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: D1121 − 11

Standard Test Method for

Reserve Alkalinity of Engine Coolants and Antirusts1
This standard is issued under the fixed designation D1121; 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.
This standard has been approved for use by agencies of the Department of Defense.

1. Scope potentiometrically with 0.100 N hydrochloric acid to a pH of

1.1 This test method covers the determination of the reserve 5.5. The volume of acid used is reported to the nearest 0.1 mL.
alkalinity of new, unused engine coolants, and liquid antirusts The concentration of coolant or additive in the coolant solution
as received, of used or unused aqueous dilutions of the shall be recorded if required, for calculation of depletion of the
concentrated materials, and of aqueous dilutions of solid reserve alkalinity during performance tests.
antirusts.
5. Significance and Use
1.2 The values stated in SI units are to be regarded as the
standard. 5.1 Reserve alkalinity is the number of millilitres, to the
1.3 This standard does not purport to address all of the nearest 0.1 mL of 0.100 N hydrochloric acid (HCl) required for
safety problems, if any, associated with its use. It is the the titration to a pH of 5.5 of a 10-mL sample of an undiluted,
responsibility of the user of this standard to establish appro- unused coolant, antirust, or coolant additive, and unused or
priate safety and health practices and determine the applica- used solutions thereof.
bility of regulatory limitations prior to use. 5.2 Reserve alkalinity is a term applied to engine coolants
and antirusts to indicate the amount of alkaline components
2. Referenced Documents present in the product. It is frequently used for quality control
2.1 ASTM Standards:2 during production, and values are often listed in specifications.
D1123 Test Methods for Water in Engine Coolant Concen- When applied to used solutions, reserve alkalinity gives an
trate by the Karl Fischer Reagent Method approximate indication of the amount of remaining alkaline
D1176 Practice for Sampling and Preparing Aqueous Solu- components. Unfortunately, the term is sometimes misused in
tions of Engine Coolants or Antirusts for Testing Purposes that its numerical value is said to be directly related to coolant
D1287 Test Method for pH of Engine Coolants and Antirusts quality, the higher the number, the better the coolant. ASTM
Committee D15 on Engine Coolants believes there is a need to
3. Terminology correct some misconceptions and place the term in its proper
3.1 Definitions: perspective.
3.1.1 reserve alkalinity, n—a term applied to engine coolant 5.3 Reserve alkalinity (R.A.) as defined in Section 3 of this
concentrates and antirusts to indicate the amount of alkaline method is the number of millilitres of 0.1-N hydrochloric acid
inhibitors present in the product. required to titrate 10 mL of concentrated coolant to a pH of 5.5.
The term is not a completely accurate description of the
4. Summary of Test Method
property being measured because “alkalinity” usually refers to
4.1 A 10-mL sample of concentrated coolant, antirust, the pH range above 7.0.
coolant additive, or an aqueous engine coolant containing these
products, is diluted to about 100 mL with water and titrated 5.4 A review of the origin of the term may be helpful in
attempting to understand its proper use. When ethylene glycol
was first used as an engine coolant, it was uninhibited. The
1
This test method is under the jurisdiction of ASTM Committee D15 on Engine need for inhibition soon became apparent and triethanolamine
Coolants and Related Fluids and is the direct responsibility of Subcommittee was incorporated. When solutions of this inhibited glycol were
D15.04 on Chemical Properties.
Current edition approved Oct. 1, 2011. Published October 2011. Originally titrated with dilute hydrochloric acid, it was found that the
approved in 1950. Last previous edition approved in 2007 as D1121 – 07. DOI: steepest part of the neutralization curve occurred at a pH of
10.1520/D1121-11.
2
about 5.0. Following the introduction of triethanolamine, other
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
buffers, such as borates and phosphates, have been used.
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 Titration to 5.5 was employed with these buffers which have an
the ASTM website. end point close to 5.5.

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

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 D1121 − 11
5.5 Generally, most metals in an automotive cooling system and in storage. The pH of the water shall be between 6.2 and
corrode less in solutions which are mildly alkaline. The 7.2 at 25°C. Take precautions to prevent contamination of the
commonly used alkaline buffers, borates and phosphates, help distilled water with traces of the material used for protection
to maintain this desirable alkalinity and a stable pH for against carbon dioxide.
substantial additions of acid. A well inhibited coolant contains 7.3 Standard Buffer Solution5—The buffer solutions for
smaller amounts of other inhibitors (in addition to the buffers), checking pH assemblies and glass electrodes shall be stored in
to give broad range corrosion protection for all of the metals bottles of chemically resistant glass or polyethylene and shall
found in the cooling system. These additional inhibitors may be prepared from salts sold specifically for use, either singly or
contribute very little to the titration, but they can provide in combination, as pH standards. The salts shall be dried for 1
excellent corrosion protection. h at 110°C before use.
5.6 The alkaline inhibitors provide buffering action and 7.4 Hydrochloric Acid (0.100 N)—Prepare and standardize
neutralize acids introduced into the coolant by exhaust gas 0.100 N hydrochloric acid (HCl).
leakage, by residual acid cleaner, or by the oxidation of
ethylene glycol and propylene glycol. Some inhibitors which 7.5 Phthalate Buffer Solution (0.05 M, pH = 4.01 at
contribute little or no reserve alkalinity may give excellent 25°C)—Dissolve 10.21 g of potassium hydrogen phthalate in
corrosion protection to certain metals but have little capacity to distilled water and dilute to 1 L.
combat acid contamination. In view of this, the magnitude of 7.6 Phosphate Buffer Solution (0.025 M with respect to each
the R. A. in a coolant is not always a good criterion in phosphate salt, pH = 6.86 at 25°C)—Dissolve 3.40 g of potas-
determining its potential protective properties. sium dihydrogen phosphate (KH2PO4) and 3.55 g of anhydrous
5.7 In summary, the precaution against the misuse of reserve disodium hydrogen phosphate (Na2HPO4) in distilled water
alkalinity is that the reserve alkalinity of an engine coolant and dilute to 1 L.
solution is not a dependable measure of its ability to prevent 7.7 Potassium Chloride Electrolyte—Prepare a saturated
corrosion, nor can it satisfactorily indicate the additional life of solution of potassium chloride (KCl) in water.
the solution.
8. Sampling
6. Apparatus 8.1 Sample the material in accordance with Standard Prac-
6.1 The pH meter, glass electrode, and calomel electrode, tice D1176.
shall be as specified in the section on Apparatus (Section 5) of 9. Preparation of Electrode System
Test Method D1287.
9.1 Maintenance of Electrodes—Clean the glass electrodes
6.2 It is recognized that many laboratories use a combina- or combination electrode at frequent intervals (not less than
tion electrode system for measuring the reserve alkalinity of once every week during continual use) in accordance with the
engine coolants. It should be noted that results obtained from manufacturer’s instructions. Drain the calomel electrodes at
using a combination electrode system have been found to be least once each week and fill with KCl electrolyte. Keep the
statistically different from results obtained when using the electrolyte level in the calomel electrode above that of the
calomel and reference electrode system.3 liquid in the titration beaker at all times. When not in use,
7. Reagents immerse the lower half of the electrodes in water and do not
allow them to be immersed in the titrated solution for any
7.1 Purity of Reagents—Reagent grade chemicals shall be appreciable period of time between titrations. Although the
used in all tests. Unless otherwise indicated, it is intended that electrodes are not extremely fragile, they should be handled
all reagents shall conform to the specifications of the Commit- carefully at all times.
tee on Analytical Reagents of the American Chemical Society, 9.1.1 A combination electrode system can also be used for
where such specifications are available.4 Other grades may be this test method.
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the 9.2 Preparation of Electrodes—Before and after using, blot
accuracy of the determination. the glass electrode or combination electrode thoroughly with a
clean cloth, or a soft, absorbent tissue, and rinse with water.
7.2 Purity of Water—References to water shall be under- Blot the calomel reference electrode with a cloth or tissue;
stood to mean distilled water or water of equal purity. Distilled carefully remove the ground-glass sleeve and thoroughly blot
water shall be boiled thoroughly, or purged with carbon both ground-glass surfaces. Replace the sleeve loosely and
dioxide-free air, to remove carbon dioxide, and shall be allow a few drops of electrolyte to drain through to flush the
protected with a soda-lime tube or the equivalent while cooling ground-glass joint. Wet the ground surfaces thoroughly with
electrolyte, set the sleeve firmly in place, and rinse the
3
Refer to ASTM Report RR:D15-1004. electrode with water. Prior to each titration, soak the prepared
4
Reagent Chemicals, American Chemical Society Specifications , American electrode in water for at least 2 min. Immediately before use,
Chemical Society, Washington, DC. For suggestions on the testing of reagents not touch the tips of the electrodes with a dry cloth or tissue to
listed by the American Chemical Society, see Analar Standards for Laboratory
remove excess water.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
5
MD. Commercially available buffer tablets or prepared buffer solutions may be used.

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 D1121 − 11
10. Electrode System in pH Units NOTE 2—In the event that the glass electrode becomes coated with an
oil, grease, or other film, it is recommended that a 1 to 1 solvent mix of
10.1 Turn on the instrument, allow to warm up, and adjust toluene and ethyl acetate be used to remove the film.
in accordance with the manufacturer’s instructions. Allow
sufficient time for the temperature of the buffer solution and 12. Calculations Using Reserve Alkalinity Data
immersed electrodes to equalize and set the temperature knob 12.1 Calculations of percent depletion during simulated or
at the temperature of the buffer solution. Calibrate the assem- actual coolant service may be obtained by use of the following
bly with a minimum of two buffer solutions to check the equation:
linearity of the response of the electrode or incorrect tempera- Percent depletion 5 100 @ ~ RA1 /C 1 2 RA2 /C 2 ! / ~ RA1 /C 1 ! # (1)
ture compensation. The presence of a faulty electrode is
indicated by a failure to obtain a reasonably correct value for where:
pH of the second standard solution when the meter has been RA1 = initial reserve alkalinity,
standardized with the first. A cracked electrode will often yield RA2 = final reserve alkalinity,
pH values that are essentially the same for both standards. C1 = initial coolant or additive concentration in percent,
Adjust the standardization or asymmetry potential control until and
the reading of the dial corresponds to the known pH of the C2 = final coolant or additive concentration in percent.
standardizing buffer solution. NOTE 3—In the case of a coolant solution, if the concentration is
unknown, it can be determined by appropriate test methods, such as
refractive index, freezing point, or specific gravity, and by reference to
11. Procedure available tables. The water content of the coolant solution can be
determined by Test Method D1123, and the concentration calculated.
11.1 Pipet 10 mL of a thoroughly mixed sample into a 250
mL tall-form spout-less beaker. Allow 1 minute drain time. 12.2 The percent depletion data allows coolant investigators
Add about 90 mL of distilled water (Note 2). to compare, on an equivalent basis, the reserve alkalinity data
from a number of identical tests on similar coolants.
NOTE 1—The amount of water added is not critical; however, it must be
sufficient to cover the electrode tips. If the reserve alkalinity is less than 12.3 In the case of vehicle service tests the percent depletion
2, the sample size may be increased to 50 mL diluted to 100 mL with should be reported on the basis of some unit of mileage, such
water, and the total titration divided by 5 to give the reserve alkalinity as as 10 000 miles. As implied in 5.2, percent depletion of the
defined. reserve alkalinity, although related to coolant durability and the
11.2 Prepare the calomel and glass electrode as described in condition or performance of cooling system, is only a part of
Section 9. Place the beaker containing the test solution on the the coolant evaluation procedure.
titration stand, adjust so that the lower half of each electrode is
13. Report
immersed, start the stirrer, and adjust the rate of the stirring so
that there is vigorous stirring without spattering. Fill the 50-mL 13.1 Report the sample description and the reserve alkalin-
buret with standardized 0.100 N HCl. The normality of the acid ity to the nearest 0.1 mL of 0.100 N HCl for the standard
used may be in the range from 0.095 to 0.105, but the actual 10-mL sample. Sample description may vary from a simple
titration will require correction to give the equivalent titration identification number to a complete history and analysis, such
with 0.100 N acid. Position the buret tip inside the beaker. as that utilized for used coolants from laboratory performance
Adjust the pH meter temperature compensator to agree with the and vehicle service tests.
solution temperature. Record the initial pH and proceed with 14. Precision and Bias
the titration to a pH of about 7. Use a slow, drop wise titration
rate from pH 7 to approach the end point of pH 5.5. Record the 14.1 Repeatability—Duplicate results by the same operator
volume of acid used, acid normality, and sample size. Switch should not be considered suspect unless they differ by more
the pH meter to standby and rinse the electrodes with water and than 60.2 mL.
dry with clean absorbent material before the next determina- 14.2 Reproducibility—The results submitted by two or more
tion. When the pH meter is not in use, immerse the electrodes laboratories should not be considered suspect unless the results
in distilled water. When a large number of reserve alkalinity differ by more than 60.2 mL.
determinations are made during a period of several hours, it is
recommended that the meter be recalibrated at various intervals 15. Keywords
as described in 10.1. 15.1 buffering; engine coolants; RA; reserve alkalinity

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 D1121 − 11
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