and
assessing the viability of the soil-plant environment. A more
detailed discussion of the usefulness of this parameter is given
in Refs (1-6)2.
1.2 Two methods for measuring the pH of soils are pro-
vided. The method to be used shall be specified by the
requesting authority. When no method is specified, Method A
shall be used. The pH is determined in test water and a calcium
chloride solution for both methods.
1.2.1 Method A—The pH is measured using a potentiometer
having a pH sensitive electrode system. This method can be
used for any application and must be used when the application
warrants a higher level of resolution.
1.2.2 Method B—The pH is measured using pH sensitive
paper. This method can be used for any application, however,
because paper typically has a lower resolution, it provides an
approximate estimate of the pH of the soil and should not be
used when the application requires a higher level of resolution
(Note 1).
NOTE 1—For example, paper with a sensitivity to the nearest 1 pH unit
placed into a buffer solution of 4 should indicate a pH of 4, however, it
would not indicate if the pH is 4.449 or 3.449.
1.3 Units—The values stated in SI units are to be regarded
as standard. No other units of measurement are included in this
standard.
1
These test methods are under the jurisdiction of ASTM Committee D18 on Soil
and Rock and is the direct responsibility of Subcommittee D18.22 on Media for
Plant Growth.
Current edition approved May 1, 2019. Published May 2019. Originally
approved in 1989. Last previous edition approved in 2018 as D4972 – 18. DOI:
10.1520/D4972-19.
2
The boldface numbers in parentheses refer to a list of references at the end of
this standard.
1.4 All measured and calculated values shall conform to the
guidelines for significant digits and rounding established in
Practice D6026.
1.4.1 The procedures used to specify how data are collected/
recorded and calculated in the standard are regarded as the
industry standard. In addition, they are representative of the
significant digits that generally should be retained. The proce-
dures used do not consider material variation, purpose for
obtaining the data, special purpose studies, or any consider-
ations for the user’s objectives; and it is common practice to
increase or reduce significant digits of reported data to be
commensurate with these considerations. It is beyond the scope
of these test methods to consider significant digits used in
analysis methods for engineering data.
1.5 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use.
1.6 This international standard was developed in accor-
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:3
C670 Practice for Preparing Precision and Bias Statements
for Test Methods for Construction Materials
D653 Terminology Relating to Soil, Rock, and Contained
Fluids
D1193 Specification for Reagent Water
D2487 Practice for Classification of Soils for Engineering
Purposes (Unified Soil Classification System)
D2488 Practice for Description and Identification of Soils
(Visual-Manual Procedures)
D3740 Practice for Minimum Requirements for Agencies
Engaged in Testing and/or Inspection of Soil and Rock as
3
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.

*A Summary of Changes section appears at the end of this standard

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1
 D4972 − 19
Used in Engineering Design and Construction
D4220/D4220M Practices for Preserving and Transporting
Soil Samples
D4753 Guide for Evaluating, Selecting, and Specifying Bal-
ances and Standard Masses for Use in Soil, Rock, and
Construction Materials Testing
D6026 Practice for Using Significant Digits in Geotechnical
Data
D6913 Test Methods for Particle-Size Distribution (Grada-
tion) of Soils Using Sieve Analysis
G51 Test Method for Measuring pH of Soil for Use in
Corrosion Testing
3. Terminology
3.1 Definitions:
3.1.1 For definitions of common technical terms used in this
standard, refer to Terminology D653.
4. Summary of Test Method
4.1 This test method is used to determine the pH of a soil.
Two similar test specimens are obtained from a representative
sample that has been air-dried and screened over a 2.00 mm
(No. 10) sieve. From the material passing the 2.00 mm (No. 10)
sieve, one specimen is mixed with test water and one is mixed
with a calcium chloride solution. They are then thoroughly
stirred and both are allowed to stand for one hour prior to
testing using Method A or B.
5. Significance and Use
5.1 The pH of the soil is a useful variable in determining the
solubility of soil minerals, the mobility of ions in the soil, and
assessing the viability of the soil-plant environment.
5.2 pH measurements are made in both test water and a
calcium chloride solution because the calcium displaces some
of the exchangeable aluminum. The low ionic strength coun-
ters the dilution effect on the exchange equilibrium by setting
the salt concentration of the solution closer to that expected in
the soil solution. The pH values obtained in the solution of
calcium chloride are slightly lower than those measured in
water due to the release of more aluminum ions which then
hydrolyses. Therefore, both measurements are needed to fully
define the character of the soil’s pH.
5.3 For the purpose of these test methods, the test specimens
are sieved through a 2.00 mm (No. 10) sieve. Measurements on
soils or soil fractions having particle sizes larger than 2.0 mm
by these test methods may be invalid. If soil or soil fractions
with particles larger than 2.0 mm are used, it must be stated in
the report since the results may be significantly different.
NOTE 2—The quality of the result produced by this standard is
dependent on the competence of the personnel performing it, and the
suitability of the equipment and facilities used. Agencies that meet the
criteria of Practice D3740 are generally considered capable of competent
and objective testing/sampling/inspection/etc. Users of this standard are
cautioned that compliance with Practice D3740 does not in itself assure
reliable results. Reliable results depend on many factors; Practice D3740
provides a means of evaluating some of those factors.
2
6. Interferences
6.1 When using Method A, a pH probe has possible inter-
ferences due to a suspension effect or sedimentation potential.
Refs (5) and (6) provide a more detailed discussion of the effect
of this mechanism.
6.2 This effect is the main reason Test Method G51 cannot
be used for general measurement of pH outside of that for
corrosion analysis. Test Method G51 measures pH, an aqueous
parameter, without adding any aqueous phase to the soil. This
lack of aqueous phase results in excessive soil particle-pH
probe contact that overestimates the activity of the hydrogen
ions in solution and is therefore unacceptable for general soil
analysis.
6.3 The suspension effect can be mitigated by careful
attention to inserting the probe into the aqueous phase of the
slurry. The aqueous phase consists of the partially settled
suspension.
7. Apparatus
7.1 Use one of the following devices to measure the pH.
7.1.1 pH Meter—Potentiometer equipped with an electrode
system with a readability to the nearest 0.1 pH unit and an
accuracy of 60.1 pH unit or better. Follow the manufacturer’s
instructions for the pH meter used. A silver/silver chloride
electrode system or similar is also acceptable.
7.1.2 pH Paper—pH-sensitive paper having a typical range
from 1 to 12 with sensitivity to the nearest 0.5 pH unit or better.
The range of the paper may vary based on the typical pH of the
materials being tested. It is acceptable to use paper ranging
between other values as long as the range is large enough to
bracket the expected pH result.
7.2 Balance—Balances shall conform to the requirements of
Specification D4753.
7.2.1 To determine the mass of the specimen, the balance
shall have readability without estimation of 0.1 g or better. The
capacity of this balance will need to exceed the mass of the
container plus soil. In general, a balance with a minimum
capacity of 300 g is sufficient.
7.3 Separation Sieve—2.00 mm (No. 10) sieve used to
separate the coarse material from the representative sample.
This sieve is subjected to rough operation and shall not be used
for quantitative testing.
7.4 Specimen-Mixing Container—A glass beaker or equiva-
lent inert container with enough capacity to hold the specimen
and the test water. Usually, a 100 mL to 250 mL glass beaker
is large enough.
7.5 Drying Oven (Optional)—Vented, thermostatically con-
trolled oven capable of maintaining uniform temperatures of
105 6 5°C and 130 6 5°C as needed throughout the drying
chamber. These requirements typically require the use of a
forced-draft oven.
7.6 Volumetric Flask or Cylinder—Two, glass or plastic;
one each with capacities of 1 L and 2 L. Required for making
calcium chloride hydrate solutions, otherwise, they are op-
tional.
 D4972 − 19
7.7 Thermometric Device—A thermometric device capable
of measuring the temperature range within which the test is
being performed readable to 0.5°C or better and having an
accuracy of at least 60.5°C.
7.8 Miscellaneous Items—Items such as a wash/rinse bottle
(squirt bottle), rubber scraper, spatula, plastic or glass contain-
ers to hold reagents, and stirring rod may be useful.
8. Reagents
8.1 Purity of Reagents—Reagent grade chemicals should be
used in all tests. Unless otherwise indicated, it is intended that
all reagents should conform to the specifications of the
Committee on Analytical Reagents of the American Chemical
Society, where such specifications are available.4 Other grades
may be used, provided it is first ascertained that the reagent is
of sufficient purity to permit its use without lessening the
accuracy of the determination.
8.2 Test Water—Type III water in accordance with Specifi-
cation D1193 or distilled/deionized water with a pH between
6.5 and 7.5.
8.3 Buffer Solutions—Buffer solutions are commercially
available and providing they meet the purity of reagents as
described above, they are an acceptable alternative to making
buffer solutions. The following NIST traceable buffer solutions
are typically needed: pH of 4.0, 7.0, and 10.0. When making
buffer solutions, refer to Annex A1 for the necessary chemicals
and instructions.
8.4 Calcium Chloride Hydrate Stock Solution (CaCl2·
2H2O)—Using the 1 L volumetric flask or cylinder, dissolve
147 g of CaCl2· 2H2O in test water and allow it to come to
room temperature. Then, dilute by adding test water to the 1 L
mark on the volumetric flask or cylinder. Mix the solution
thoroughly. The molarity of this solution is 1.0 M (Note 3).
8.5 Calcium Chloride Hydrate Solution (CaCl2· 2H2O)
Using the 2 L volumetric flask or cylinder, add 20.0 mL of the
calcium chloride hydrate stock solution and test water by
adding test water to the 2 L mark on the volumetric flask or
cylinder. Mix the solution thoroughly. The pH of this solution
should be between 5 and 7 and the molarity is 0.01 M.
NOTE 3—It is acceptable to purchase the calcium chloride solutions
provided they have the same molarity and pH as described above.
9. Hazards
9.1 These solutions may cause eye and skin irritation. Care
should be taken to avoid contact with skin and eyes and
solutions should not be ingested. The use of latex or rubber
gloves, and possibly safety glasses, when working with the
solutions is recommended. Wipe up spills immediately. Rinse
skin coming into contact with the solutions with water quickly.
4
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
MD.
3
10. Sampling and Test Specimens
10.1 General—These test methods do not address, in any
detail, procurement of the sample. It is assumed the sample is
obtained using appropriate methods and is representative of the
soil under evaluation. However, the testing agency shall
preserve all samples in accordance with Practice D4220/
D4220M, Group B, except if the as-received sample does not
meet those requirements. In which case, the water content of
the material does not have to be maintained.
10.2 Sampling—Obtain a representative sample from the
bulk sample. Follow guidance given in Test Method D6913,
Annex A2, for specimen splitting/reducing. The moist mass of
the representative sample must be large enough such that, after
air drying and screening over the 2.00 mm (No. 10) sieve, the
air-dried mass will be large enough to yield two test specimens.
10.2.1 Place the representative sample on a tray, pan, or flat
surface to facilitate uniform air-drying. Be careful not to lose
fines during this process. After drying, if the sample appears to
have particles larger than 2.0 mm, the sample must be screened
over the 2.00 mm (No. 10) sieve. If there are no coarse
particles present, screening is not necessary. See 5.3 for soils
having coarse particles and tested using these methods.
10.2.2 Air drying is necessary to accomplish sieving and to
control the amount of water present at the time of measure-
ment.
10.3 Test Specimens—Since the soil is in the air-dried state,
segregation and loss of fines are common problems and care
should be taken to make sure the test specimens accurately
represent the sample. From the soil passing the 2.00 mm (No.
10) sieve, obtain two similar specimens for testing. Typically,
a mass of 10 6 0.1 g is adequate, however, 20 6 0.1 g or 40
6 0.1 g specimens may be necessary to allow for the pH
electrode to be fully submerged.
10.3.1 For both methods, determine and record the mass of
the test specimens to the nearest 0.1 g.
11. Standardization
11.1 Before each use standardize the pH meter using the
buffer solutions in 8.3 or Annex A1 following the manufactur-
er’s instructions of the meter. Select buffers so that the
expected pH value of the tested soil is bracketed. Typically
buffers of 4, 7, and 10 meet this requirement for most soils;
however, in some applications buffers with higher or lower pH
values are needed. Follow the manufacturer’s instructions to
adjust the pH meter accordingly. Record the date, time, and
name or initials of person completing the standardization. If
other data in association with the standardization is
determined, record this information (Note 4).
11.1.1 After every 10 specimens or at the end of testing,
whichever occurs first, verify the pH meter’s standardization
by inserting the probe into the pH 7.0 buffer solution. The
value should be between 6.9 and 7.1. Read and record the pH
value to the nearest 0.1 pH unit. If the value falls outside of this
range, the pH meter must be re-standardized and the previous
specimens must be retested to verify the results.
11.2 Check the pH sensitive paper by inserting a small
portion of the paper into the pH 4.0, 7.0, and 10.0 buffer
 D4972 − 19
solutions and compare each portion to the color guide provided
by the manufacturer of the pH paper. This check is typically
undocumented.
NOTE 4—Some pH meters output a linearity or other data to indicate the
meter is working properly.
12. Procedure
12.1 Preparation—Place one of the test specimens in a
specimen mixing container and add the same amount of test
water in mL as the specimen mass in g to make a 1 to 1 slurry.
Place the other test specimen into a specimen mixing container
and add the same amount of calcium chloride solution in mL as
the specimen mass in g to make a 1 to 1 slurry (Note 5). Mix
both slurries thoroughly and allow them to stand for 1 h. The
slurry should be at approximately room temperature (15 to
25°C) at the time of pH measurement. In cases where the test
specimen readily absorbs the water such that no aqueous phase
exists, it is permissible to make a 1 to 2 slurry. This situation
can occur with clay soils that swell.
12.2 Method A—After 1 h, verify the temperature of the
slurry is at room temperature then, fully submerge the pH
electrode into the aqueous part of the slurry. Be careful not to
insert the electrode into the solids. Read and record the pH of
the slurry to the nearest 0.1 pH unit. If the pH meter does not
automatically compensate for temperature, determine and re-
cord it to the nearest 0.5°C or better.
12.3 Method B—After 1 h, determine and record the tem-
perature of the slurry to the nearest 0.5°C then, carefully insert
a strip of the pH sensitive paper into the aqueous part of the
slurry. Be careful not to insert it into the solids. Read and
record the pH of the slurry to the nearest 0.5 pH unit.
NOTE 5—For example, if the mass of the test specimen is 20.1 g, then
20.1 mL of test water or calcium chloride solution is added to the test
specimen to make a 1 to 1 ratio. In rare instances and usually only for
clays that, can and do, absorb significant amounts of water relative to their
mass, a 1 to 5 ratio may be used when a 1 to 2 ratio does not yield an
adequate amount of aqueous phase.
13. Report: Test Data Sheet(s)/Form(s)
13.1 The methodology used to specify how data are re-
corded on the test data sheet(s)/form(s), as given below, is
covered in 1.4 and in Practice D6026.
13.2 Record as a minimum the following general informa-
tion (data):
13.2.1 Identification of the soil being tested, such as the
project identification, boring number, sample number, and
depth.
13.2.2 Test number, if any, testing dates and the initials of
the person(s) who performed the test.
13.2.3 Describe any material that was excluded from the
specimen and any special selection and preparation process.
13.2.4 The following apparatus identification used during
the test:
13.2.4.1 Balance identification number.
13.2.4.2 pH meter and electrode identification number
(Method A only).
4
13.2.4.3 Thermometric device identification number.
13.2.4.4 Specimen mixing container identification number.
13.2.5 Description and classification of the soil in accor-
dance with Practice D2488 or when Atterberg limit data are
available, Practice D2487.
13.2.6 Describe any problems that were encountered.
13.3 Record as a minimum the following test specimen
data:
13.3.1 Method used, A or B.
13.3.2 The pH of the soil in test water and in the calcium
chloride solution.
13.3.3 The temperature of the slurry at the time of
measurement, as applicable.
13.3.4 If testing was performed on soil that contained coarse
particles as discussed in 5.3, include a statement indicating the
results may be significantly different.
14. Precision and Bias
14.1 Precision:
14.1.1 Within-Laboratory Precision—The within laboratory
standard deviations for Method A are 0.031 (pH units) for the
water mixture and 0.1395 (pH units) for the calcium chloride
mixture. Therefore, results of two properly conducted tests in
the same or different laboratories should not differ by more
than 0.0655 (pH units) for the water mixture and 0.389 pH units
for the calcium chloride mixture. The within-laboratory stan-
dard deviations for Method B are 0.189 (pH units) for the water
mixture and 0.2125 (pH units) for the calcium chloride mixture.
Therefore, results of two properly conducted tests in the same
or different laboratories should not differ by more than 0.535
(pH units) for the water mixture and 0.60 pH units for the
calcium chloride mixture.
14.1.1.1 The precision of Method A presented was deter-
mined by the National Technical Center of the United States
Department of Agriculture. In their evaluation they used 174
replicates for the water mixture and 32 replicates in testing the
calcium chloride mixture.
14.1.1.2 The precision of Method B presented was deter-
mined by the United States Army Environmental Hygiene
Agency. In their evaluation they used 25 replicates in testing
each mixture.
14.1.2 Between-Laboratory Precision—The between-
laboratory standard deviation has not been determined for
either method. Subcommittee D18.22 is actively seeking data
to evaluate the between laboratory precision of this test
method.
14.2 Bias—There is no accepted reference value for this test
method; therefore, bias cannot be determined.
15. Keywords
15.1 acidity; alkalinity; pH; reaction; soil
5
These data satisfy the 1S and D2S requirements outlined in Practice C670.
 D4972 − 19
ANNEX

A1. MAKING BUFFER SOLUTIONS

(Mandatory Information)

A1.1 General—Commercially available buffer solutions can Stir the solution thoroughly. The pH of this solution should be
be used to standardize and verify a pH meter; however, buffer 6.9 at 20°C. The molarity is 0.025 M. The effect of temperature
solutions can be made. The following sections provide the is as follows:
necessary information and chemicals to make pH solutions of Temperature (°C) pH
4, 7, and 10. For all buffers, record the temperature to the 0 7.0
nearest 0.5°C. 10 6.9
20 6.9
A1.1.1 pH 4—Potassium Phthalate Buffer Solution (10.21 30 6.8
g/L)—Dry the potassium phthalate (C8H4K2O4) in the oven for 40 6.8

1 hour at 105 6 5°C, then dissolve 10.21 g of it in test water A1.1.3 pH 10—Carbonate Buffer Solution—Dry both salts
and dilute to 1 L by adding test water to the 1 L mark on the in the oven for 2 h at 130 6 5°C before use, then dissolve 2.10
volumetric flask or cylinder. Stir the solution thoroughly. The g of sodium bicarbonate (NaHCO3) and 2.65 g sodium
pH of this solution should be 4.0 at 20°C. Protect the solution carbonate (Na2CO3) in test water and dilute to 1 L by adding
against evaporation and against contamination with molds. test water to the 1 L mark on the volumetric flask or cylinder.
Replace the solution when mold is noticed. There is no
Stir the solution thoroughly. The pH of this solution should be
temperature correction needed if the temperature of the solu-
10.1 at 20°C. The molarity is 0.025 M. The effect of tempera-
tion is between 5°C and 37°C. The molarity of this buffer is
ture is as follows:
0.05 M.
Temperature (°C) pH
A1.1.2 pH 7—Potassium Phosphate Buffer Solution—Dry 0 10.3
both salts in the oven for 2 h at 130 6 5°C before use, then 10 10.2
20 10.1
dissolve 3.40 g of monopotassium phosphate (KH2PO4) and 30 10.0
3.55 g of KH2HPO4 in test water and dilute to 1 L by adding 40 9.9
test water to the 1 L mark on the volumetric flask or cylinder.

REFERENCES

(1) Garrels, R. M., and Christ, C. L., Solutions, Minerals, and Equilibria,
Freeman Cooper, San Francisco, CA, 1965.
(2) Greenland, D. J., and Hayes, M. H. B., The Chemistry of Soil
Processes, Wiley, New York, NY, 1981.
(3) Sposito, G., The Thermodynamics of Soil Solutions, Clarendon,
Oxford, United Kindom, 1981.
(4) Davies, J. T., and Rideal, E. K., Interfacial Phenomena, Academic,
New York, NY, 1963.
(5) Hunter, R. J., Zeta Potential in Colloid Science, Academic, New York,
NY, 1981.
(6) Perrin, D. D., and Dempsey, B., Buffers for pH and Metal Ion Control,
Chapman and Hall, London, United Kindom, 1974.

SUMMARY OF CHANGES

Committee D18 has identified the location of selected changes to this standard since the last issue
(D4972 – 18) that may impact the use of this standard. (May 1, 2019)

(1) Included ratios other than 1 to 1 in 12.1 and Note 5. (2) Clarified aqueous phase as it relates to suspension effect.

Committee D18 has identified the location of selected changes to this standard since the last issue
(D4972 – 13) that may impact the use of this standard. (July 1, 2018)

(1) Updated the Scope section to include descriptions of the (4) Moved making buffer solutions to annex and included
test methods. information about commercially available buffers; updated
(2) Updated Summary of Test Method section. water requirements.
(3) Added missing apparatus to apparatus section. (5) Added Hazards and Sampling and Test specimen sections.

5
 D4972 − 19
(6) Clarified the standardization of the pH meter. (8) Updated the Report section.
(7) Reworded procedure section for clarity.

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