ASTM D500-95(2023)

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: D500 − 95 (Reapproved 2023)
Standard Test Methods of
Chemical Analysis of Sulfonated and Sulfated Oils
This standard is issued under the fixed designation D500; 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 mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
1.1 These test methods cover the chemical analysis of
sulfonated and sulfated oils. The analytical procedures appear
2. Referenced Documents
in the following order:
2.1 ASTM Standards:
Section
D1193 Specification for Reagent Water
Moisture:
Test Method A. Water by Distillation with Volatile Solvent 4 – 9
3. Purity of Reagents
Test Method B. Moisture and Volatile Matter by Hot-Plate Method 10 – 14
Organically Combined Sulfuric Anhydride:
3.1 Purity of Reagents—Reagent grade chemicals shall be
Test Method A. Titration Test 15 – 19
Test Method B. Extraction-Titration Test 20 – 24 used in all tests. Unless otherwise indicated, it is intended that
Test Method C. Ash-Gravimetric Test (in the Presence of True 25 – 28
all reagents shall conform to the specifications of the Commit-
Sulfonates)
tee on Analytical Reagents of the American Chemical Society,
Total Desulfated Fatty Matter 29 – 32
Total Active Ingredients 33 – 36 where such specifications are available. Other grades may be
Unsaponifiable Nonvolatile Matter 37 – 41
used, provided it is first ascertained that the reagent is of
Inorganic Salts 42 – 46
sufficiently high purity to permit its use without lessening the
Total Alkalinity 47 – 49
Total Ammonia 50 – 52
accuracy of the determination.
Acidity as Free Fatty Acids or Acid Number:
3.2 Purity of Water—Unless otherwise indicated, references
Test Method A. In the Absence of Ammonium or Triethanolamine 53 – 56
Soaps
to water shall be understood to mean reagent water conforming
Test Method B. In the Presence of Dark Colored Oils but in the 57 – 60
to Specification D1193.
Absence of Ammonium or Triethanolamine Soaps (Brine Test)
Test Method C. In the Presence of Ammonium or Triethanolamine 61 – 63
MOISTURE
Soaps
Water-Immiscible Organic Solvents Volatile with Steam 64 – 70
Method A. Water by Distillation with Volatile Solvent
1.2 The values stated in inch-pound units are to be regarded
as the standard. The metric equivalents of inch-pound units
4. Scope
may be approximate.
4.1 This test method covers the determination of water
1.3 This standard does not purport to address all of the
existing in a sample of sulfonated or sulfated oil, or both, by
safety concerns, if any, associated with its use. It is the
distilling the sample with a volatile solvent. The method is
responsibility of the user of this standard to establish appro-
applicable only to sulfonated and sulfated oils that do not
priate safety, health, and environmental practices and deter-
contain the following: mineral acids, free sulfonic acids, or free
mine the applicability of regulatory limitations prior to use.
sulfuric acid esters; or alkali hydroxides, carbonates or ac-
Material Safety Data Sheets are available for reagents and
etates; or alcohol, glycerin, diethylene glycol, acetone, or other
materials. Review them for hazards prior to usage.
water-miscible volatile compounds.
1.4 This international standard was developed in accor-
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom- 2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
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
These test methods are under the jurisdiction of ASTM Committee D12 on the ASTM website.
Soaps and Other Detergents and is the direct responsibility of Subcommittee D12.12 ACS Reagent Chemicals, Specifications and Procedures for Reagents and
on Analysis and Specifications of Soaps, Synthetics, Detergents and their Compo- Standard-Grade Reference Materials, American Chemical Society, Washington,
nents. DC. For suggestions on the testing of reagents not listed by the American Chemical
Current edition approved July 1, 2023. Published July 2023. Originally approved Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
in 1937. Last previous edition approved in 2016 as D500 – 95 (2016). DOI: U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
10.1520/D0500-95R23. copeial Convention, Inc. (USPC), Rockville, MD.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D500 − 95 (2023)
5. Apparatus with each 1 mL line numbered (5 mL at top). The error in any
indicated capacity may not be greater than 0.05 mL.
5.1 The apparatus required consists of a glass flask heated
by suitable means and provided with a reflux condenser
6. Reagents
discharging into a trap and connected to the flask. The
6.1 Oleic Acid, heated previous to use for 5 min to 10 min
connections between the trap and the condenser and flask shall
over a free flame at a temperature of 130 °C to 135 °C.
be interchangeable ground joints. The trap serves to collect and
6.2 Xylene.
measure the condensed water and to return the solvent to the
flask. A suitable assembly of the apparatus is illustrated in Fig.
7. Calibration
1.
7.1 To calibrate the apparatus add approximately 1 g of
5.1.1 Flask, 500 mL, of either the short-neck, round-bottom
water to a mixture of 80 g of xylene and 10 g of oleic acid.
type or the Erlenmeyer type.
Conduct the distillation as described in 8.2 – 8.4. When all the
5.1.2 Heat Source—The source of heat may be either an oil
water has distilled, cool the apparatus, add another g of water,
bath (stearic acid, paraffin wax, etc.), or an electric heater
and repeat the distillation. Continue the calibration up to the
provided with a sliding rheostat or other means of heat control.
capacity of the receiving tube.
5.1.3 Condenser—A water-cooled glass reflux condenser
(Fig. 1), having a jacket approximately 400 mm (15 ⁄4 in.) in
8. Procedure
3 1
length with an inner tube 9.5 nm to 12.7 mm ( ⁄8 in. to ⁄2 in.)
8.1 Clean the condenser and the receiving tube thoroughly
in outside diameter. The end of the condenser to be inserted in
with soap and warm water before using. Rinse well, then treat
the trap shall be ground off at an angle of 30° from the vertical
with hot cleaning solution (a mixture of 10 mL of saturated
axis of the condenser. When inserted into the trap, the tip of the
potassium dichromate (K Cr O ) and 990 mL of sulfuric acid
2 2 7
condenser shall be about 7 mm ( ⁄4 in.) above the surface of the
(H SO , sp gr 1.84)), and finally thoroughly wash and dry.
2 4
liquid in the trap after the distillation conditions have been
8.2 Take enough of the sample to be tested for analysis to
established. Fig. 1 shows a conventional sealed-in type of
condenser, but any other condenser fulfilling the detailed yield about 4 mL of water. Introduce the approximate quantity
into a weighing bottle and make the weighings from the bottle
requirements above may be used.
5.1.4 Trap—A trap made of well-annealed glass constructed into the flask, taking care that after removal of the sample no
drops of oil are left on the outside of the weighing bottle. Add
in accordance with Fig. 1 and graduated as shown to contain
5 mL at 20 °C. It shall be subdivided into 0.1 mL divisions, 80 g of xylene and oleic acid equivalent to about two and
one-half times the weight of the bone-dry sample to prevent
foaming and jellying of the contents of the flask. Introduce
glass beads to prevent bumping and mix the contents of the
flask thoroughly by swirling, taking care to avoid any loss of
material. Fill the trap with xylene and immediately connect the
flask with the distillation apparatus. Insert a loose cotton plug
in the top of the condenser tube to prevent condensation of
atmospheric moisture in the condenser tube.
8.3 Heat the flask and regulate the heating so that the
condenser tube immediately below the water jacket is just
barely hot. In this way a minimum of water will condense
farther up the condenser where it may be difficult to volatilize
any moisture condensed on the walls.
8.4 Continue the distillation at the specified rate until
practically no water is visible on any part of the apparatus
except within the graduations of the trap. This operation
usually requires less than 1 h. Increase the rate of distillation in
order to remove all traces of condensed water in the condenser
tube, and continue the distillation until the water level in the
trap remains unchanged after a 10 min interval. Dislodge any
droplets adhering to the side of the receiver with a thin copper
wire twisted into a loop. Immerse the receiving tube in warm
A = 45 mm to 55 mm water at about 40 °C for 15 min or until the xylene layer
B = 22 to 24 mm in inside diameter
becomes clear, then read and record the temperature and the
C = 9 to 11 mm in inside diameter
exact volume of the water in the trap.
D = 235 mm to 240 mm
E = 146 mm to 156 mm
9. Calibration
F and G are interchangeable joints, standard taper 24/40.
9.1 The volume of condensed water measured in the trap
may be converted into its equivalent weight in grams by means
FIG. 1 Apparatus for Water Determination by Distillation with
Volatile Solvent, Method A of Table 1. Calculate the percentage of water as follows:
D500 − 95 (2023)
A
TABLE 1 Specific Gravity of Water
13. Procedure
Temperature, °C Specific Gravity
13.1 Weigh approximately 5 g of oleic acid into the beaker
4 1.00000
and insert the thermometer. Heat the oleic acid gradually, while
35 0.99406
36 0.99371 stirring with the thermometer, until the temperature reaches
37 0.99336
130 °C. Place the beaker in an oven at 105 °C to 110 °C for
38 0.99299
15 min, cool in a desiccator, and weigh. Repeat the heating
39 0.99262
40 0.99224 over the hot plate and in the oven until two successive
41 0.99186
weighings differ by less than 1.5 mg.
42 0.99147
43 0.99107
13.2 Place about 6 g of the sample in the weighing flask and
44 0.99066
determine the weight accurately. Transfer the sample to the
45 0.99025
beaker (containing the oleic acid and the thermometer) and
A
This table is taken from Smithsonian Tables, compiled from various authors.
weigh the flask again. Heat the mixture exactly as in the taring
of the beaker as described in 13.1. The loss in weight is
equivalent to the moisture in the sample.
14. Calculation
Water, % 5 A/B × 100 (1)
~ !
14.1 Calculate the percentage of moisture and volatile
where:
matter in the sample as follows:
A = weight of water, g, and
Moisture and volatile matter, % 5 A/B × 100 (2)
~ !
B = weight of sample, g.
where:
Method B. Moisture and Volatile Matter by Hot-Plate
A = loss of weight, g, and
Method
B = weight of sample, g.
10. Scope
ORGANICALLY COMBINED SULFURIC
ANHYDRIDE
10.1 This test method covers the determination of the
Method A. Titration Test (For Sulfated Oils)
percentage of water and other compounds volatile at about
100 °C existing in a sample of sulfonated or sulfated oil, or
15. Scope
both, by rapid evaporation. The test method is applicable only
to sulfonated and sulfated oils that do not contain the follow- 15.1 This test method covers the determination of the
organically combined sulfuric anhydride existing in a sample
ing: mineral acids, free sulfonic acids or free sulfuric acid
esters, ammonia, acetic acid or similar volatile acids, alkali of sulfated oil by boiling the sample with sulfuric acid and
determining the acidity of the reaction mixture. This method is
hydroxides, carbonates, acetates or similar salts that may react
with oleic acid at elevated temperatures liberating volatile applicable only to oils that split off their combined SO upon
boiling with mineral acids and that do not contain compounds
acids, or glycerin, diethylene glycol, xylene, or other com-
pounds of similar volatility. that cannot be accurately titrated in water solution with methyl
orange as the indicator.
11. Apparatus
16. Apparatus
11.1 The apparatus required consists of a glass-stoppered
16.1 The apparatus required consists of a glass flask pro-
weighing flask, a glass beaker, and a suitable thermometer.
vided with a glass stopper and an air condenser. The connection
11.1.1 Weighing Flasks—Any suitable glass-stoppered
between the flask and the condenser shall be a ground joint.
weighing flask of 10 mL to 15 mL capacity.
Perforated glass beads shall be used to prevent bumping.
11.1.2 Beaker—A Griffin low-form glass beaker with an
16.1.1 Flask—An Erlenmeyer flask (Fig. 2) made of a
approximate capacity of 150 mL and a diameter of about 5 cm.
borosilicate glass, having a capacity of approximately 300 mL
11.1.3 Heat Source—The source of heat may be either an
and provided with a glass stopper.
electric hot plate with or without asbestos paper or board cover,
16.1.2 Condenser—The condenser required consists of a
or an open flame under a suitable asbestos board and a wire
glass tube, 915 mm (36 in.) in length, and 8 mm ( ⁄16 in.) in
gauze (to spread the heat).
outside diameter. The lower end of the tube shall be flared and
11.1.4 Thermometer, graduated from 90 °C to 150 °C, about
ground to fit the mouth of the Erlenmeyer flask.
3 in. in length, and substantially constructed.
16.1.3 Glass Beads—Perforated glass beads, made of
chemically-resistant glass, approximately 4 mm ( ⁄32 in.) in
12. Reagents
diameter. Before using, the glass beads shall be boiled thor-
12.1 Desiccating Agent—Any suitable desiccating agent
oughly in several portions of water or until the wash water
may be used.
reacts neutral to methyl orange indicator.
NOTE 1—Recent investigations seem to indicate that calcium chloride is
17. Reagents
unreliable as a laboratory desiccating agent.
12.2 Oleic Acid. 17.1 Ethyl Ether.
D500 − 95 (2023)
after each addition of reagent. Drain burets for 3 min before
taking readings. Calculate the alkalinity, A, as follows:
A 5 @ B × D 2 C × E #/W (3)
~ ! ~ !
where:
A = total alkalinity, mg of KOH/g,
B = millilitres of H SO required for titration of the sample,
2 4
C = millilitres of NaOH solution required for titration of the
sample,
D = str
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