NOTICE: This standard has either been superseded and replaced by a new version or discontinued.

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Designation: D 1287 – 91 (Reapproved 1997)e1

Standard Test Method for

pH of Engine Coolants and Antirusts1
This standard is issued under the fixed designation D 1287; 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 (e) indicates an editorial change since the last revision or reapproval.

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

e1 NOTE—Editorial corrections were made throughout in June 1998.

1. Scope indicates whether an engine coolant, antirust, or a solution of

1.1 This test method covers the determination of the pH of these compounds is acidic, alkaline, or neutral.
unused engine coolants and antirusts, and used or unused 4.2 pH is sometimes used for production quality control. It
aqueous dilutions of the concentrated products. is generally desirable that engine coolants have an alkaline pH.
4.3 pH is not significant from the standpoint of predicting
NOTE 1—Antirusts in solid form are not included in this test method. service life. The pH of used engine coolants or antirust
NOTE 2—It is believed that this procedure gives all the information
solutions is not a dependable indication of either existing
required for determining the pH of samples of engine coolant or antirust
likely to be encountered. Should additional information on pH determi- effectiveness or remaining life of the solution.
nations be needed, reference should be made to Test Method E 70.
5. Apparatus
1.2 This standard does not purport to address all of the
5.1 The pH meter, glass electrode, and calomel electrode,
safety concerns, if any, associated with its use. It is the
shall be as specified in the Annex.
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica- 6. Reagents
bility of regulatory limitations prior to use. 6.1 Purity of Reagents—Reagent grade chemicals shall be
2. Referenced Documents used in all tests. Unless otherwise indicated, it is intended that
all reagents shall conform to the specifications of the Commit-
2.1 ASTM Standards:
tee on Analytical Reagents of the American Chemical Society,
D 1176 Practice for Sampling and Preparing Aqueous So-
where such specifications are available.3 Other grades may be
lutions of Engine Coolants or Antirusts for Testing Pur-
used, provided it is first ascertained that the reagent is of
poses2
sufficiently high purity to permit its use without lessening the
E 70 Test Method for pH of Aqueous Solutions with the
accuracy of the determination.
Glass Electrode2
6.2 Purity of Water— Unless otherwise indicated, refer-
3. Summary of Test Method ences to water shall be understood to mean distilled water or
water of equal purity. Distilled water shall be boiled thor-
3.1 A sample, as received or after dilution with a specified
oughly, or purged with carbon dioxide-free air, to remove
volume of distilled water, is placed in a beaker or sample cup
carbon dioxide and shall be protected with a soda-lime tube or
and the pH measured with a pH meter and associated glass-
its equivalent while cooling and in storage. The pH of the water
saturated calomel electrode pair.
shall be between 6.2 and 7.2 at 25°C.
NOTE 3—The readings of the meter in the case of the concentrated 6.3 Standard Buffer Solutions—The buffer solutions for
products are not pH values according to the accepted definition, but are calibrating the pH meter and electrode pair shall be prepared
apparent pH values which are useful in the interpretation of the condition from salts sold specifically for use, either singly or in combi-
of the product.
nation, as pH standards. The salts shall be dried for 1 h at
4. Significance and Use 110°C before use, except in the case of borax which shall be
4.1 pH is a measure of the hydrogen ion concentration and used as the decahydrate. The solutions with pH less than 9.5

1 3
This test method is under the jurisdiction of ASTM Committee D-15 on Engine Reagent Chemicals, American Chemical Society Specifications, American
Coolants and is the direct responsibility of Subcommittee D15.04 on Chemical Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Properties. listed by the American Chemical Society, see Analar Standards for Laboratory
Current edition approved June 15, 1991. Published October 1991. Originally Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
published as D 1287 – 53 T. Last previous edition D 1287 – 85. and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
2
Annual Book of ASTM Standards, Vol 15.05. MD.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

1
NOTICE: This standard has either been superseded and replaced by a new version or discontinued.
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D 1287
shall be stored in chemically resistant bottles. The alkaline electrode or incorrect temperature compensation. The two
phosphate solution shall be stored in glass bottles coated on the buffer solutions selected should bracket the anticipated pH of
side with paraffin. the solutions being tested.
9.1.1 Turn on the instrument, allow it to warm up, and
NOTE 4—Commercially available buffer tablets or prepared buffer
solutions may be used. adjust according to the manufacturer’s instructions. Immerse
the tips of the electrodes in the standard buffer solution chosen
6.4 Potassium Hydrogen Phthalate Buffer Solution (0.05 and allow sufficient time for the temperature of the buffer
M, pH = 4.01 at 25°C)—Dissolve 10.21 g of potassium solution and the electrodes to equalize. Set the temperature
hydrogen phthalate (KHC 8H4O4) in water, and dilute to 1 L. knob at the temperature of the buffer solution. Adjust the
6.5 Neutral Phosphate Buffer Solution (0.025 M with re- standardization or asymmetry potential control until the meter
spect to each phosphate salt, pH = 6.86 at 25°C)—Dissolve registers a scale reading, in pH units, equal to the known pH of
3.40 g of potassium dihydrogen phosphate (KH2PO4) and 3.55 the standardizing buffer solution.
g of anhydrous disodium hydrogen phosphate (Na2HPO4) in 9.1.2 Rinse the electrodes with distilled water and touch the
water and dilute to 1 L. tips with a dry cloth or tissue to remove excess water. Immerse
6.6 Borax Buffer Solution (0.01 M, pH = 9.18 at 25°C)— the electrodes in a second standard buffer solution. The reading
Dissolve 3.81 g of disodium tetraborate decahydrate (Na2B4O of the meter shall agree with the known pH of the second
7·10H2O) in water, and dilute to 1 L. Protect this solution from
standard buffer solution within 60.05 unit without changing
atmospheric carbon dioxide; stopper the bottle at all times the setting of the standardization of asymmetry potential
except when actually in use. control. If it does not agree or if the meter gives a slow
6.7 Alkaline Phosphate Buffer Solution (0.01 M trisodium response time and drifts, the electrode should be cleaned in
phosphate, pH = 11.72 at 25°C)—Dissolve 1.42 g of anhy- accordance with the manufacturer’s instructions.
drous disodium hydrogen phosphate (Na2HPO4) in 100 mL of 9.1.3 The presence of a faulty electrode is indicated by
a 0.1 M carbonate-free solution of sodium hydroxide and dilute failure to obtain a correct value for the pH of the second
to 1 L with water. standard buffer solution after the meter has been standardized
6.8 Potassium Chloride Electrolyte— Prepare a saturated with the first. A cracked electrode will often yield pH values
solution of potassium chloride (KCl) in water. that are essentially the same for both standard buffer solutions.
7. Sampling
10. Procedure
7.1 Sample material in accordance with Practice D 1176.
10.1 Make the pH determination on ( 1) the unused concen-
8. Preparation of Electrode System trated engine coolant or antirust (as received), or (2) any
desired dilution, with distilled water, of the concentrated
8.1 Maintenance of Electrodes—Clean the glass electrode at
product, or (3) used engine coolant or antirust solution. For
frequent intervals (not less than once every week during
dilute solutions, suggested engine coolant concentrations are
continual use) in accordance with the manufacturer’s instruc-
50 and 33 volume %; antirust solution concentration should be
tions. Drain the calomel electrode at least once each week and
in the range of proposed usage. Prepare solutions as follows:
fill with KCl electrolyte. Keep the electrolyte level in the
Unused engine coolant or antirust solution samples to be tested
calomel electrode above that of the solution being tested at all
should be obtained following the applicable portions of the
times. When not in use, immerse the lower halves of the
procedure outlined in Practice D 1176.
electrodes in distilled water, or the appropriate buffer solution
10.1.1 When a small, insoluble liquid layer is present,
recommended by the manufacturer. Do not immerse the
remove it prior to testing the unused sample or preparing
electrodes in the solution being tested for any appreciable
diluted samples for testing. Using a 100-mL mixing cylinder
period of time between determinations. Although the elec-
and a pipet or other suitable measuring device, make up a
trodes are not extremely fragile, they should be handled
solution of the concentration desired for testing by measuring
carefully at all times.
the necessary amount of antifreeze or antirust solution into the
8.2 Preparation of Electrodes—Before and after using,
cylinder and adding sufficient distilled water to bring the
wipe the electrode thoroughly with a clean cloth, or a soft
solution volume to 100 mL.
absorbent tissue, and rinse with distilled water. Follow the
10.1.2 Thoroughly mix the contents of the cylinder by
manufacturer’s recommendations if further preparation is re-
shaking, and transfer into a 250-mL tall-form spoutless or other
quired. Prior to each pH determination, soak the prepared
suitable beaker.
electrode in distilled water for at least 2 min. Immediately
before use, touch the tips of the electrodes with a dry cloth or NOTE 5—Some pH apparatus is equipped with a sample cup. It is
tissue to remove excess water. satisfactory to use these cups and the smaller sample required with them,
as an alternative to the 100-mL sample and beaker specified.
9. Standardization and Testing of Electrode System in 10.2 Prepare the calomel and glass electrodes as directed in
pH Units Section 8. Immerse the tip of the electrode in the solution and
9.1 The assembly shall always be standardized with one of agitate. Where the instrument has a mechanical stirrer, this may
the standard buffer solutions. A second standard buffer solution be used. Allow the system to come to equilibrium, and record
shall be used to check the linearity of the response of the the pH value. Remove and wash the electrodes with distilled
electrodes at different pH values and to detect a faulty glass water and immerse them in distilled water until the next

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D 1287
determination is made. 12. Precision and Bias
NOTE 6—In the event that the glass electrodes become coated with an 12.1 Repeatability— Duplicate results by the same operator
oil film, as the result of testing two-phase products, it is necessary to should not be considered suspect unless they differ by more
remove such film with a suitable solvent, such as 1 + 1 mixture of toluene
than 6 0.1 pH units.
and ethyl acetate.
NOTE 7—With silicate-containing engine coolant, it is important to 12.2 Reproducibility— The results submitted by two or
specify that the pH reading be taken either immediately after preparing the more laboratories should not be considered suspect unless the
dilution or after a specified period of time, such as 30 min. In contrast to results differ by more than 6 0.2 pH units.
an immediate pH, the 30-min value has been shown to be approximately
0.2 units lower and a measurement made after 24 h can be from 0.3 to 0.5
pH units lower. 13. Keywords
13.1 antirusts; engine coolants; pH of engine coolants
11. Report
11.1 Report the pH.

ANNEX

(Mandatory Information)

A1. APPARATUS

A1.1 Meter shall be surrounded by an electrical shield that will prevent

A1.1.1 A voltmeter or potentiometer that will operate with electrostatic interference when the shield is grounded. The
an accuracy of 60.005 V and a sensitivity of 60.002 V, over shield shall be insulated from the electrical connection by
a range of at least 6 0.5 V, when the meter is used with the insulating material of the highest quality, such as rubber and
electrodes specified in A1.2 and A1.3 and when the resistance glass, so that the resistance between the shield and the entire
between the electrodes falls within the range from 0.2 to 20 length of electrical connection is greater than 50 000 MV.
MV. The meter shall be protected from stray electrostatic fields
so that no permanent change in the meter readings over the A1.3 Calomel Electrode
entire operating range is produced by touching with a grounded A1.3.1 A pencil-type calomel electrode 125 to 180 mm in
lead, any part of the exposed surface of the glass electrode, the length and 8 to 14 mm in diameter. This electrode shall be
glass electrode lead, the titration stand, or the meter. A made of glass and shall be provided with an external, remov-
desirable apparatus may consist of a continuous-reading elec- able glass sleeve on the sealed end that is dipped into the
tronic voltmeter with specified range, accuracy, and sensitivity, titration solution. The glass sleeve shall be 8 to 25 mm in
that is designed to operate on an input of less than 5 3 10−12 A length, shall be slightly tapered, and shall be ground to fit the
when an electrode system having 1000 MV resistance is electrode, so that the sealed end of the electrode protrudes 2 to
connected across the meter terminals; that is provided with a 20 mm beyond the sleeve. The ground surface shall be
metal shield connected to the ground; and is provided with a continuous and free of smooth spots. At a point midway
satisfactory terminal to connect the shielded connection wire between the extremities of the ground surface, the electrode
from the glass electrode to the meter without interference from shall be pierced by a hole or holes 1 mm in diameter. The
the presence of external electrostatic fields. electrode shall contain the necessary mercury, calomel, and
electrical connection to the mercury, all arranged in a perma-
A1.2 Glass Electrode nent manner. The electrode shall be filled almost to capacity
A1.2.1 A pencil-type glass electrode 125 to 180 mm in with saturated KCl electrolyte and shall be equipped with a
length and 8 to 14 mm in diameter. The body of the electrode stoppered port through which the electrolyte may be replen-
shall be made of a chemically resistant glass tube with a wall ished. When suspended in the air, and with the sleeve in place,
thickness of 1 to 3 mm. The end dipping into the solution shall the electrode shall not leak electrolyte at a rate greater than 1
be closed with a hemisphere of glass4 sealed on the electrode drop in 10 min.
tube and the radius of this hemisphere shall be above 7 mm.
The thickness of the glass in the hemisphere shall be great A1.4 Stirrer
enough so that resistance of the hemisphere is 100 to 1000 mV A1.4.1 A variable-speed mechanical stirrer of any suitable
at 25°C. The electrode shall contain a reproducible, perma- type (Note A1.1), equipped with a glass, propeller-type stirring
nently sealed liquid cell for making electrical connections with paddle. A propeller with blades 6 mm in radius and set at a
the inner surface of the hemisphere. The entire electrical pitch of 30 to 45° is satisfactory. If electrical stirring apparatus
connection, from the sealed contact cell to the meter terminal, is used, it must be electrically correct and grounded so that
connecting or disconnecting the power to the motor will not
produce a permanent change in meter reading during the course
4
Corning 015 glass has been found satisfactory for this purpose. of the titration.

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NOTICE: This standard has either been superseded and replaced by a new version or discontinued.
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D 1287
NOTE A1.1—Magnetic stirrers may be used in place of the mechani-
cally driven types.

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