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: D7637 − 10 (Reapproved 2015)

Standard Test Method for

Determination of Glycerin Assay by Titration (Sodium Meta
Periodate)1
This standard is issued under the fixed designation D7637; 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 2.2 Other Standards:

The United States Pharmacopoeia 31 Glycerin Monograph –
1.1 This test method provides the quantitative determination
Assay Method3
of glycerin by the titrimetric method. It is applicable to all AOCS Official Method EA 6-94 (Replaces AOCS EA 6-51),
glycerin or glycerin/water mixtures >75 %. Determination of Crude Glycerin, Titrimetric Method4
1.2 The values stated in SI units are to be regarded as BS 5711: Part 3, 1979 Sampling and Test for Glycerol -
standard. No other units of measurement are included in this Determination of Glycerol Content5
standard.
3. Terminology
1.3 This standard may involve hazardous materials, opera-
3.1 Definitions:
tions and equipment. This standard does not purport to address
3.1.1 glycerin—propane-1,2,3-triol, C 3 H 5 (OH) 3 (also
all of the safety problems associated with its use. It is the
known as glycerine), 1,2,3-propanetriol, 1,2,3-
responsibility of whoever uses this standard to consult the
trihydroxypropane, glyceritol, glycyl alcohol, glycerol. CAS
established and appropriate safety and health practices and #56-81-5.
determine the applicability of regulatory limitations prior to
use. Specific precautions are listed in Section 8. 3.1.2 SMP—Sodium Meta Periodate.
3.1.3 For other definitions of terms used in this
1.4 This international standard was developed in accor-
specification, refer to Terminology D4725.
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the 4. Significance and Use
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical 4.1 This test method is based on the cold oxidation of the
Barriers to Trade (TBT) Committee. glycerol by sodium metaperiodate in a strong acidic medium.
Formaldehyde and formic acid are produced in this reaction
2. Referenced Documents and the latter is used to measure the glycerol content by
titration with standard sodium hydroxide solution, to a pH 8.1
2.1 ASTM Standards:2 6 0.1. The glycerol content is expressed as a percentage
D1193 Specification for Reagent Water (m/m).
D4725 Terminology for Engine Coolants and Related Fluids CH2 OH 2 CHOH 2 CH2 OH12 NaIO4 → (1)
E177 Practice for Use of the Terms Precision and Bias in
ASTM Test Methods HCOOH12 HCHO12 NaIO3 1H 2 O
E691 Practice for Conducting an Interlaboratory Study to 4.2 Interferences—The glycerin sample should be free of
Determine the Precision of a Test Method organic compounds with more than two hydroxyl groups on
adjacent carbon atoms (for example, sugars, glycols). These
types of compounds may produce formic acid which interferes
1
This test method is under the jurisdiction of ASTM Committee D15 on Engine with the determination of the glycerol content.
Coolants and Related Fluids and is the direct responsibility of Subcommittee
D15.04 on Chemical Properties.
Current edition approved May 1, 2015. Published June 2015. Originally
3
approved in 2010. Last previous edition approved in 2010 as D7637–10. DOI: Available from U.S. Pharmacopeia (USP), 12601 Twinbrook Parkway,
10.1520/D7637-10R15. Rockville, MD 20852-1790, http://www.usp.org.
2 4
For referenced ASTM standards, visit the ASTM website, www.astm.org, or Available from American Oil Chemists’ Society (AOCS), 2710 S. Boulder,
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM Urbana, IL 61802-6996, http://www.aocs.org.
5
Standards volume information, refer to the standard’s Document Summary page on Available from British Standards Institute (BSI), 389 Chiswick High Rd.,
the ASTM website. London W4 4AL, U.K., http://www.bsigroup.com.

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 D7637 − 10 (2015)
5. Apparatus 7.9 Potassium Iodide, aqueous solution—Dissolve 16.5 g of
5.1 Burette—50 mL “Type A” unit that can deliver 30 drops potassium iodide in water to make 100 mL. Store tightly
per mL and calibrated to meet the NIST standards. capped in a light-resistant container.
7.10 Starch Solution—Mix 1g of soluble starch with suffi-
NOTE 1— It is critical that all glassware be “Type A” and thoroughly
cleaned before use as dirty glassware will impact the analysis results.
cient cold water to make a thin paste. Add 200 mL of boiling
water, and boil for 1 min with continuous stirring. Cool, and
5.2 pH meter, fitted with glass electrode. use only the clear solution.
NOTE 2—The pH meter should be standardized with a minimum of two NOTE 4—It is recommended that freshly prepared starch solution be
buffer solutions at 10.0 and 7.0. (See 7.12.) used to ensure a sharper endpoint. Commercially available, stabilized
starch indicator solution may be also used in place of freshly prepared
5.3 Stirrer—preference should be given to a magnetic stir-
starch.
rer. In this case, check that it does not influence the pH meter.
7.11 Bromothymol blue indicator solution—Dissolve 100
6. Purity of Reagents and Water mg of bromothymol blue in 100 mL of water to make 100 mL
of indicator solution.
6.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that 7.12 pH Buffers (7.0 6 0.01 and 10.0 6 0.01 at 25°C)
all reagents conform to the specifications of the Committee on needed for pH meter standardization.
Analytical Reagents of the American Chemical Society where 7.13 Freshly boiled water, or equivalent. (See 6.2.)
such specifications are available. Other grades may be used
provided it is first ascertained that the reagent is of sufficiently 8. Precautions
high purity to permit its use without lessening the accuracy of 8.1 Sulfuric acid and sodium hydroxide solutions are cor-
the determination. rosive. Avoid eye and skin contact.
6.2 Purity of Water—Unless indicated otherwise, references 8.2 Please study and be aware of the Material Safety Data
to water shall be understood to mean Type II reagent water as Sheet and correct laboratory performance for the appropriate
defined in Specification D1193. health and safety precautions that may apply to any of the
chemicals and equipment prior to use.
NOTE 3—The presence of carbon dioxide can introduce errors; therefore
it is advisable to prepare 500 mL of water by boiling for 5 min and cooling 8.3 It is the responsibility of each organization to conduct a
to room temperature. Check the pH of the distilled water before use. The job hazard analysis to assess safety risks and PPE needed for
pH should be 7.0 6 0.1. If not, adjust the pH with 0.1 N sodium hydroxide performance of this test method.
(NaOH) or 0.1 N hydrogen chloride (HCl), whichever is appropriate. Store
the freshly boiled and neutralized water in a tightly closed container.
9. Procedure
7. Reagents 9.1 Sodium Periodate Solution Suitability Test—Pipet 10
mL of the prepared sodium periodate solution (Reagent 7.1)
7.1 Sodium Metaperiodate, NaIO4, acidic solution— into a 250-mL volumetric flask, dilute with water to volume,
Dissolve 60 g of sodium metaperiodate in sufficient water and mix.
containing 120 mL of 0.1 N sulfuric acid to make 1000 mL. Do
not heat to dissolve the periodate. If the solution is not clear, 9.2 Weigh approximately 550 mg of glycerin into flask.
pass it through a sintered-glass filter. Store the solution in a Dissolve the sample in 50 mL of water and pipette 50 mL of the
glass-stoppered, light-resistant container. diluted periodate solution prepared in 9.1. Allow the solution to
stand for 30 min.
7.2 Hydrochloric Acid, aqueous solution, approximately 0.1
N. 9.3 Add 5 mL of hydrochloric acid solution (Reagent 7.2)
and 10 mL of potassium iodide solution (Reagent 7.9), and
7.3 Sodium Hydroxide, aqueous solution, approximately gently swirl to mix. Allow the solution to stand for 5 min.
0.05 N.
9.4 Add 100 mL of water and 3 mL of starch solution
7.4 Sodium Hydroxide, 0.1 N, Standardized —Dissolve four (Reagent 7.10). Titrate slowly with 0.1 N sodium thiosulfate
grams of sodium hydroxide (NaOH) in water and dilute to one (Reagent 7.8) to the starch endpoint, mixing continuously to
liter. Standardize accurately to 60.0001 N. The standardized ensure the solution has stabilized after each addition.
sodium hydroxide solution should be protected against evapo- 9.5 Blank Test for Sodium Periodate Solution Suitability
ration and absorption of carbon dioxide (CO2) from the air. Test—For the blank, pipet 50 mL of the diluted periodate
7.5 Ethylene glycol (1,2-ethanediol, free from glycerol) solution into a flask containing 50 mL of water. Carry out, at
solution in water. 1:1 (v/v). the same time as the determination and under the same
conditions, a blank test without the glycerin test portion using
7.6 Sulfuric Acid Solution, aqueous solution, approximately
the same quantities of reagents and diluting water for the
0.1 N.
determinations as outlined in 9.1 through 9.4.
7.7 Sulfuric Acid Solution, aqueous solution, approximately
9.6 The ratio of the volume of 0.1 N sodium thiosulfate
0.2 N.
(Reagent 7.8) required for the glycerin-periodate mixture to
7.8 Sodium Thiosulfate, 0.1 N, aqueous solution. that required for the blank should be between 0.750 and 0.765.

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 D7637 − 10 (2015)
9.7 Glycerol Assay Determination—Transfer about 400 V1 = number of mL of 0.1 N sodium hydroxide solution used
mg of glycerin, accurately weighed on an analytical balance, for the sample titration,
into a 600 mL beaker. VB = number of mL of 0.1 N sodium hydroxide solution used
9.8 Dilute the sample in the beaker with 50 mL of water and for the blank titration,
add approximately 3 mL of bromothymol blue indicator F = Factor = 9.210,
(Reagent 7.11). Carefully acidify with 0.2 N sulfuric acid N = exact normality of sodium hydroxide that was used for
(Reagent 7.7) to a definite green or greenish yellow color. the titration, and
Neutralize with 0.05 N sodium hydroxide (Reagent 7.3) to a W = mass, in g, of glycerin subjected to the reaction with
definite blue endpoint, free from green color. sodium metaperiodate solution.

9.9 Pipette 50 mL of sodium metaperiodate solution (Re- 11. Report

agent 7.1) into the beaker. Mix using moderate agitation and 11.1 Report the glycerin content of the sample to the nearest
cover the beaker with a watch glass. Allow the beaker to stand 0.1 %.
for 30 min at room temperature (not exceeding 35°C) in the
dark or in subdued light. 12. Precision and Bias
NOTE 5—The presence of carbon dioxide can introduce errors; therefore 12.1 The precision of this test method is based on an
it is advisable to cover the beaker containing the test solution with a watch interlaboratory study conducted in 2009. Each of eight labora-
glass during all standing periods. tories tested two different materials. Every “test result” repre-
9.10 Add 10 mL of the ethylene glycol solution (Reagent sents an individual determination, and every laboratory re-
7.5) into the beaker. Mix using moderate agitation and cover ported two replicate test results for each of the materials.
the beaker with a watch glass. Allow the beaker to stand for 20 Except for the use of only two test materials, Practice E691
min at room temperature (not exceeding 35°C) in the dark or in was followed for the design and analysis of the data; the details
subdued light. are given in an ASTM Research Report.6
9.11 Dilute the solution with water to about 300 mL. 12.1.1 Repeatability Limit (r)—Two test results obtained
within one laboratory shall be judged not equivalent if they
9.12 Insert the glass electrode and using moderate stirring, differ by more than the “r” value for that material; “r” is the
titrate slowly as the endpoint is approached with 0.1 N sodium interval representing the critical difference between two test
hydroxide (Reagent 7.4) to a pH of 8.1 6 0.1 for the specimen results for the same material, obtained by the same operator
under assay. using the same equipment on the same day in the same
NOTE 6—When approaching the endpoint, it is critical that the titration laboratory.
is conducted slowly and the solution is well mixed after each addition to 12.1.1.1 Repeatability limits are listed in Table 1.
ensure a stable pH reading for the endpoint determination. 12.1.2 Reproducibility Limit (R)—Two test results shall be
9.13 Blank Determination for Glycerine Assay judged not equivalent if they differ by more than the “R” value
Determination—Carry out, at the same time as the assay for that material; “R” is the interval representing the critical
determination and under the same conditions, a blank test difference between two test results for the same material,
without the test portion using the same quantities of reagents obtained by different operators using different equipment in
and diluting water for the determinations as outlined in 9.5 different laboratories.
through 9.12. Titrate with 0.1 N sodium hydroxide to a pH of 12.1.2.1 Reproducibility limits are listed in Table 1.
6.5 6 0.1 for the blank. 12.1.3 The terms (repeatability limit and reproducibility
limit) are used as specified in Practice E177.
9.14 Each mL of 0.1 N sodium hydroxide, after correction
12.1.4 Any judgment in accordance with statements 12.1.1
for the blank, is equivalent to 9.210 mg of glycerol (C3H8O3).
and 12.1.2 would have an approximate 95 % probability of
10. Calculation being correct.
10.1 The glycerol content, expressed as a percentage, is 12.2 Bias—At the time of the study, there was no accepted
given by the formula: reference material suitable for determining the bias for this test
method, therefore no statement on bias is being made.
~ V 1 2 V B! 3 F 3 N
Glycerol ~ % ! 5 (2)
W
6
Supporting data have been filed at ASTM International Headquarters and may
where: be obtained by requesting Research Report RR:D15-1025.

TABLE 1 Glycerin (%)

Material AverageA Repeatability Reproducibility Repeatability Reproducibility
Standard Standard Limit Limit
Deviation Deviation
x̄ Sx̄ Sr SR r R
A 99.48 0.14 0.29 0.29 0.81 0.81
B 97.48 0.36 0.17 0.38 0.48 1.05
A
The average of the laboratories’ calculated averages.

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 D7637 − 10 (2015)
12.3 The precision statement was determined through sta- 13. Keywords
tistical examination of 26 results, from eight laboratories, on 13.1 antifreeze; engine coolant; ethylene; glycerin; glycer-
two materials. These two materials were described as the ine; glycerol; titrimetric
following:
Glycerin A: a 99.5 % pure glycerine (data from
seven laboratories included)
Glycerin B: a 97.5 % solution of glycerine (data
from six laboratories included)
12.4 To judge the equivalency of two test results, it is
recommended to choose the type of glycerin closest in char-
acteristics to the test fluid.

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