THIS DOCUMENT IS NOT AN ASTM STANDARD; IT IS UNDER CONSIDERATION WITHIN AN ASTM TECHNICAL COMMITTEE BUT HAS

NOT RECEIVED ALL APPROVALS REQUIRED TO BECOME AN ASTM STANDARD. IT SHALL NOT BE REPRODUCED OR CIRCULATED OR
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THE COMMITTEE HAVING JURISDICTION AND THE PRESIDENT OF THE SOCIETY. COPYRIGHT ASTM, 100 BARR HARBOR DRIVE, WEST

CONCHOHOCKEN, PA 19428-2959 ALL RIGHTS RESERVED Designation: E70 – 07 (Reapproved 2015)

ITEM 19
Date: August 30, 2019
To: Subcommittee D16.04 members (both for concurrent ballots)
Tech Contact: Michael D. Taylor, [email protected], Work phone: 832.783.6563
Work Item #: WK67555
Ballot Action: Revision of Standard Test Method for pH of Aqueous Solutions with the Glass Electrode

Rationale: This ballot addresses the negatives and comments from the spring 2019 ballot for the periodic 5 year
review to update the method to current D16 Editorial Guidelines

Standard Test Method for

pH of Aqueous Solutions With the Glass Electrode1
This standard is issued under the fixed designation E70; 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 (ε) indicates an editorial change
since the last revision or reapproval.

This standard has been approved for use by agencies of the U.S. Department of Defense.

1. Scope *

1.1 This test method covers the apparatus and procedures for the electrometric measurement of pH values of aqueous
solutions with the glass electrode. It does not deal with the manner in which the solutions are prepared. pH measurements of
good precision can be made in aqueous solutions containing high concentrations of electrolytes or water-soluble organic
compounds, or both. It should be understood, however, that pH measurements in such solutions are only a semiquantitative
indication of hydrogen ion concentration or activity. The measured pH will yield an accurate result for these quantities only
when the composition of the medium matches approximately that of the standard reference solutions. In general, this test
method will not give an accurate measure of hydrogen ion activity unless the pH lies between 2 and 12 and the concentration
of neither electrolytes nor nonelectrolytes exceeds 0.1 mol/L (M).
1.2 Units - The values stated in SI units are to be regarded as standard. The values in parentheses are for information only.
1.3 In determining the conformance of the test results using this method to applicable specifications, results shall be
rounded off in accordance with the rounding-off method of Practice E29.
1.4 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 appropriate safety, health, and environmental practices and determine
the applicability of regulatory limitations prior to use.
1.5 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.

2. Referenced Documents

2.1 ASTM Standards:2

D1193 - 06(2018) Standard Specification for Reagent Water
D1293-18 Standard Test Methods for pH of water

E180 Standard Practice for Determining the Precision of ASTM Methods for Analysis and Testing of Industrial and

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 E70– 07 (Reapproved 2015)

Specialty Chemicals

E691 Standard Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method

E1910 / E1910M-15 Standard Test Method for Agricultural pH Control Agents, Measurement of pH Change and
Buffering Capacity
D5128 Standard Test Method for On-Line pH Measurement of Water of Low Conductivity
D5464 Test Method for pH Measurement of Water of Low Conductivity
D6569 Standard Test Method for On-Line Measurement of pH
E29 Practice for Using Significant Digits in Test Data to Determine Conformance with Specifications
E691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
2.2 Other Documents: OSHA Regulations, 29 CFR, paragraphs 1910.1000 and 1910.1200 3

3. Terminology

3.1 Definitions:
3.1.1 pH—defined formally as the negative logarithm to the base 10 of the conventional hydrogen ion activity. See
Appendix X1.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 For the purpose of this test method, the term “meter” shall apply to the instrument used for the measurement of
potential (either in millivolts or in terms of pH units), the term “electrodes” to the glass electrode and the reference electrode,
and the term “assembly” to the combination of the meter and the electrodes. The performance of the meter shall be
differentiated from that of the electrodes.

4. Significance and Use

4.1 pH is, within the limits described in 1.1, an accurate measurement of the hydrogen ion concentration and thus is widely
used for the characterization of aqueous solutions.
4.2 pH measurement is one of the main process control variables in the chemical industry and has a prominent place in
pollution control.

5. Apparatus

5.1 pH meters—Many excellent pH meters are available from commercial sources. To some extent, the choice of meter
will depend on the desired precision of measurement. The meter may operate on a null-detection principle or may utilize
digital readout or a direct deflection meter with a large scale. Power may be supplied by batteries or a-c operation may be
provided. The maximum grid current drawn from the glass electrode during measurement shall not exceed 2 × 10 –12 A.
Automatic or manual adjustment shall allow for changes in F/(RT ln 10) when the temperature of the assembly is altered. For
referee work, or in case of dispute, meters capable of discriminating changes of pH to 0.01 unit (0.6 mV) or less shall be used.
5.2 Reference Electrodes and Glass Electrodes:
5.2.1 The saturated calomel electrode and the 3.5 mol/L (M) calomel silver/silver chloride electrode are is suitable as
reference electrodes in pH assemblies (Note 1 & 7.2). If the saturated electrode is used, a few crystals of solid potassium
chloride shall be present in the chamber surrounding the electrode element at each temperature. The design of the electrode
shall permit a fresh liquid junction between the solution of potassium chloride and the buffer or test solution to be formed for
each test and shall allow traces of solution to be readily removed by washing.
NOTE 1—Other reference electrodes of constant potential may be used, provided no difficulty is experienced in standardizing the
assembly as described in Section 8. Combination pH electrodes with or without integrated temperature sensor are permitted for use with
this test method.
5.2.2 The silver-silver chloride electrode also is used widely as a reference electrode and has replaced the mercury
containing calomel electrode.

3
Available from Superintendent of Documents, U.S. Government Printing Office, 732 N. Capitol St. NW, Mail Stop: SDE,
Washington, DC 20401.

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5.2.3 Commercial glass electrodes are designed for certain specific ranges of pH and temperature; consequently, the pH
and temperature of the test solutions shall be considered in selecting the glass electrode for use. The pH response shall
conform with the requirements set forth in Section 7. The leads shall be shielded from the effects of body capacitance.
5.2.4 If the assembly is in intermittent use, the ends of the electrodes shall be immersed between measurements in distilled
water a solution that follows the manufacturer’s recommendation for electrode storage, (i.e. 3 M KCL) . If you do not have
storage solution, you may use a pH 4 buffer solution as backup ). The high-alkalinity type of glass electrode shall be stored in
the borax buffer solution. For prolonged storage, follow the manufacturer’s recommendations for electrode storage. Glass
electrodes may be allowed to become dry (see note 2), and reference electrodes shall be capped to prevent undue evaporation.

NOTE 2—New glass electrodes and those that have been stored dry shall be conditioned as recommended by the manufacturer.
Requirements for the physical dimensions and shape of the electrodes and the composition of the internal reference solution are not
considered part of this test method.

6. Reagents and Materials

6.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society where
such specifications are available.5 Other grades may be used, provided it is first ascertained that the reagent is of sufficiently
high purity to permit its use without lessening the accuracy of the determination. Commercially prepared solutions are
acceptable for use.

6.2 Buffer Solutions—Commercially available, water–based buffer solutions with pH values of 4, 7 9, 10 or other values to
bracker the measurement of samples are acceptable for the standardization.

6.1 3 Preparation of pH buffers - The pH(S) of six recommended standard solutions at several temperatures is listed in
Table 1. The buffer solutions shall be prepared from highly purified materials sold specifically as pH standards (Note 3).
Potassium hydrogen phthalate and the two phosphate salts shall be dried at 110°C for 1 h before use, but borax and sodium
bicarbonate shall not be heated above room temperature. Potassium dihydrogen citrate shall be dried for 1 h at 80°C, and
sodium carbonate shall be ignited for 1 h at 270°C before use. The standard solutions shall be prepared as described in 6.4 –
6.9. They shall be preserved in bottles of chemically resistant glass or polyethylene and shall be replaced at an age of six
weeks, or earlier if a visible change should occur in the solution.

TABLE 1 pH(S) of Standard SolutionsA,B

Temperature, °C A B C D E F
0 3.863 4.003 6.984 7.534 9.464 10.317
10 3.820 3.998 6.923 7.472 9.332 10.179
20 3.788 4.002 6.881 7.429 9.225 10.062
25 3.776 4.008 6.865 7.413 9.180 10.012
30 3.766 4.015 6.853 7.400 9.139 9.966
35 3.759 4.024 6.844 7.389 9.102 9.925
40 3.753 4.035 6.838 7.380 9.068 9.889
50 3.749 4.060 6.833 7.367 9.011 9.828
60 ... 4.091 6.836 ... 8.962 ...
70 ... 4.126 6.845 ... 8.921 ...
80 ... 4.164 6.859 ... 8.885 ...
90 ... 4.205 6.877 ... 8.850 ...

A
The compositions of the standard solutions are:
A—KH2 citrate, m = 0.05 mol kg–1
B—KH phthalate, m = 0.05 mol kg–1
C—KH2PO4, m = 0.025 mol kg–1; Na2HPO4, m = 0.025 mol kg–1

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Reagent Chemicals, American Chemical Society Specifications , American Chemical Society, Washington, D.C. 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. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.

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 E70– 07 (Reapproved 2015)

D—KH2PO4, m = 0.008695 mol kg–1; Na2HPO4, m = 0.03043 mol kg–1

E—Na2B4O7, m = 0.01 mol kg–1
F—NaHCO3, m = 0.025 mol kg–1; Na2CO3, m = 0.025 mol kg–1
where m denotes molality.
B
For a discussion of the manner in which these pH(S) values were assigned, see Chapter 4 of the book by Bates, R. G., Determination of pH, Theory and
Practice, John Wiley and Sons, Second edition, New York, 1973.

NOTE 3—Six of the buffer salts can be obtained in the form of standard reference materials from the National Bureau of Standards. These
materials are numbered as follows:

Buffer Salt SRM No.

Potassium hydrogen phthalate 185
Potassium dihydrogen phosphate 186I
Disodium hydrogen phosphate 186II
Borax 187
Sodium bicarbonate 191
Sodium carbonate 192
The pH(S) values may vary slightly from one lot to another; consequently, the values given on the SRM certificate should be used in
preference to those given in Table 2, if slight differences exist.
TABLE 2 Bias of pH Measurements
Nominal pH Hydrogen Electrode Glass Electrode Difference
3.7 3.715 3.73 + 0.015
6.5 6.519 6.53 + 0.011
8.2 8.174 8.18 + 0.006
8.4 8.478 8.45 – 0.028
6.2 4 Commercial standard buffers are available. For the most exact measurements, the value of the commercial buffer
should be verified using one of the recommended standard buffers in Table 1.
6.3 5 Distilled Water—The conductivity of the distilled water shall not exceed 2 × 10 –6 s · cm–1. For the preparation of the
citrate, phthalate, and phosphate solutions, the water need not be freed of dissolved carbon dioxide. The water used for the
borax standard and the carbonate standard shall be boiled for 15 min or purged with air free of carbon dioxide and shall be
protected with a soda-lime tube or equivalent (Note 4) while cooling and in storage. The pH of the carbon dioxide-free water
shall be between 6.6 and 7.5 at 25°C. The temperature of the water used to prepare the standards shall be within 2°C of 25°C.
The amounts of the buffer salts given in 5.3 through 5.8 are weights in air near sea level determined with brass weights.
NOTE 4—The water used for preparing the standard buffer solutions shall be Types I or II reagent water in accordance with Specification
D1193. Precautions shall be taken to prevent contamination of the distilled water with traces of the material used for protection against
carbon dioxide.
6.4 6 Citrate, Standard Solution A (molality = 0.05 mol/kg; pH(S) = 3.776 at 25°C)—Dissolve 11.41 g of potassium
dihydrogen citrate in distilled water and dilute to 1 L.
6.5 7 Phthalate, Standard Solution B (molality = 0.05 mol/kg; pH(S) = 4.008 at 25°C)—Dissolve 10.12 g of potassium
hydrogen phthalate in distilled water and dilute to 1 L.
6.6 8 Phosphate, Standard Equimolal Solution C (molality of each phosphate salt = 0.025 mol/kg; pH(S) = 6.865 at
25°C)—Dissolve 3.388 g of potassium dihydrogen phosphate and 3.533 g of disodium hydrogen phosphate in distilled water
and dilute to 1 L.
6.7 9 Phosphate, Standard Solution D (1 + 3) (molality of KH2PO4 = 0.008695 mol/kg, molality of Na2HPO4 = 0.03043
mol/kg); pH(S) = 7.413 at 25°C)—Dissolve 1.179 g of potassium dihydrogen phosphate and 4.302 g of disodium hydrogen
phosphate in distilled water and dilute to 1 L.
6.8 10 Borax, Standard Solution E (molality = 0.01 mol/kg; pH(S) = 9.180 at 25°C)—Dissolve 3.80 g of sodium tetraborate
decahydrate (borax) in distilled water and dilute to 1 L.
6.9 11 Carbonate, Standard Solution F (molality of each carbonate salt = 0.025 mol/kg; pH(S) = 10.012 at 25°C)—
Dissolve 2.092 g of sodium bicarbonate and 2.640 g of sodium carbonate in distilled water and dilute to 1 L.

7. Hazards
7.1 Consult current OSHA regulations, suppliers' Safety Data Sheets, and local regulations for all materials used in this test
method.
7.2 The use of the more toxic calomel (mercuric chloride) electrodes has been almost completely eliminated in commercial
laboratories in the United States. They have been supplanted for the most part by safer silver-silver chloride reference
electrodes, and to a smaller extent, by redox coupled systems such as an iodide salt system. Therefore, for safety reasons, it is

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 E70– 07 (Reapproved 2015)

recommended to use the safer, newer reference electrodes than the calomel reference electrode.

8. 7. Performance Tests of Meter and Electrodes <== Note: Moved rewrite of this section to APPENDIX

NOTE 5—Except for measurements of the highest precision, it will usually be unnecessary to perform the tests described in this section. In
the usual pH measurement, the stability of the meter, the accuracy of the scale reading, and the pH response of the glass electrode over the
range of the measurements are verified by checking the assembly with a series of standard buffer solutions.
8 7.1 Assembly—The assembly shall be judged to be performing satisfactorily if it furnishes, within acceptable limits of
accuracy, the correct pH values for the standard buffer solutions listed in Table 2. When the electrodes are immersed in a
buffer solution, the measured potential difference shall be substantially constant, and the cause of any instability shall be
determined.
8.2 7.2 Meter—The meter shall be brought to electrical balance in accordance with the manufacturer's instructions. The
performance shall then be tested by applying a known variable potential through a resistance of approximately 200 MΩ to the
terminals of the meter, the high-resistance lead being connected to the terminal corresponding to the glass electrode. The
source of potential may be a precision-type potentiometer with a range of 1100 mV or more and a limit of error not greater
than 0.1 mV. The 200-MΩ resistor shall be properly shielded to avoid capacity pickup. Commencing with a value of zero, the
applied potential shall be increased in increments of 100 mV, and the readings of the dial of the meter at balance shall be
noted. The process shall be extended to cover the entire range of the meter. In no case shall the difference between the applied
voltage and that indicated by the meter differ by more than 1 mV per increment of applied voltage.
NOTE 6—If the cumulative error at the end of the scale exceeds ±3 mV, a calibration curve for the meter shall be constructed and
corrections applied to each measurement of electromotive force or pH. Differences of electromotive force (volts) are converted to
corresponding differences of pH by multiplying by F/(RTln 10) (Table X1.1). Inasmuch as the meter is made to read correctly at the pH of
the standard, the calibration correction to be applied to a pH measurement is the difference between the scale corrections at the pH of the
standard and that of the unknown, with due regard for sign.
8.3 7.3 Glass Electrodes—The difference of potential between the glass electrode and the standard hydrogen gas electrode
shall be measured when both electrodes are immersed in the same portion of various buffer solutions over the pH range in
which the glass electrode is to be used. For these comparisons the cell shall be placed in a water bath thermostatically
controlled to ±0.1°C near 25°C. The solutions used for this test shall be those listed in Section 6. The standards of pH 9.18 and
below (at 25°C) shall be used to test electrodes of the general-purpose type. The borax and carbonate standards shall be used
to test the high-alkalinity type of electrode. These buffer solutions shall be supplemented by a 0.1 mol/kg (M) carbonate-free
solution of sodium hydroxide, the pH of which is approximately 12.8 at 25°C. The difference of potential between the
general-purpose glass electrode and the hydrogen electrode shall be independent, within ±1 mV, of pH changes in the range
from 3.8 to 9.18 pH. The difference of potential between the hydrogen electrode and a glass electrode of the high-alkalinity
type shall be the same, within +3 mV, at pH 12.8 as at pH 9.18.

9 8. Calibration and Standardization

9.1 8.1 Turn on the instrument, allow to warm up thoroughly, and bring to electrical balance in accordance with the
manufacturer's instructions. Wash the glass and reference electrodes and the sample cup three times with distilled water.
Allow the water to drain from the electrodes, but the sample cup may be dried gently with clean absorbent tissue. Note the
temperature of the test (unknown) solution and adjust the temperature dial of the meter to the proper setting.
9.2 8.2 Select two standard solutions (Note 7) to bracket the anticipated pH, if possible, and warm or cool these standards
as necessary to match within 2°C the temperature of the unknown. Fill the sample cup with the first standard and immerse the
electrodes. Set the dial of the meter to the pH(S) value of the standard at the appropriate temperature as read from Table 2 or
interpolated in the data therein (see Note 3). Engage the operating button and rotate the standardizing knob or asymmetry
potential knob until the meter is brought to balance. In direct-reading meters engage the operating-button, or turn the range
switch to the proper position, and rotate the asymmetry potential knob until the reading of the dial corresponds to the known
pH of the standardizing buffer solution. Fill the sample cup repeatedly with additional portions of the standard solution until
the instrument remains in balance with ±0.02 pH unit for two successive portions without a change in the position of the
asymmetry potential knob. If the temperature of the electrodes differs appreciably from that of the solutions, use several
portions of solution and immerse the electrodes deeply to assure that both electrodes and standard are at the desired
temperature. In order to reduce the effects of thermal and electrical hysteresis, keep the temperature of electrodes, standard
solutions, and wash water as close to that of the unknowns as possible.
9.2.1 8.2.1 Wash the electrodes and sample cup three times with distilled water. Place the second standard in the sample
cup, adjust the instrument to the new balance point, and read the pH from the dial. Do not change the setting of the asymmetry
potential knob. Use additional portions of the second standard until successive readings of the pH agree within 0.02 unit.
Judge the assembly to be operating satisfactorily if the reading obtained for the second standard agrees with the assigned

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pH(S) of that standard within 0.02 pH unit. When the meter is equipped with a slope control, use this control to correct small
errors in the response of the glass electrode by adjusting the reading for the second standard to the known pH value. Discard
used portions of the standard buffer solutions.
NOTE 7—Always calibrate the assembly with two buffer solutions to check the response of the electrode at different pH values and to
detect a faulty glass electrode or incorrect temperature compensation. The presence of a faulty electrode is indicated by failure to obtain a
reasonably correct value for the pH of the second standard solution when the meter has been standardized with the first. A cracked electrode
will often yield pH values that are essentially the same for both standards. If an electrode gives an incorrect value or has a sluggish response,
it may be dirty. Follow the manufacturer's instructions for cleaning.
9.3 8.3 If the anticipated pH of the test solution is less than 3.8, use the phthalate solution for the initial standardization and
the citrate solution as the second standard. If the anticipated pH of the test solution is greater than 10.0, use an electrode
designed for use at high alkalinities and observe the manufacturer’s instructions. Use the borax solution for initial
standardization of the assembly. The second standard shall be the carbonate solution. Judge the assembly to be operating
satisfactorily if the reading obtained for the carbonate solution agrees with the assigned pH of this standard (Note 8) within
0.03 unit. When the meter is equipped with a slope control use this control to adjust the reading for the second standard
(citrate solution or carbonate solution) to the known pH value.
NOTE 8—The change of pH(S) with change of temperature is large for the borax and carbonate standards. Hence, note the temperature of
these standards to the nearest 1°C and use to obtain pH(S) by interpolation in the data of Table 1.
9.4 8.4 If only an occasional pH determination is made, standardize the assembly each time it is used. In a long series of
measurements, supplement initial and final standardizations by a check at intervals of 1 h, or longer if little or no change is
found between successive standardizations.

9.1 Set up the instrument in accordance with the manufacturer's instructions. Rinse the glass and reference electrodes with
Type 1 or Type 2 water into a container. Allow the water to drain from the electrodes. Note the temperature of the buffer and
test specimens. Adjust the temperature setting of the meter to the proper setting. Set the meter temperature setting to the
ambient temperature of the lab and buffers.
9.2 Calibrate the instrument with at least two standard solutions (Note 7) to bracket the anticipated pH, if possible, Warm
or cool test specimen to agree within 2° C of buffer solutions used to calibrate the instrument. Follow the manufacturer’s
instructions for the calibration sequence taking care to rinse the electrodes after each measurement of buffer or standard
solution. Calibrate the instrument with at least two standard solutions (Note 7) to bracket the anticipated pH, if possible Measurement of calibration
standards (buffers) and samples, and the Type 1 or 2 water for rinsing instrument should In order to reduce the effects of
thermal and electrical hysteresis, keep the temperature of electrodes, standard solutions, and wash water within 2° C or as
close as possible. The calibration slope shall be in the 95 % to 100 % range, or the electrode will have to be cleaned or
replaced.
NOTE 7—Always It is recommended to calibrate the assembly with two three buffer solutions and reverify middle buffer meets method
precision in order to check the response of the electrode at different pH values and to detect a faulty glass electrode or incorrect temperature
compensation. A procedure to test the pH electrode performance is found in Appendix X1
9.3 If the anticipated pH of the test solution is less than 3.8, use the phthalate solution or appropriate commercial buffer for
the initial standardization and the citrate solution as the second standard. If the anticipated pH of the test solution is greater
than 10.0, use an electrode designed for use at high alkalinities and observe the manufacturer’s instructions.
9.4 If only an occasional pH determination is made, standardize the assembly each time it is used. In a long series of
measurements, supplement initial and final standardizations by a check at intervals of 1 h, or longer if little or no change is
found between successive standardizations

10 9. Procedure

10.1 9.1 pH of Test Solutions:

10.1.1 9.1.1 After the meter has been standardized with two standard solutions (Section 8) Rinse the electrodes with Type 1
or Type 2 water. Fill the sample container beaker with a wash and dry the electrodes and the sample cup as described in 8.1.
Fill the cup with a portion of the test solution, sample aliquot sufficient to submerge electrodes and obtain a value for pH.
obtain a preliminary value for pH. In the case of well-buffered test solutions, one to three portions will usually be sufficient to
yield pH values reproducible to ±0.02 unit and that show drifts of less than ±0.01 unit in 1 or 2 min.
10.1.2 9.1.2 Measure the pH of water samples and slightly buffered solutions that are in equilibrium with the air as
described in 9.1, except measure the pH of successive portions of water or test solutions, with vigorous agitation, until the
observed results for two successive portions agree within 0.1 unit. Six or more portions may be necessary. The flow cell may
also be used (see 9.2). If the water sample or the slightly buffered test solution is not in equilibrium with the carbon dioxide of
the atmosphere, measure with external electrodes in a wide-mouth flask that has been flushed with carbon dioxide-free air, and

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protect the contents of the flask from exposure to air during the measurement.
10.2 9.2 pH of Flowing Streams:
10.2.1 9.2.1 Flow cells and electrode units for immersion in flow channels are an important feature of industrial pH control.
In conjunction with electronic recorders and recorder-controllers, they provide the continuous measurements necessary for
fully automatic regulation of pH. The flow cell is particularly advantageous for the determination of the pH of water or of
sparingly buffered solutions. Simple dip measurements without agitation are subject to appreciable errors due to inadequate
washing of the electrodes, solubility of the glass, and absorption of carbon dioxide during the measurement. A rapid flow of
solution past the electrode maintains a clean glass interface, retards the tendency for fine solids to collect at the surface,
minimizes errors resulting from solubility of the glass, and protects the sample from atmospheric contaminants.
10.2.2 9.2.2 Flow Cell—The flow unit may be of metal, glass, rubber, or plastic. If metal pipe connections are employed,
they shall all be of the same metal. The volume of the unit shall be small, to permit a high rate of flow. If the cell is not
provided with a resistance thermometer for automatic temperature compensation (or if it is used in conjunction with a meter
not equipped to utilize this feature), arrangements for monitoring the temperature of the solutions shall be provided. The unit
and the leads shall be free from the effects of body capacitance.
10.2.3 9.2.3 Standardization and pH Determination—If the assembly is in continuous use, standardize it daily in
accordance with the instructions given in Section 8. Use two standards in order to check the proper functioning of the
electrodes. For a precision greater than ±0.1 pH unit below pH 9, the temperature of the standard should be within 2°C of that
of the flowing solution. For the measurement of pH, carefully observe the instructions furnished by the manufacturer of the
meter or recorder.
10.2.4 9.2.4 pH of Water and Slightly Buffered Solutions—Maintain a flow rate sufficient to change the solution in the cell
five times per minute. Do not read the pH of water or of a slightly buffered solution until the flow of water or test solution has
been continued for at least 15 min following immersion of the electrodes in the standard buffer solution, or until a drift of less
than 0.1 pH unit in 2 min is observed. If the pH of the flowing solution is changing, the glass electrode measurement may lag
considerably behind the true pH.

11. 10. Report

11.1 10.1 Report the pH to 0.01 unit and the temperature of the test solution to the nearest 1°C.

12 11. Precision and Bias4

12.1 11.1 The following criteria should be used for judging the acceptability of results obtained using separate glass and
calomel electrodes (Notes 9 and 10):
12.1.1 11.1.1 Repeatability (Single Analyst)—The standard deviation for a single determination has been estimated to be
0.006 pH unit at 106 dF. The 95 % limit for the difference between two such runs is 0.02 pH unit.
12.1.2 11.1.2 Laboratory Precision (Within-Laboratory, Between-Days Variability)—The standard deviation of results,
each the average of duplicates, obtained by the same analyst on different days, has been estimated to be 0.022 pH unit at 53
dF. The 95 % limit for the difference between two such averages is 0.06 pH unit.
12.1.3 11.1.3 Reproducibility (Multilaboratory)—The standard deviation of results, each the average of duplicates,
obtained by analysts in different laboratories, has been estimated to be 0.040 pH unit at 12 dF. The 95 % limit for the
difference between two such averages is 0.11 pH unit.
NOTE 9—The above precision estimates are based on an interlaboratory study performed in 1973 on four buffer solutions having pH
values of approximately 3.7, 6.5, 8.2, and 8.4. Fourteen laboratories analyzed each solution in duplicate and replicated the analysis on
another day for a total of 224 determinations. A variety of commercial meters equipped with glass and calomel electrodes were used in this
study. Practice E180 was used in developing these precision estimates.
12.2 11.2 Bias—The pH values of the buffer solutions, as determined using a hydrogen electrode at 25°C, are compared
with the average values obtained using this test method in Table 2.
12.3 11.3 The following limited interlaboratory study by ten laboratories in one company suggests that the precision
obtainable with new combination electrodes is comparable to that in the 1973 study using separate electrodes.
12.3.1 11.3.1 In 1994 a standard buffer solution of pH 4.63 was sent each laboratory which measured the pH once per day
for three days. Each laboratory made the measurements using both a new and an old electrode. The results were analyzed
using the techniques in Practice E691. Because of the design, no estimates for repeatability are possible. The estimates for
Laboratory Precision and Repeatability are given in Table 3.

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TABLE 3 Precision Using Combination Electrodes

New Old
Electrodes Electrode
Laboratory precision
Standard deviation 0.020 0.033
Degrees of freedom 20 18
95 % range 0.06 0.04
Reproducibility
Standard deviation 0.037 0.033
Degrees of freedom 9 8
95 % range 0.10 0.09

NOTE 10—These estimates of precision apply to optimum conditions, namely for pH measurements of well-buffered aqueous solutions.
The precision attainable in measurements of the pH of water and other poorly buffered solutions will, in general, be of a considerably lower
order.
13 Quality
13.1 Laboratories shall have a quality control system in place
13.1.1 Confirm the performance of the test instrument or test method by analyzing a quality control sample following
the guidelines of standard statistical quality control practices
13.1.1.1 A quality control sample is a stable material isolated from the production process and
representative of the sample being analyzed
13.1.1.2 When QA/QC protocols are already established in the testing facility, these protocols are
acceptable when they confirm the validity of test results
13.1.1.3 When there are no QA/QC protocols established in the testing facility, use the guidelines described
in ASTM D6809 or similar statistical quality control practices
13.1.1.4 A reference material meeting precision of method may be used in validating calibration and
method performance.
13.2 A practice used for pH systems that has only one calibration point is to calibrate the pH meter using buffer pH 7,
then read the pH of buffers 4 and 10. If you do not get a correct reading for pH 4 and pH 10 buffers, first the
buffers are checked using fresh buffer then maintenance on the electrodes and the rest of the analytical system is
corrected or brought back into control. (see Note 7)

14 12. Keywords

14.1 12.1 aqueous solution; buffer; combination electrode; glass electrode; pH; pH meter; reference electrode
APPENDIX
(Nonmandatory Information)
X1. MISCELLANEOUS NOTES
X1.1 The pH of an aqueous solution is derived from Er, the electromotive force (emf) of the cell:
reference electrode || solution || glass electrode
where:
the double vertical line represents a liquid junction when the electrodes are immersed in the solution, and
Es, the electromotive force obtained when the electrodes are immersed in a standard solution, whose assigned pH is designated
pH(S), by the following equation (Note X1.1):

where:
F = faraday, 96 487 C × mol–1,

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 E70– 07 (Reapproved 2015)

R = gas constant, 8.314 33 J × K–1 × mol–1, and

T = absolute temperature, (t °C + 273.15).

NOTE X1.1—Values of F/(RT ln 10) are given in Table X1.1.

TABLE X1.1 Values of F/(RT ln 10)

Temperature, °C F/(RT ln 10), V–1
0 18.451
5 18.120
10 17.800
15 17.491
20 17.192
25 16.904
30 16.625
35 16.356
40 16.095
45 15.841
50 15.596
55 15.359
60 15.128

X1.2 For additional information on the concepts of pH and its measurement see the book by R. G. Bates. 5

X2 CHECK FOR ELECTRODE PERFORMANCE

X2.1.1 The kinetic electrode test measures the kinetic response of the electrode. Electrodes can calibrate with acceptable
slope and intercept values yet still not have a response good enough for titration. The speed of response and subsequent
stability is important for a titration electrode. A manual check is described in this Appendix that can be carried out with a pH
meter or titrator set to read millivolts continuously.
X2.1.2 The essence of this check is to challenge the electrode coming from rest in a water solution with buffers and measure
the potential after 30 s and 60 s. A fast electrode reaches a stable point in less than 30 s and changes little from 30 s to 60 s.
Use buffers pH 4, pH 7, and pH 10 for this check, as needed.
X2.1.3 Procedure
X2.1.3.1 Set the pH meter to read millivolts continuously. Have provision for stirring the buffer solution at the same speed
used for the titrations.
X2.1.3.2 Allow the electrode to stabilize for 1 min in distilled or equivalent deionized water.
X2.1.3.3 Remove the electrodes from the water, and place them in the pH 4 buffer. Start a stopwatch at about the moment
when the buffer touches the electrode.
X2.1.3.4 After 30 s, note the potential. After an additional 30 s, note the potential again. The difference between the two
potentials is termed the drift.
X2.1.3.5 Repeat the procedure for pH 7 buffer and pH 10 buffer.
X2.1.4 Calculate the drift for each of the three buffers. The electrode response may be judged as follows:

drift < 1 excellent

1 < drift < 2 good
2 < drift < 3 acceptable
3 < drift < 4 questionable
4 < drift unacceptable

X2.1.5 The difference between the 60 s potentials for pH 4 buffer and pH 7 buffer should be greater than 162 mV, or 54
mV/pH number. Electrodes with a slope less than 54 mV/pH number are not reliable for measurements.

SUMMARY OF CHANGES

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 E70– 07 (Reapproved 2015)

Committee D16.04 E15.01 has identified the location of selected changes to this standard since the last issue (E70 - 15)
that may impact the use of this standard.
(1) Updated units of measure to comply with the International System of Units (SI).
(2) Added numbered paragraph in Scope stating that the SI units are to be considered standard.
(3) Deleted (Formerly called Repeatability) from the title of 11.1.2.
(4) Added Summary of Changes section.
(5) Added ASTM reference methods D1193, E180, E691
(6) In scope, added rounding reference.
(7) In 5.2.4 between measurements, soak probes in pH 4 buffer instead of distilled or deionized water.
(7) Updated 5.2.4 with “ follows the manufacturer’s recommendation for electrode storage, (i.e pH 4 buffer)”.
(8) Added the Hazards section 7
(9) Added the QC section 13

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