Designation: D4251 − 89 (Reapproved 2009)

Standard Test Method for

Active Matter in Anionic Surfactants by Potentiometric
Titration1
This standard is issued under the fixed designation D4251; 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 3. Terminology
1.1 This test method describes a potentiometric titration 3.1 Definitions of Terms Specific to This Standard:
procedure for determining the anionic active matter in deter- 3.1.1 active matter—the organic surface-active material
gents. It is intended for the analysis of anionic surfactants such present in the detergent and defined in Terminology D459 as
as detergent range alkylbenzenesulfonates, α-olefin sulfonates, active ingredient of a synthetic detergent.
alcohol sulfates, and alcohol ethosulfates. It has not been tested
for surfactant formulations. 4. Summary of Test Method
4.1 A detergent sample containing active matter is titrated
1.2 The values stated in SI units are to be regarded as
potentiometrically in an aqueous medium with a standard
standard. No other units of measurement are included in this
solution of Hyamine 1622 using a nitrate ion-selective elec-
standard.
trode. The titration reaction involves the formation of a
1.3 This standard does not purport to address all of the complex between the cationic quaternary ammonium titrant
safety concerns, if any, associated with its use. It is the (Hyamine 1622) and the anionic surfactant which precipitates.
responsibility of the user of this standard to establish appro- The nitrate electrode probably responds to the concentration of
priate safety and health practices and determine the applica- unreacted anionic surfactant.
bility of regulatory limitations prior to use. Material Safety
Data Sheets are available for reagents and materials. Review 5. Significance and Use
them for hazards prior to usage. 5.1 Anionic surfactants are the most widely used of the
synthetic detergents. ASTM methods in current use for their
2. Referenced Documents determination involve two-phase aqueous/chloroform titrations
2.1 ASTM Standards:2 with the organic dyes methylene blue (Test Method D1681) or
D459 Terminology Relating to Soaps and Other Detergents disulphine blue/dimidium bromide (Test Method D3049) as
D1193 Specification for Reagent Water indicators. One advantage of the potentiometric method is that
D1681 Test Method for Synthetic Anionic Active Ingredient it eliminates the use of chloroform whose use is restricted for
in Detergents by Cationic Titration Procedure environmental and toxicological reasons.
D3049 Test Method for Synthetic Anionic Ingredient by 5.2 This test method is intended for use as described in 1.1.
Cationic Titration
E180 Practice for Determining the Precision of ASTM 6. Apparatus
Methods for Analysis and Testing of Industrial and Spe- 6.1 Potentiometric Titration Assembly, consisting of an
cialty Chemicals (Withdrawn 2009)3 automatic titrator (Metrohm E536 or equivalent) fitted with a
nitrate ion-selective electrode (Orion Model 93-07 Nitrate ISE,
or equivalent) and a Ag/AgCl reference electrode (Metrohm
1
This test method is under the jurisdiction of ASTM Committee D12 on Soaps EA 440 or equivalent) together with a buret assembly having a
and Other Detergents and is the direct responsibility of Subcommittee D12.12 on 5-mL buret (Metrohm E575) and 150-mL beaker. A TFE-
Analysis and Specifications of Soaps, Synthetics, Detergents and their Components. fluorocarbon star-head stirring bar can be used to provide
Current edition approved Oct. 1, 2009. Published December 2009. Originally
mixing and eliminate foaming during titration. Use of the
approved in 1983. Last previous edition approved in 2003 as D4251 – 89(2003).
DOI: 10.1520/D4251-89R09. Orion electrode with a Metrohm E536 requires an adapter
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or (Metrohm EA-1046/2).
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 NOTE 1—The conditioning of the electrode is essential for obtaining a
the ASTM website. good break in the titration curve. Conditioning new electrodes in 0.01 M
3
The last approved version of this historical standard is referenced on NaNO3 aqueous solution for 60 min (or more) prior to use is recom-
www.astm.org. mended. Condition previously used electrodes by using again for the

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

1
 D4251 − 89 (2009)
TABLE 1 Active Matter Content of Various Anionic Surfactants by B = normality of sodium lauryl sulfate, and
the Potentiometric Titration and Two-Phase Titration Methods
C = Hyamine solution consumed during titration, mL.
Active Matter Content, % weight
Potentiometric Titration Two-
Anionic Surfactant 9. Procedure
Orion Orion “Old” HNU Phase
NO3− (#1) NO3− (#2) NO3 − Titration
Sulframin AOS (alpha- 41.03 41.49 40.91 39.21A 9.1 Add to a 150-mL beaker a known weight of detergent
olefin sulfonate) 42.50 40.74 41.05 39.26 sample together with enough water to make 50 mL of solution
42.64 41.34 41.05
Sulframin 1298 (alkylaryl 94.15 96.26 94.91 95.12B
(Note 4). The solution should cover the sensing tips of the
sulfonate) 95.31 95.67 95.50 95.12 electrodes. Titrate initially by adding Hyamine solution at
94.73 96.26 94.91 approximately 0.5 mL/min while stirring constantly. As the
NEODOL® 25-3S (alcohol 58.12 57.94 57.75 58.19B
ethoxysulfate sodium 58.81 57.74 57.95 58.24 inflection point is approached, reduce the addition rate, and
salt) 58.12 57.94 57.95 continue titrating well past the inflection in the titration curve.
A
Methylene blue method. (Automatic titrators can be preset to automatically slow down
B
Mixed indicator method. the addition rate as the inflection point is approached.)
NOTE 4—To determine the amount of sample needed for an approxi-
mate 3.75-mL titration (0.15 meq) use the following equation:
titration of aqueous sodium lauryl sulfate with Hyamine.
NOTE 2—Other electrodes (for example a calomel electrode) are ~ 0.015! M
W5 (3)
suitable as the reference electrode provided they give a stable reference ~D!
potential during the titration. Reference electrodes having a ceramic or an
asbestos junction tend to clog with use. Therefore, a ground-glass sleeve where:
electrode (such as the Metrohm EA 440) is suggested. W = weight of sample to be taken for analysis, g,
M = average equivalent weight of the anionic active matter present,
7. Reagents and
D = approximate concentration of anionic active matter expected,
7.1 Hyamine 1622, diisobutylphenoxyethoxyethyl dimethyl weight %.
benzyl ammonium chloride.
9.1.1 To obtain accurate weights of sample, it is convenient
7.2 Sodium Lauryl Sulfate, primary standard (Note 3). to make up an aqueous solution (for example 250 mL) and take
NOTE 3—Sodium lauryl sulfate must be analyzed for purity according an aliquot corresponding to 0.15 meq of active matter.
to the Reagent section of Test Method D3049, before using as a primary 9.1.2 The electrode should be cleaned between each titra-
standard. tion. A satisfactory procedure is to first rinse it with water, then
7.3 Water, type III reagent water conforming to Specifica- with alcohol (ethyl alcohol) (Note 5) and again with water
tion D1193. followed by wiping the surface with a Kimwipe.
8. Preparation of Standard Reagents NOTE 5—The electrode can be quickly washed with ethyl alcohol when
followed immediately by a water rinse. Prolonged contact of the electrode
8.1 Sodium Lauryl Sulfate Solution, 4 × 10−2 N—Weigh with alcohol or other organic solvent can cause failure of the electrode
accurately 11.5 6 0.5 g of sodium lauryl sulfate to 0.1 mg; membrane.
dissolve in water and dilute to a final volume of 1 L. Calculate 9.2 Graphically select the inflection point of the curve on
the normality of the solution with the following equation: the recorder chart. Typical titration curves of several anionic
~ W !~ P ! surfactants are shown in Fig. 1.
Normality of sodium lauryl sulfate 5 (1)
~ 288.38!~ 100!
where: 10. Calculation
P = purity of the sodium lauryl sulfate, weight %, and 10.1 Calculate the anionic active matter content of the
W = weight of sodium lauryl sulfate, g. sample as follows:
8.1.1 Keep the solution no longer than 1 month before ~ V !~ N !~ M !
Anionic Active Matter, % w 5 (4)
making a fresh solution. ~ 10!~ W !
8.2 Hyamine 1622 Solution, 4 × 10−2 N—Dissolve 18 6 0.5 where:
g of Hyamine 1622 in deionized water. Transfer to a 1-L V = Hyamine 1622 solution consumed in titration, mL,
volumetric flask. Add 0.4 mL of 50 % NaOH and dilute to N = normality of Hyamine,
volume with water. Standardize following the same procedure W = weight of sample g, and
described for the sample titration using 5 mL of the sodium M = average equivalent weight of the anionic active matter
lauryl sulfate solution. Calculate the normality of the Hyamine present.
solution as follows:
10.2 Calculate the milliequivalents of active matter per 100
~ A !~ B ! g sample as follows:
Normality of Hyamine 1622 5 (2)
~C!
~ V !~ N !~ 100!
meq Active Matter/100 g 5 (5)
where: ~W!
A = sodium lauryl sulfate solution used, mL,
where V, N, and W are as listed previously.

2
 D4251 − 89 (2009)

FIG. 1 Potentiometric Titration Curves of Various Anionic Surfactants versus 0.03757 N Hyamine 1622 Using the Orion Model 93-07 Ni-
trate ISE

11. Precision considered suspect (95 % confidence level) if they differ by

11.1 The following criteria should be used to judge the more than 4.5 weight % relative.
acceptability of the results (Note 6):4,5 11.1.3 Checking Limits for Duplicates—Report the weight
11.1.1 Repeatability (Single Analyst)—The standard devia- % active matter of the sample to the nearest 0.1 weight %.
tion of results (each the average of duplicates), obtained by the Duplicate runs that agree within 1.8 weight % relative are
same analyst on different days, has been estimated to be 0.66 acceptable for averaging (95 % confidence level).
weight % relative at 28 df. Two such averages should be
considered suspect (95 % confidence level) if they differ by NOTE 6—The precision data were derived from results of the coopera-
tive tests by eight laboratories on the following surfactants (equivalent
more than 1.9 weight % relative. weights in parenthesis): sodium lauryl sulfate (302), alcohol ethoxysulfate
11.1.2 Reproducibility (multilaboratory)—The standard de- ammonium salt (434), α-olefin sulfonate (325), alkylaryl sulfonic acid
viation of results (each the average of duplicates), obtained to (318).
be 1.3 weight % relative at 6 df. Two such averages should be
12. Keywords
4
A research report supporting the precision statements is on file at ASTM 12.1 active matter; anionic surfactants; titration
International Headquarters. Request RR: RR:D12-1003.
5
The statistical analysis was performed in accordance with Practice E180 for
developing precision estimates.

3
 D4251 − 89 (2009)
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