ASTM D4252-89(1995)e1
(Test Method)Standard Test Methods for Chemical Analysis of Alcohol Ethoxylates and Alkylphenol Ethoxylates
Standard Test Methods for Chemical Analysis of Alcohol Ethoxylates and Alkylphenol Ethoxylates
SCOPE
1.1 These test methods cover the various test methods used to evaluate those properties pertinent to the characterization of alcohol ethoxylates and alkylphenol ethoxylates with respect to suitability for desired uses.
1.2 The procedures for sampling and analysis appear in the following order: Sections Sampling Liquids 6 Solids 7 Methods of Chemical Analysis Water or moisture 8 Refractive index 9 and 10 pH 11 Acidity or basicity 12 and 13 Hydroxyl number 14 to 20 Cloud point 21 Iodine number 22 Ash 23 Iron 24 Ethylene oxide content 25 Polyethylene glycols 26 to 32
1.3 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 and health practices and determine the applicability of regulatory limitations prior to use. Material Safety Data Sheets are available for reagents and materials. Review them for hazards prior to usage. Specific hazard statements appear in Section 5 and Notes 1 and 3.
General Information
Relations
Standards Content (Sample)
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e1
Designation: D 4252 – 89 (Reapproved 1995)
Standard Test Methods for
Chemical Analysis of Alcohol Ethoxylates and Alkylphenol
Ethoxylates
This standard is issued under the fixed designation D 4252; 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.
e NOTE—Keywords were added editorially in February 1995.
1. Scope D 1068 Test Methods for Iron in Water
D 1172 Test Method for pH of Aqueous Solutions of Soaps
1.1 These test methods cover the various test methods used
and Detergents
to evaluate those properties pertinent to the characterization of
D 1193 Specification for Reagent Water
alcohol ethoxylates and alkylphenol ethoxylates with respect to
D 1209 Test Method for Color of Clear Liquids (Platinum-
suitability for desired uses.
Cobalt Scale)
1.2 The procedures for sampling and analysis appear in the
D 1218 Test Method for Refractive Index and Refractive
following order:
Dispersion of Hydrocarbon Liquids
Sections
D 1613 Test Method for Acidity in Volatile Solvents and
Sampling
Liquids 6
Chemical Intermediates Used in Paint, Varnish, Lacquer,
Solids 7
and Related Products
Methods of Chemical Analysis
D 1959 Test Method for Iodine Value of Drying Oils and
Water or moisture 8
Refractive index 9 and 10
Fatty Acids
pH 11
D 2024 Test Method for Cloud Point of Nonionic Surfac-
Acidity or basicity 12 and 13
Hydroxyl number 14-20 tants
Cloud point 21
D 2959 Test Method for Ethylene Oxide Content of Poly-
Iodine number 22
ethoxylated Surfactants
Ash 23
E 180 Practice for Determining the Precision of ASTM
Iron 24
Ethylene oxide content 25
Methods for Analysis and Testing of Industrial Chemicals
Polyethylene glycols 26-32
E 200 Practice for Preparation, Standardization, and Stor-
1.3 This standard does not purport to address all of the
age of Standard Solutions for Chemical Analysis
safety concerns, if any, associated with its use. It is the
E 203 Test Method for Water Using Karl Fischer Reagent
responsibility of the user of this standard to establish appro-
E 394 Test Method for Iron in Trace Quantities Using the
priate safety and health practices and determine the applica-
1,10-Phenanthroline Method
bility of regulatory limitations prior to use. Material Safety
3. Significance and Use
Data Sheets are available for reagents and materials. Review
them for hazards prior to usage. Specific hazard statements
3.1 Alcohol ethoxylates and alkylphenol ethoxylates are
appear in Section 5 and Note 1 and Note 3. important surfactants in household and industrial cleaners.
They may be used as either nonionic surfactants or sulfated and
2. Referenced Documents
used as anionic surfactants. Careful control of the ethoxylate
2.1 ASTM Standards:
characteristics is desired as variations may result in either
D 459 Terminology Relating to Soaps and Other Deter-
desirable or undesirable end-use properties.
gents
4. Purity of Reagents
D 482 Test Method for Ash from Petroleum Products
4.1 Reagent-grade chemicals shall be used in all tests.
Unless otherwise indicated, it is intended that all reagents shall
conform to the specifications of the Committee on Analytical
These test methods are under the jurisdiction of ASTM Committee D-12 on
Soaps and Other Detergents and are the direct responsibility of Subcommittee 12.12
on Analysis of Soaps and Synthetic Detergents.
Current edition approved May 26, 1989. Published July 1989. Originally Annual Book of ASTM Standards, Vol 11.01.
published as D 4252 – 83. Last previous edition D 4252 – 88. Annual Book of ASTM Standards, Vol 06.04.
2 6
Annual Book of ASTM Standards, Vol 15.04. Annual Book of ASTM Standards, Vol 06.03.
3 7
Annual Book of ASTM Standards, Vol 05.01. Annual Book of ASTM Standards, Vol 15.05.
Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
D 4252
Reagents of the American Chemical Society, where such same analyst on different days, has been estimated to be
specifications are available. Other grades may be used, pro- 0.00021 units absolute at 36 df. Two such averages should be
vided it is first ascertained that the reagent is of sufficiently considered suspect (95 % confidence level) if they differ by
high purity to permit its use without lessening the accuracy of more than 0.00059 units absolute.
the determination. 10.1.2 Reproducibility (Multilaboratory)—The standard de-
4.2 Unless otherwise indicated, references to water shall be viation of results (each the average of duplicates), obtained by
understood to mean Type III reagent water conforming to analysts in different laboratories, has been estimated to be
Specification D 1193. 0.00059 units absolute at 7 df. Two such averages should be
considered suspect (95 % confidence level) if they differ by
5. Safety Precautions
more than 0.0020 units absolute.
10.1.3 Checking Limits for Duplicates—Report the refrac-
5.1 All reagents and chemicals should be handled with care.
Before using any chemical, read and follow all safety precau- tive index of the sample to the nearest 0.0001. Duplicate runs
that agree within 0.00025 units are acceptable for averaging
tions and instructions on the manufacturer label. Clean up any
spill immediately. For information on cleaning up spills refer to (95 % confidence level).
the Laboratory Disposal Manual, Manufacturing Chemists
pH
Association, Washington, DC.
11. Procedure
SAMPLING
11.1 Determine the pH in accordance with Test Method
6. Liquids
D 1172, except prepare the solution by transferring 1 6 0.001
g of the sample to a 100 mL volumetric flask and diluting in
6.1 Thoroughly mix the sample before sampling. If a solid
accordance with Test Method D 1172. Measure the pH 10 min
layer or crystals have formed on the bottom of the bottle, melt
after diluting the sample solution to volume.
in an oven or water bath at 55°C and mix well before sampling.
ACIDITY OR BASICITY
7. Solids
7.1 Melt in an oven or water bath at 55°C and mix well
12. Procedure
before sampling. If it is necessary to heat at temperatures above
12.1 Determine acidity or basicity in accordance with Test
60°C, replace the gas cap with an inert gas, such as oxygen-free
Method D 1613 using a 3+1 solution of isopropyl alcohol and
nitrogen, helium, or argon before heating.
water as the solvent and a 10-g sample.
WATER OR MOISTURE
13. Precision
8. Procedure
13.1 The following criteria should be used for judging the
,
10 11
acceptability of results:
8.1 Determine water or moisture in accordance with Test
13.1.1 Repeatability (Single Analyst)—The standard devia-
Method E 203.
tion of results (each the average of duplicates), obtained by the
REFRACTIVE INDEX
same analyst on different days, has been estimated to be 0.017
meq/100 g at 27 df. Two such averages should be considered
9. Procedure
suspect (95 % confidence level) if they differ by more than
9.1 Measure the refractive index at 50°C in accordance with
0.049 meq/100 g.
Test Method D 1218.
13.1.2 Reproducibility (Multilaboratory)—The standard de-
viation of results (each the average of duplicates), obtained by
10. Precision
analysts in different laboratories, has been established to be
10.1 The following criteria should be used for judging the
0.12 meq/100 g at 5 df. Two such averages should be
9,10
acceptability of results:
considered suspect (95 % confidence level) if they differ by
10.1.1 Repeatability (Single Analyst)—The standard devia-
more than 0.44 meq/100 g.
tion of results (each the average of duplicates), obtained by the
13.1.3 Checking Limits for Duplicates—Report the acidity
or basicity of the sample to the nearest 0.05 meq/100 g.
Duplicate runs that agree within 0.051 meq/100 g are accept-
Reagent Chemicals, American Chemical Society Specifications, American
able for averaging (95 % confidence level).
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
HYDROXYL NUMBER
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
14. Terminology
MD.
The precision estimates are based on an interlaboratory study on ALFONICt
14.1 Definition:
1412-60, MAKONt-10, NEODOLt 25-9, PLURONICt 25R1, and TERGITOL
15-S-3 by nine laboratories.
Statistical analysis was performed in accordance with Practice E 180 for
developing precision estimates. Data supporting the precision statements are on file The precision estimates are based on an interlaboratory study on ALFONICt
at ASTM Headquarters, 100 Barr Harbor Drive, West Conshohocken, PA 19428 as 1412-60, MAKONt-10, NEODOLt 25-9, PLURONICt 25R1 and TERGITOLt
RR: D12-1004. 15-S-3 by six laboratories.
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
D 4252
14.1.1 hydroxyl number—the number of milligrams of po-
where:
tassium hydroxide equivalent to the hydroxyl content of1gof
M 5 molecular weight of sample and
sample.
F 5 number of hydroxyl groups per molecule.
18.2 Pipet accurately 25 mL of phthalic anhydride reagent
15. Summary of Test Method
into the flask and swirl to effect solution. Add two boiling
15.1 The hydroxyl groups are esterified by reaction with
chips, attach a dry reflux condenser with a ground glass joint
phthalic anhydride in a pyridine medium at the temperature of
fitted with a TFE-fluorocarbon sleeve to the flask, and reflux
reflux of the mixture. After cooling, the excess of phthalic
for1honan electric hotplate.
anhydride is hydrolyzed with water and the phthalic acid
18.3 Turn off the hotplate and insert an insulated pad
formed is titrated to the phenolphthalein end point with
between the flask and the hot plate. Allow to cool for 20 min.
standard sodium hydroxide solution. The hydroxyl content is
Wash down the condenser, first with 25 mL of pyridine and
calculated from the difference in titration of the blank and of
then with 25 mL of water.
the sample solution.
18.4 Remove the flask from the condenser. Add 4 or 5 drops
of phenolphthalein indicator to the flask and titrate with
16. Apparatus
standard 1 N sodium hydroxide solution to a faint pink end
16.1 Reflux Assembly, consisting of a reflux condenser and
point (Note 2).
a 250-mL Erlenmeyer flask, 24/40 standard taper joint with
18.5 Make a blank determination following 18.2-18.4.
TFE-fluorocarbon sleeves.
16.2 Buret, 50 mL, graduated in 0.1-mL intervals. Class A
NOTE 2—It is essential that the sample titration requires at least three
or equivalent. fourths of the blank titration. The difference between the two titrations
should be of the order of 10 mL. If this is not the case the sample size
16.3 Pipet, 25-mL capacity, Class A or equivalent.
1 1 should be adjusted accordingly and the analysis rerun.
16.4 Insulating Pad,3 ⁄2 by 3 ⁄2 by 1 in., preferably not
asbestos.
18.6 Determine the free acidity or free alkalinity as de-
scribed in Section 12 or as follows: To 25 mL of a 3 + 1
17. Reagents
isopropyl alcohol/water mixture in a 250-mL Erlenmeyer flask
17.1 Pyridine, A. R.—To be acceptable, each lot should pass
add 2 to 3 drops of phenolphthalein indicator solution and
the following quality test: Place7gof phthalic anhydride and
titrate with standard 0.1 N sodium hydroxide solution to a faint
50 mL of pyridine (Warning—see Note 1) in a glass-stoppered
pink. Accurately weigh 10 to 20 g of sample and add to the
flask, shake vigorously until dissolved. Heat at 50 or 60°C for
contents of the flask.
30 min, allow to stand at room temperature in the dark for 24
18.7 If the solution is colorless titrate with standard 0.1 N
h and then measure the Pt-Co color (Test Method D 1209). The
sodium hydroxide solution to a faint pink. If the solution is
pyridine is acceptable if the color does not exceed 200.
pink titrate with standard 0.1 N hydrochloric acid to just
colorless.
NOTE 1—Warning: Avoid breathing pyridine vapors, as they are toxic.
Dispose of pyridine wastes in a well ventilated hood.
19. Calculations
17.2 Sodium Hydroxide,(1 N), carbonate free. Purchase or
prepare, standardize, and store according to Practice E 200. 19.1 Calculate the hydroxyl number from the following
17.3 Phthalic Anhydride Reagent—Dissolve 98 6 1gof
equations:
phthalic anhydride in 700 mL of pyridine (Note 1), shake to 19.1.1 For samples containing free acidity:
effect solution. Store in a brown bottle. Preferably, the solution
~B 2 S!N C 3 N
Hydroxyl Number, mg KOH/g 5 1 3 56.1
should stand overnight before using. Prepare a fresh reagent F G
W W
each week or more frequently if the Pt-Co color (Test Method (2)
D 1209) exceeds a value of 200.
19.1.2 For samples containing free alkalinity:
17.4 Sodium Hydroxide (0.1 N)—Purchase or prepare, stan-
~B 2 S!N C 3 N
dardize, and store according to Practice E 200.
Hydroxyl Number, mg KOH/g 5 2 3 56.1
F G
W W
17.5 Hydrochloric Acid (0.1 N)—Purchase or prepare by
(3)
diluting 8.3 mL of concentrated hydrochloric acid to 1 L with
distilled water. Standardize and store according to Practice where:
B 5 volume of 1 N sodium hydroxide solution required
E 200.
for blank titration (18.5), mL,
17.6 Phenolphthalein Indicator Solution—Dissolve1gof
S 5 volume of 1 N sodium hydroxide solution required
phenolphthalein in 100 mL of pyridine.
for sample titration (18.4), mL,
17.7 Isopropyl Alcohol,A. R.
N 5 normality of 1 N sodium hydroxide solution,
18. Procedure
W 5 weight of sample taken (18.1), g,
C 5 volume of 0.1 N sodium hydroxide/hydrochloric acid
18.1 Weigh into a clean and dry 250-mL Erlenmeyer flask
required for acidity/alkalinity titration (18.7), mL,
with ground glass joint to the nearest 0.1 mg an amount of
N 5 normality of 0.1 N sodium hydroxide/hydrochloric
sample calculated by means of the following equation but do 1
acid used for acidity/alkalinity titration (18.7), and
not use more than 10 g of sample:
W 5 weight of sample used for acidity/alkalinity titration
M
(18.6), g.
Amount of Sample, g 5 (1)
F 3 100
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
D 4252
19.2 Calculate the apparent molecular weight from the in 10
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