ASTM D3673-89(2003)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation: D3673 – 89 (Reapproved 2003)
Standard Test Methods for
Chemical Analysis of Alpha Olefin Sulfonates
This standard is issued under the fixed designation D3673; 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 Reagents of the American Chemical Society, where such
specifications are available. Other grades may be used, pro-
1.1 These test methods cover the chemical analysis of alpha
vided it is first ascertained that the reagent is of sufficiently
olefin sulfonates. The analytical procedures appear in the
high purity to permit its use without lessening the accuracy of
following order:
the determination.
Sections
3.2 Unless otherwise indicated, references to water shall be
Moisture by the Distillation Method 4-8
Sodium Sulfate 9-14
understood to mean Type III reagent water conforming to
Neutral Oil 15-19
Specification D1193.
Chlorides Calculated as Sodium Chloride (NaCl) 20-24
Alkalinity 25-29
MOISTURE BY THE DISTILLATION
pH 30 and 31
Determination of Color 32-37
METHOD
Determination of Active Content by Methylene Blue Titration 38-47
4. Apparatus
1.2 This standard does not purport to address all of the
4.1 The apparatus required shall consist of a glass flask
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- heated by suitable means and provided with a reflux condenser
discharging into a trap and connected to the flask. The
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. For specific connections between the trap and the condenser and flask shall
beinterchangeablegroundjoints.Thetrapservestocollectand
precaution statement see 36.1. Material safety data sheets are
available for reagents and materials. Review them for hazards measure the condensed water and to return the solvent to the
prior to usage. flask.Asuitable assembly of the apparatus is illustrated in Fig.
1.
2. Referenced Documents
4.1.1 Flask, 1-L capacity, either the short-neck, round-
2.1 ASTM Standards:
bottom type, or the Erlenmeyer type.
D1172 Guide for pH of Aqueous Solutions of Soaps and 4.1.2 Heat Source—Either an oil bath (for example, stearic
Detergents acid or paraffin wax) or an electric heater provided with a
D1193 Specification for Reagent Water sliding rheostat or other means of heat control.
D1209 Test Method for Color of Clear Liquids (Platinum- 4.1.3 Condenser—A water-cooled glass reflux condenser
Cobalt Scale) (Fig. 1), having a jacket approximately 15 ⁄4 in. (400 mm) in
3 1
D3049 Test Method for Synthetic Anionic Ingredient by length, with an inner tube ⁄8 to ⁄2 in. (9.5 to 12.7 mm) in
Cationic Titration outside diameter, and not less than ⁄4 in. (6.35 mm) in inside
diameter. The end of the condenser to be inserted in the trap
3. Purity of Reagents
may be ground off at an angle of 30° from the vertical axis of
3.1 Reagent-grade chemicals shall be used in all tests. the condenser. When inserted into the trap, the tip of the
Unless otherwise indicated, it is intended that all reagents shall
condenser shall be about ⁄4 in. (7 mm) above the surface of the
conform to the specifications of the Committee on Analytical liquid in the trap after the distillation conditions have been
established. Fig. 1 shows a conventional sealed-in type of
condenser, but any other condenser fulfilling the detailed
requirements of this paragraph may be used.
These test methods are under the jurisdiction of ASTM Committee D12 on
Soaps and Other Detergents, and are the direct responsibility of Subcommittee
D12.12 on Analysis of Soaps and Synthetic Detergents.
Current edition approved May 26, 1989. Published July 1989. Originally
published as D3673 – 78. Last previous edition D3673 – 87. DOI: 10.1520/D3673- Reagent Chemicals, American Chemical Society Specifications, American
89R03. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
For referenced ASTM standards, visit the ASTM website, www.astm.org, or listed by the American Chemical Society, see Analar Standards for Laboratory
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Standards volume information, refer to the standard’s Document Summary page on and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
the ASTM website. MD.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D3673 – 89 (2003)
4.1.4.3 Trap, 25-mLcapacity, subdivided from 0 to 1 mLin
0.1-mL divisions and from 1 to 25 mL in 0.2-mL divisions.
NOTE 1—The condenser and trap should be thoroughly cleaned before
use.
5. Solvent
5.1 Xylene—Saturate xylene with water by shaking with a
small quantity of water and distill. Use the distillate for the
determination.
6. Procedure
6.1 Transfer to the 1000-mLflask (equipped with the size of
the trap specified in 4.1.4) an amount of sample according to
the percentage of moisture expected, as follows:
Weight of Sample
A
Moisture Expected, % to Be Used, g
0 to 5, incl 50 6 5
Over 5 to 17, incl 50 6 5
Over 17 to 30, incl 40 6 4
Over 30 to 50, incl 30 6 3
Over 50 to 70, incl 30 6 3
Over 70 to 85, incl 25 6 2
A
Weighed to the nearest 0.25 g.
Immediatelyaddabout250mLofxylene.Placeasmall,thin
sheet of long-fiber, chemical-resistant glass wool on the
surface of the xylene. The glass wool should be thoroughly
dried in the oven and held in the desiccator before use.
6.2 Connecttheflaskandreceivertothecondenserandpour
sufficient xylene down the condenser tube to cause a slight
overflowthroughthesidetube.Wraptheflaskandtubeleading
to the receiver with glass wool, so that refluxing will be under
better control.
6.3 Heat the oil bath with a gas burner or other source of
heat, or apply heat directly to the flask with an electric heater
and distill slowly.The rate at the start should be approximately
100 drops per minute. When the greater part of the water has
distilled over, increase the distillation rate to 200 drops per
minute until no more water is collected. Rinse during the
distillation with 5-mL portions of xylene to wash down any
FIG. 1 Assembly of Distillation Apparatus
moisture adhering to the walls of the condenser. The water in
the receiver may be made to separate from the xylene by using
4.1.4 Trap—For greatest accuracy several trap sizes are
aspiralcopperorNichrome wire.Movethewireupanddown
allowable, depending upon the percentage of moisture ex-
in the condenser occasionally, thus causing the water to settle
pected:
at the bottom of the receiver. Reflux for at least 2 h, and shut
Moisture Expected, % Size of Trap, mL
off the heat at the end of this period.
0to5,incl 5
Over 5 to 17, incl 10 NOTE 2—In especially difficult cases of boil-over, add 10 to 15 mL of
Over 17 to 30, incl 25
oleicacidbeforebeginningthedistillation.Washdownthecondenserwith
Over 30 to 50, incl 25
10 mLof xylene.Adjust the temperature of the distillate to 20°C and read
Over 50 to 70, incl 25
the volume of water.
Over 70 to 85, incl 25
Traps made of well-annealed glass, constructed essentially
7. Calculation
as shown in Fig. 1, and graduated to contain one of the
7.1 Calculate the percentage of moisture as follows:
following specified volumes at 20°C shall be used:
Moisture, % 5 [~V 3 0.998!/W] 3 100 (1)
4.1.4.1 Trap, 5-mL capacity, subdivided into 0.1-mL divi-
sions with each 1-mL line numbered (5 mL at top). The error
in any indicated capacity may not be greater than 0.05 mL.
4.1.4.2 Trap, 10-mLcapacity, subdivided from 0 to 1 mLin
Borosilicate glass has been found satisfactory for this purpose.
0.1-mL divisions and from 1 to 10 mL in 0.2-mL divisions. “Nichrome” is a trademark of the Driver-Harris Co.
D3673 – 89 (2003)
where W = grams of Na SO .
where:
2 4
10.8 Sulfonazo III Indicator Solution —Dissolve 0.1 g of
V = volume of water, mL at 20°C, and
Sulfonazo III in 100 mL of water. Pass the solution through a
W = weight of sample, g.
cation exchange column if it looks blue rather than lavender
8. Precision and Bias
when edge-lighted by a tungsten lamp.
8.1 Repeatability (Single Analyst)—The standard deviation 10.9 Filter Paper, smooth, hardened, ashless.
ofresults(eachtheaverageofduplicates)obtainedbythesame
11. Standardization
analyst on different days, has been estimated to be 0.16 %
absolute at 9 degrees of freedom.Two such averages should be
11.1 Pipet 5.0-mLaliquots of standard Na SO solution into
2 4
considered suspect (95 % confidence level) if they differ by each of two 50-mL beakers. Place stirring bars in each beaker.
more than 0.5 % absolute.
Add 20 mL of acetone, 2 drops of 1 N HCl, and 4 to 5 drops
8.2 Reproducibility(Multilaboratory)—The standard devia- of Sulfonazo III indicator solution to each beaker.
tion of results (each the average of duplicates) obtained by
11.2 Titrate each Na SO solution with Ba(ClO ) solution
2 4 4 2
analysts in different laboratories, has been estimated to be using a 10-mL buret. Stir the solution magnetically. Illuminate
0.47 % absolute at 8 degrees of freedom. Two such averages the solution horizontally with a small tungsten lamp at the side
should be considered suspect (95 % confidence level) if they of the beaker. Titrate slowly to a color change from lavender-
differ by more than 1.5 % absolute. pink to blue (about 0.3 mLof Ba(ClO ) solution is required to
4 2
8.3 Checking Limits for Duplicates—Report the moisture produce a good initial lavender color).
contentofthesampletothenearest0.01 %.Duplicaterunsthat 11.3 From each titration, calculate the normality of the
agree within 1.3 % are acceptable for averaging (95 % confi- Ba(ClO ) solution as follows. Average the values obtained.
4 2
dence level).
5 3N
Normality,N 5 (3)
V
SODIUM SULFATE
where:
9. Apparatus
N = normality of the Na SO solution, and
1 2 4
9.1 Beakers, 50 and 100-mL capacity.
V = millilitres of Ba(ClO ) solution required for 5-mL
4 2
9.2 Buret, 10-mL capacity, with 0.05-mL divisions.
aliquot of Na SO solution.
2 4
9.3 Volumetric Flasks, 50, 250, and 1000-mL capacity.
12. Procedure
9.4 Magnetic Stirrer, with TFE-fluorocarbon-coated stirring
bars.
12.1 Weigh a 2-g sample into a 100-mL beaker or a 50-mL
9.5 Transfer Pipet, 5-mL capacity.
flask. Record the weight to 61 mg.
9.6 Viewing Lamp—Small tungsten lamp or flashlight.
12.2 Place a stirring bar in the container. Add 25 mL of
water and stir until the sample is dissolved.
10. Reagents and Materials
12.3 Add a few drops of phenolphthalein indicator solution.
10.1 Acetone.
Add 0.1 N HCl until the solution is just acid. Do not
10.2 Barium Perchlorate Solution (0.02N)—Dissolve 3.4 g
over-acidify.
of anhydrous Ba(ClO ) in water and dilute the solution to 1 L.
12.4 Place the container in a cold-water bath (below 20°C)
4 2
10.3 2-Benzyl-2-thiopseudourea Hydrochloride Solution
on the magnetic stirrer. Add 10 mL of 2-benzyl-2-
—(7 %) —Dissolve 7 g in 100 mL of water. Prepare the
thiopseudourea hydrochloride at a fast drip through a buret
solution fresh daily.
with vigorous stirring. Do not whip the liquid into a foam.
10.4 HydrochloricAcid (1N)—Dilute83mLofhydrochlo-
12.5 Stir the solution for 15 min more in the cold bath.
ric acid (HCl, sp gr 1.19) to 1 L with water.
Remove the solution from the bath and let it settle for a few
10.5 Hydrochloric Acid (0.1 N)—Dilute 8.3 mL of HCl (sp
minutes at room temperature.
gr 1.19) to 1 L with water.
12.6 Filter the solution through filter paper into a 50-mL
10.6 Phenolphthalein Indicator Solution (10 g/L)—
volumetric flask. Wash the filter cake with water. Use the
Dissolve1gof phenolphthalein in 100 mL of 95 % ethanol.
washes to dilute the solution to volume.
10.7 SodiumSulfateSolution (0.02N)—Drytheanhydrous,
12.7 Pipet a 5-mL aliquot into a 50-mL beaker. Add 20 mL
reagent-grade salt (Na SO)for4hat 105°C. Weigh about
2 4 of acetone, 2 drops of 1 N HCl, and 4 to 5 drops of Sulfonazo
0.355 g of the dried salt into a 100-mL beaker. Record the
III indicator solution.
weight within 60.1 mg. Dissolve the salt water. Quantitatively
12.8 Titrate the solution slowly with 0.02 N Ba(ClO )
4 2
transfer the solution to a 250-mL volumetric flask and dilute it
solution. Use magnetic stirring. Illuminate the solution hori-
tovolumewithwater.Calculatethenormalityofthesolutionas
zontally with a small tungsten lamp at the side of the beaker.
follows:
Titratetoacolorchangefromlavender-pinktoabluecolorthat
persists for 1 min.
Normality,N 5 0.05632 3W (2)
NOTE 3—The titration should be between 1 and 5 mL. If the titration is
Supporting data are available from ASTM Headquarters, 100 Barr Harbor
Drive, West Conshohoken, PA 19428. Request D12-1002 and D12-1007.
7 8
Eastman Organic Chemical No. 2124 has been found satisfactory for this Sulfonazo III [3,6-bis-(o-sulfophenylazo)-4,5-dihydroxy-2,7-naphthalenedi-
purpose. sulfonic acid] is available from the Aldrich Chemical Co.
D3673 – 89 (2003)
greater than 5 mL, use a smaller aliquot of the sample and add water to
17. Procedure
bring the aqueous volume to 5 mL total. If the titration is less than 1 mL,
17.1 Introduce into a 250-mL Erlenmeyer flask sample
pipet a 10-mL aliquot into a 100-mL beaker and add 40 mL of acetone, 4
equivalent to 6 to8gof active matter, weighed to the nearest
drops of 1 N HCl, and 8 to 10 drops of Sulfonazo III indicator solution.
0.01 g.Add an equivalent volume of 1 + 1 ethanol-water. If, on
the addition of 2 drops of phenolphthalein indicator solution,
13. Calculation
the sample solution remains colorless, neutralize the sample
13.1 Calculate the concentration of Na SO as follows:
2 4
with 0.1 N NaOH solution to the appearance of the pink color.
355N 3V
17.2 Quantitatively transfer the neutralized solution to a
Na SO,wt% 5 (4)
2 4
A 3W
250-mLseparatory funnel, rinsing the flask, first with 10 mLof
water, followed by 10 mL of ethanol and then by 100 mL of
where:
1 + 1 ethanol-water.Add each rinsing to the separatory funnel.
N = normality of Ba(ClO ) solution,
2 4 2
Finally, rinse the flask with 30 mL of petroleum ether, using
V = volume of Ba(ClO ) solution, mL,
4 2
this rinsing to extract the alcoholic solution in the separatory
A = volume of aliquot, mL, and
W = weight of sample, g. funnel.
17.3 To achieve efficient extraction, shake the separatory
funnel vigorously for 1 min, venting it as necessary.Allow the
14. Precision and Bias
phase
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