ASTM D500-95(2003)
(Test Method)Standard Test Methods of Chemical Analysis of Sulfonated and Sulfated Oils
Standard Test Methods of Chemical Analysis of Sulfonated and Sulfated Oils
ABSTRACT
These test methods cover the chemical analysis of sulfonated and sulfated oils. Water by distillation with volatile solvent and moisture and volatile matter by hot-plate shall be tested to meet the requirements prescribed. Titration test, extraction-titration test, and ash-gravimetric test shall be performed to meet the requirements specified. Total desulfated fatty matter, total active ingredients, unsaponifiable non-volatile matter, inorganic salts, total alkalinity, and total ammonia shall be tested to meet the requirements prescribed. In the absence of ammonium or triethanolamine soaps test method, brine test method, and in the presence of ammonium or triethanolamine soaps test method shall be performed to meet the requirements prescribed. Water-immiscible organic solvents volatile with steam shall be tested to meet the requirements prescribed.
SCOPE
1.1 These test methods cover the chemical analysis of sulfonated and sulfated oils. The analytical procedures appear in the following order:
SectionMoisture:Test Method A. Water by Distillation with Volatile Solvent4-9Test Method B. Moisture and Volatile Matter by Hot-Plate Method10-14Organically Combined Sulfuric Anhydride:Test Method A. Titration Test15-19Test Method B. Extraction-Titration Test20-24Test Method C. Ash-Gravimetric Test (in the Presence of True Sulfonates)25-28Total Desulfated Fatty Matter29-32Total Active Ingredients33-36Unsaponifiable Nonvolatile Matter37-41Inorganic Salts42-46Total Alkalinity47-49Total Ammonia50-52Acidity as Free Fatty Acids or Acid Number:Test Method A. In the Absence of Ammonium or Triethanolamine Soaps53-56Test Method B. In the Presence of Dark Colored Oils but in the Absence of Ammonium or Triethanolamine Soaps (Brine Test)57-60Test Method C. In the Presence of Ammonium or Triethanolamine Soaps61-63Water-Immiscible Organic Solvents Volatile with Steam64-70
1.2 The values stated in inch-pound units are to be regarded as the standard. The metric equivalents of inch-pound units may be approximate.
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.
General Information
Relations
Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information.
Designation: D500 – 95 (Reapproved 2003)
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.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope 3. Purity of Reagents
1.1 These test methods cover the chemical analysis of 3.1 Purity of Reagents—Reagent grade chemicals shall be
sulfonated and sulfated oils. The analytical procedures appear used in all tests. Unless otherwise indicated, it is intended that
in the following order: all reagents shall conform to the specifications of the Commit-
tee onAnalytical Reagents of theAmerican Chemical Society,
Section
where such specifications are available. Other grades may be
Moisture:
used, provided it is first ascertained that the reagent is of
Test Method A. Water by Distillation with Volatile Solvent 4-9
sufficiently high purity to permit its use without lessening the
Test Method B. Moisture and Volatile Matter by Hot-Plate Method 10-14
Organically Combined Sulfuric Anhydride:
accuracy of the determination.
Test Method A. Titration Test 15-19
3.2 Purity of Water—Unlessotherwiseindicated,references
Test Method B. Extraction-Titration Test 20-24
Test Method C. Ash-Gravimetric Test (in the Presence of True 25-28 towatershallbeunderstoodtomeanreagentwaterconforming
Sulfonates)
to Specification D1193.
Total Desulfated Fatty Matter 29-32
Total Active Ingredients 33-36
MOISTURE
Unsaponifiable Nonvolatile Matter 37-41
Inorganic Salts 42-46
Total Alkalinity 47-49
Method A. Water by Distillation with Volatile Solvent
Total Ammonia 50-52
Acidity as Free Fatty Acids or Acid Number:
4. Scope
Test Method A. In the Absence of Ammonium or Triethanolamine 53-56
Soaps
4.1 This test method covers the determination of water
Test Method B. In the Presence of Dark Colored Oils but in the 57-60
existing in a sample of sulfonated or sulfated oil, or both, by
Absence of Ammonium or Triethanolamine Soaps (Brine Test)
Test Method C. In the Presence of Ammonium or Triethanolamine 61-63 distilling the sample with a volatile solvent. The method is
Soaps
applicable only to sulfonated and sulfated oils that do not
Water-Immiscible Organic Solvents Volatile with Steam 64-70
containthefollowing:mineralacids,freesulfonicacids,orfree
1.2 The values stated in inch-pound units are to be regarded
sulfuric acid esters; or alkali hydroxides, carbonates or ac-
as the standard. The metric equivalents of inch-pound units etates;oralcohol,glycerin,diethyleneglycol,acetone,orother
may be approximate.
water-miscible volatile compounds.
1.3 This standard does not purport to address all of the
5. Apparatus
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- 5.1 The apparatus required consists of a glass flask heated
priate safety and health practices and determine the applica- by suitable means and provided with a reflux condenser
bility of regulatory limitations prior to use. Material Safety discharging into a trap and connected to the flask. The
Data Sheets are available for reagents and materials. Review connections between the trap and the condenser and flask shall
them for hazards prior to usage. beinterchangeablegroundjoints.Thetrapservestocollectand
measure the condensed water and to return the solvent to the
2. Referenced Documents
flask.Asuitable assembly of the apparatus is illustrated in Fig.
2.1 ASTM Standards:
1.
D1193 Specification for Reagent Water
5.1.1 Flask,500-mL,ofeithertheshort-neck,round-bottom
type or the Erlenmeyer type.
These test methods are under the jurisdiction of ASTM Committee D12 on
SoapsandOtherDetergentsandisthedirectresponsibilityofSubcommitteeD12.12 Reagent Chemicals, American Chemical Society Specifications, American
on Analysis of Soaps and Synthetic Detergents. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved April 15, 1995. Published June 1995. Originally listed by the American Chemical Society, see Analar Standards for Laboratory
published as D500–37. Last previous edition D500–89. DOI: 10.1520/D0500- Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
95R03. and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
Annual Book of ASTM Standards, Vol 11.01. MD.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D500 – 95 (2003)
and repeat the distillation. Continue the calibration up to the
capacity of the receiving tube.
8. Procedure
8.1 Clean the condenser and the receiving tube thoroughly
with soap and warm water before using. Rinse well, then treat
with hot cleaning solution (a mixture of 10 mL of saturated
potassium dichromate (K Cr O ) and 990 mL of sulfuric acid
2 2 7
(H SO , sp gr 1.84)), and finally thoroughly wash and dry.
2 4
8.2 Take enough of the sample to be tested for analysis to
yield about 4 mLof water. Introduce the approximate quantity
into a weighing bottle and make the weighings from the bottle
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
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.Fillthetrapwithxyleneandimmediatelyconnectthe
flask with the distillation apparatus. Insert a loose cotton plug
A=45to55mm
B = 22 to 24 mm in inside diameter
in the top of the condenser tube to prevent condensation of
C = 9 to 11 mm in inside diameter
atmospheric moisture in the condenser tube.
D = 235 to 240 mm
8.3 Heat the flask and regulate the heating so that the
E = 146 to 156 mm
F and G are interchangeable joints, standard taper 24/40.
condenser tube immediately below the water jacket is just
barely hot. In this way a minimum of water will condense
FIG. 1 Apparatus for Water Determination by Distillation with
farther up the condenser where it may be difficult to volatilize
Volatile Solvent, Method A
any moisture condensed on the walls.
8.4 Continue the distillation at the specified rate until
5.1.2 Heat Source—The source of heat may be either an oil
practically no water is visible on any part of the apparatus
bath (stearic acid, paraffin wax, etc.), or an electric heater
except within the graduations of the trap. This operation
providedwithaslidingrheostatorothermeansofheatcontrol.
usuallyrequireslessthan1h.Increasetherateofdistillationin
5.1.3 Condenser—A water-cooled glass reflux condenser
order to remove all traces of condensed water in the condenser
(Fig. 1), having a jacket approximately 400 mm (15 ⁄4 in.) in
tube, and continue the distillation until the water level in the
3 1
length with an inner tube 9.5 to 12.7 mm ( ⁄8 to ⁄2 in.) in
trap remains unchanged after a 10-min interval. Dislodge any
outsidediameter.Theendofthecondensertobeinsertedinthe
droplets adhering to the side of the receiver with a thin copper
trapshallbegroundoffatanangleof30°fromtheverticalaxis
wire twisted into a loop. Immerse the receiving tube in warm
of the condenser. When inserted into the trap, the tip of the
water at about 40°C for 15 min or until the xylene layer
condensershallbeabout7mm( ⁄4in.)abovethesurfaceofthe
becomes clear, then read and record the temperature and the
liquid in the trap after the distillation conditions have been
exact volume of the water in the trap.
established. Fig. 1 shows a conventional sealed-in type of
9. Calibration
condenser, but any other condenser fulfilling the detailed
requirements above may be used.
9.1 The volume of condensed water measured in the trap
5.1.4 Trap—Atrapmadeofwell-annealedglassconstructed
maybeconvertedintoitsequivalentweightingramsbymeans
in accordance with Fig. 1 and graduated as shown to contain 5
of Table 1. Calculate the percentage of water as follows:
mLat 20°C. It shall be subdivided into 0.1-mLdivisions, with
each 1-mL line numbered (5 mL at top). The error in any
A
TABLE 1 Specific Gravity of Water
indicated capacity may not be greater than 0.05 mL.
Temperature, °C Specific Gravity
4 1.00000
6. Reagents
35 0.99406
6.1 Oleic Acid, heated previous to use for 5 to 10 min over
36 0.99371
37 0.99336
a free flame at a temperature of 130 to 135°C.
38 0.99299
6.2 Xylene.
39 0.99262
40 0.99224
7. Calibration
41 0.99186
42 0.99147
7.1 To calibrate the apparatus add approximately1gof
43 0.99107
water to a mixture of 80 g of xylene and 10 g of oleic acid.
44 0.99066
45 0.99025
Conduct the distillation as described in 8.2-8.4. When all the
A
water has distilled, cool the apparatus, add another g of water, This table is taken from Smithsonian Tables, compiled from various authors.
D500 – 95 (2003)
Water,% 5 ~A/B! 3100 (1) 14. Calculation
14.1 Calculate the percentage of moisture and volatile
where:
matter in the sample as follows:
A = weight of water, g, and
B = weight of sample, g.
Moistureandvolatilematter,% 5 ~A/B! 3100 (2)
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
10.1 This test method covers the determination of the
ANHYDRIDE
percentage of water and other compounds volatile at about
100°C existing in a sample of sulfonated or sulfated oil, or
Method A. Titration Test (For Sulfated Oils)
both, by rapid evaporation. The test method is applicable only
15. Scope
to sulfonated and sulfated oils that do not contain the follow-
ing: mineral acids, free sulfonic acids or free sulfuric acid
15.1 This test method covers the determination of the
esters, ammonia, acetic acid or similar volatile acids, alkali
organically combined sulfuric anhydride existing in a sample
hydroxides, carbonates, acetates or similar salts that may react
of sulfated oil by boiling the sample with sulfuric acid and
with oleic acid at elevated temperatures liberating volatile
determining the acidity of the reaction mixture.This method is
acids, or glycerin, diethylene glycol, xylene, or other com-
applicable only to oils that split off their combined SO upon
pounds of similar volatility.
boiling with mineral acids and that do not contain compounds
that cannot be accurately titrated in water solution with methyl
11. Apparatus orange as the indicator.
11.1 The apparatus required consists of a glass-stoppered
16. Apparatus
weighing flask, a glass beaker, and a suitable thermometer.
16.1 The apparatus required consists of a glass flask pro-
11.1.1 Weighing Flasks—Any suitable glass-stoppered
videdwithaglassstopperandanaircondenser.Theconnection
weighing flask of 10 to 15-mL capacity.
between the flask and the condenser shall be a ground joint.
11.1.2 Beaker—A Griffin low-form glass beaker with an
Perforated glass beads shall be used to prevent bumping.
approximatecapacityof150mLandadiameterofabout5cm.
16.1.1 Flask—An Erlenmeyer flask (Fig. 2) made of a
11.1.3 Heat Source—The source of heat may be either an
borosilicate glass, having a capacity of approximately 300 mL
electrichotplatewithorwithoutasbestospaperorboardcover,
and provided with a glass stopper.
or an open flame under a suitable asbestos board and a wire
16.1.2 Condenser—The condenser required consists of a
gauze (to spread the heat).
glass tube, 915 mm (36 in.) in length, and 8 mm ( ⁄16 in.) in
11.1.4 Thermometer, graduated from 90 to 150°C, about 3
outside diameter. The lower end of the tube shall be flared and
in. in length, and substantially constructed.
ground to fit the mouth of the Erlenmeyer flask.
16.1.3 Glass Beads—Perforated glass beads, made of
12. Reagents
chemically-resistant glass, approximately 4 mm ( ⁄32 in.) in
12.1 Desiccating Agent—Any suitable desiccating agent
may be used.
NOTE 1—Recent investigations seem to indicate that calcium chloride
is unreliable as a laboratory desiccating agent.
12.2 Oleic Acid.
13. Procedure
13.1 Weigh approximately5gof oleic acid into the beaker
andinsertthethermometer.Heattheoleicacidgradually,while
stirring with the thermometer, until the temperature reaches
130°C.Placethebeakerinanovenat105to110°Cfor15min,
coolinadesiccator,andweigh.Repeattheheatingoverthehot
plate and in the oven until two successive weighings differ by
less than 1.5 mg.
13.2 Placeabout6gofthesampleintheweighingflaskand
determine the weight accurately. Transfer the sample to the
beaker (containing the oleic acid and the thermometer) and
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
FIG. 2 Apparatus for Determination of Organically Combined
equivalent to the moisture in the sample. Sulfuric Anhydride, Method A
D500 – 95 (2003)
diameter. Before using, the glass beads shall be boiled thor- bumping. The volume of H SO added shall be sufficient to
2 4
oughly in several portions of water or until the wash water neutralize the total alkalinity, A, of the sample plus 25 mL in
reacts neutral to methyl orange indicator. excess. Regulate the heating so that the solution boils rather
vigorously but with very little evaporation taking place.At the
17. Reagents
end of the heating period allow the contents to cool, wash the
condenser with a spray of water from a wash bottle, and
17.1 Ethyl Ether.
disconnectthecondenser.Add30gofNaCl,25mLofether,50
17.2 Methyl Orange Indicator Solution (1 g/L)—Dissolve
mL of water, and 5 drops of indicator solution and titrate the
0.1 g of methyl orange in 100 mL of water.
solution with 1 N NaOH solution to the same end point as in
17.3 Sodium Chloride (NaCl), solid.
the total alkalinity titration, 18.1.1. During the titration stopper
17.4 Sodium Hydroxide, Standard Solution (1 N)—
the flask frequently and shake the contents of the flask
Accurately prepare and standardize a 1 N sodium hydroxide
thoroughly. Drain the burets for 3 min before readings are
(NaOH) solution. Express the strength or concentration of the
taken.
solution as milligrams of KOH per millilitre; 1 mL of 1 N
NaOH solution is equivalent to 56.1 mg of KOH.
NOTE 2—Reservethetitratedsolutionforthesubsequentdetermination
17.5 Sodium Hydroxide, Standard Solution (0.5 N)—
of total desulfated fatty matter (Sections 29-32).
Accurately prepare and standardize a 0.5 N NaOH solution.
18.1.2.1 Make a b
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.