ASTM D4337-89(1995)e1
(Test Method)Standard Test Methods for Analysis of Linear Detergent Alkylates
Standard Test Methods for Analysis of Linear Detergent Alkylates
SCOPE
1.1 These test methods cover chemical and physical tests applicable to linear detergent alkylates, evaluating those properties which characterize linear detergent alkylates with respect to its suitability for desired uses. Note 1-Linear detergent alkylates comprises linear alkylbenzenes prepared by varying processes of varying linear alkyl chain length. The alkylate is sulfonated for surfactant use, the largest application being in detergent products. Careful control of linear detergent alkylate characteristics is desired; during sulfonation, variations of the sulfonate can occur that may result in either desirable or undesirable end-use properties.
1.2 The test methods appear as follows: Section Composition by Gas Chromatography 7-15 Chlorides 16-27 Color 28-30 Refractive Index 31-33 Specific Gravity 34-36 Water 37-39
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. See also Note 1 and Section 21.
General Information
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Standards Content (Sample)
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e1
Designation: D 4337 – 89 (Reapproved 1995)
Standard Test Methods for
Analysis of Linear Detergent Alkylates
This standard is issued under the fixed designation D 4337; 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 1209 Test Method for Color of Clear Liquids (Platinum-
Cobalt Scale)
1.1 These test methods cover chemical and physical tests
D 1218 Test Method for Refractive Index and Refractive
applicable to linear detergent alkylates, evaluating those prop-
Dispersion of Hydrocarbon Liquids
erties which characterize linear detergent alkylates with respect
D 1364 Test Method for Water in Volatile Solvents (Fischer
to its suitability for desired uses.
Reagent Titration Method)
NOTE 1—Linear detergent alkylates comprises linear alkylbenzenes
E 180 Practice for Determining the Precision of ASTM
prepared by varying processes of varying linear alkyl chain length. The
Methods for Analysis and Testing of Industrial Chemicals
alkylate is sulfonated for surfactant use, the largest application being in
detergent products. Careful control of linear detergent alkylate character-
3. Significance and Use
istics is desired; during sulfonation, variations of the sulfonate can occur
3.1 These test methods are suitable for setting specifications
that may result in either desirable or undesirable end-use properties.
on linear detergent alkylates and for quality control where
1.2 The test methods appear as follows:
these alkylates are manufactured or are used in a manufactur-
Section
ing process.
Composition by Gas Chromatography 7-15
Chlorides 16-27 3.2 The gas chromatography test is useful in identifying
Color 28-30
linear detergent alkylates produced by the various manufactur-
Refractive Index 31-33
ing processes and for determining the applicability of a linear
Specific Gravity 34-36
Water 37-39
detergent alkylate to a particular end use. Test conditions have
been optimized for resolution of the C-9 to C-15 linear
1.3 This standard does not purport to address all of the
detergent alkylates and the presence of higher or lower chain
safety concerns, if any, associated with its use. It is the
lengths will be readily apparent but may produce erroneous
responsibility of the user of this standard to establish appro-
results. The tetralin structures have not been sufficiently
priate safety and health practices and determine the applica-
identified to allow determination of tetralins, and small uni-
bility of regulatory limitations prior to use. Material Safety
dentified components are reported as tetralins and unidenti-
Data Sheets are available for reagents and materials. Review
fieds.
them for hazards prior to usage. See also Note 1 and Section
3.3 Some linear detergent alkylates use a manufacturing
21.
process with an organic chloride as a precursor. This test may
be used to ensure that the chloride content of the alkylate is not
2. Referenced Documents
excessive for a particular end use.
2.1 ASTM Standards:
3.4 The platinum-cobalt color test is useful in determining
D 270 Method of Sampling Petroleum and Petroleum Prod-
that the color of the linear detergent alkylate will not contribute
ucts
to the color of the end use product.
D 1122 Test Method for Specific Gravity of Engine Coolant
3.5 The refractive index and specific gravity tests are
Concentrates and Engine Coolants by the Hydrometer
4 possible aids in the identification of linear detergent alkylates
D 1193 Specification for Reagent Water
and in evaluating alkylates for gross contaminants.
3.6 The water test is suitable for determining that linear
detergent alkylates do not contain amounts of water deleterious
These test methods are under the jurisdiction of ASTM Committee D-12 on to further processing.
Soaps and other Detergents and are the direct responsibility of Subcommittee
D12.12on Analysis of Soaps and Synthetic Detergents.
4. Purity of Reagents
Current edition approved May 26, 1989. Published June 1990. Originally
4.1 Purity of Reagents—Reagent grade chemicals shall be
published as D 4337 – 84. Last previous edition D 4337 – 84a.
Discontinued, see 1984 Annual Book of ASTM Standards, Vol 05.01.
Annual Book of ASTM Standards, Vol 15.05.
Annual Book of ASTM Standards, Vol 06.04.
Annual Book of ASTM Standards, Vol 11.01.
Annual Book of ASTM Standards, Vol 05.01.
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 4337
FIG. 1 Typical Gas Chromatic Scan of an Alkylate
used in all tests. Unless otherwise indicated, it is intended that alkylate, this test would not necessarily detect them and may
all reagents shall conform to the specifications of the Commit- produce erroneous results.
tee on Analytical Reagents of the American Chemical Society,
8. Summary of Test Method
where such specifications are available. Other grades may be
used, provided it is first ascertained that the reagent is of
8.1 A sample is injected by means of a microsyringe into a
sufficiently high purity to permit its use without lessening the
vaporization chamber of a gas chromatograph. A stream splitter
accuracy of the determination.
allows the majority of the sample to be vented into the
4.2 Unless otherwise indicated, references to water shall be
atmosphere through a valve that is incorporated in the vapor-
understood to mean Type III water conforming to Specification
ization chamber. A small portion of the sample is then swept by
D 1193.
the carrier gas into a capillary column that has been coated with
a thin layer of the stationary phase. A hydrogen flame ioniza-
5. Precautions
tion detector provides a very sensitive means of detecting the
5.1 Consult the latest OSHA regulations regarding all re-
extremely small concentrations of separated vapor components
agents and materials used in these test methods.
as they elute from the column. An electrometer-amplifier
converts the detector signal into a suitable signal that can be
6. Sampling
recorded on a standard strip-chart recorder and integrated by a
6.1 Unless otherwise indicated in a specific test method,
suitable integration device. The concentrations of the compo-
sample the material in accordance with Method D 270, with
nents are obtained by normalizing the integrated areas, based
special application of Sections 41 and 42 pertaining to indus-
on the assumption that all components of the mixture are eluted
trial aromatic hydrocarbons, Section 12 pertaining to Bottle or
under the conditions used.
Beaker Sampling, and Section 15 pertaining to Tap Sampling.
9. Apparatus
Samples must be taken and stored in amber, screw-cap, glass
bottles to protect them from light.
9.1 Gas Chromatograph, with the following characteristics:
9.1.1 Sample Injection Port, operable at 250°C and contain-
COMPOSITION BY GAS CHROMATOGRAPHY
ing a stream splitter capable of linearly splitting sample
injections up to 1000 to 1.
7. Scope
9.1.2 Column Oven, capable of temperature programming
7.1 The gas chromatography test was developed to allow
from 120 to 165°C at a rate of 1 or 2°C per min.
determination of C-9 through C-15 linear detergent alkylate
9.1.3 Flame Ionization Detector, capable of operating at
isomer distribution before sulfonation. The analyses of stocks
300°C.
having a chain length distribution above or below the interval
9.2 Recorder, 0 to 1 mv range with 0.1 second full scale
covered in this test method will require a different set of
deflection.
operating conditions. If water, extremely high boiling compo-
9.3 Integration Device, capable of accurately measuring
nents, or unusual impurities are present in the linear detergent
areas of up to 250 components.
9.4 Column, 150 ft (45.7 m) by 0.01 in. (0.25 mm) inside
diameter stainless steel wall; open tubular capillary column
Reagent Chemicals, American Chemical Society Specifications, American
coated with phenyl methyl silicone DC-550 or other column
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
that will perform required separation as indicated in Fig. 1.
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
MD.
8 9
Available from Occupational Safety and Health Review Commission, 1825 K Capillary column, Part 009-0354, available from Perkin-Elmer Corporation,
Street, Washington, DC 20006. Norwalk, CT, has been found satisfactory.
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 4337
9.5 Syringe, 10-μL capacity with fixed 2-in. (5.1 cm) Label all peaks whose identity has been established. Many
needle. unidentified minor peaks will appear as minor constituents of
the sample and may be attributed to tetralin structures. Include
10. Reagents
these peaks in the calculations and report in a pooled percent-
age as tetralins and unknowns.
10.1 Carrier Gas, high-purity nitrogen.
10.2 Hydrogen, 99.996 mol % pure.
13. Calculations
10.3 Compressed Air.
13.1 Calculate the percentage for each component by divid-
ing the area of each component by the total area of all
11. Calibration
components and multiplying by 100.
11.1 No calibration or correction factors are necessary as the
13.2 Calculate the total 2-phenyl isomer by summing to-
response of the flame ionization detector is essentially constant
gether the 2-phenyl isomers for all chain lengths.
for aromatic hydrocarbons. The individual peak area percent-
13.3 Calculate the chain length distribution by summing
ages may be regarded as the actual weight percent in the
together all percentages for the identified linear alkyl benzene
sample.
isomers of each chain length.
13.4 Calculate lights (components eluting before C alkyl
12. Procedure
benzene) by summing together the percentages of all the
12.1 Adjust the chromatograph to the following conditions:
components eluting before 5-phenyldecane.
Column temperature, °C (Note 2) 120 programmed to 160 at 1 to 2°C
13.5 Calculate heavies (components eluting after C alkyl
per min
Injection port temperature, °C 250
benzene) by summing together all the percentages of the
Detector temperature, °C 300
components eluting after 2-phenyltetradecane.
Carrier gas pressure, lbf 60
13.6 Calculate tetralins and unknowns by summing together
Sample size (Note 3), μL 0.5 to 1
Chart speed, cm/min 1
the percentages of all unidentified peaks eluting between the
Hydrogen flow (Note 4), mL/min 30
5-phenyldecane peak and the 2-phenyltetradecane peak.
Air flow (Note 4), mL/min 240
13.7 Determine the average molecular weight by assuming
Range X1
Attenuator setting X4 the tetralins and unknowns to have a molecular weight of 244.
Splitter (Note 3) 1000/1
The average molecular weight is calculated to the third decimal
NOTE 2—These conditions should give adequate separation. It may be place using the following equation:
necessary to adjust conditions slightly to meet the separation criteria of the
Average molecular weight 5 @1002~lights (1)
sample chromatogram (Fig. 1), depending upon the performance of the
capillary column. 1 heavies!#/@~( C isomers/218!
NOTE 3—Sample size and splitter ratio should be adjusted to obtain a
1 ~( C isomers/232! 1 ~( C isomers/246!
11 12
peak height of 10 to 15 mV for the largest components.
1 ~( C isomers/260! 1 ~( C isomers/274!
NOTE 4—Hydrogen and air flows should be adjusted to give maximum 13 14
detector sensitivity. See instructions in instrument instruction manual.
1 ~( tetralins 1 unknowns/244!#
12.2 When a new column is installed, leak-test the plumb-
14. Report
ing connections by applying the operating carrier gas pressure.
14.1 Report the components and average molecular weight
The air and hydrogen connections to the detector should be
as specified in Table 1. Duplicate runs that agree within the
leak tested periodically. In particular, the hydrogen supply
checking limits shown in Table 1 are acceptable for averaging
should be leak-tested at the cylinder each time the cylinder is
(95 % confidence level).
changed, due to the hazardous nature of hydrogen gas.
12.3 Wet and rinse the syringe with the sample and draw an
15. Precision and Bias
excess of liquid into the syringe barrel. Exercise caution that all
15.1 The following criteria should be used for judging the
air bubbles are excluded from the liquid in the syringe.
acceptability of results:
Carefully depress the plunger until the exact amount of liquid
15.1.1 Repeatability (Single Analyst)— The standard devia-
desired is contained in the syringe.
tion of results (each the average of duplicates), obtained by the
12.4 Open the split valve and quickly pierce the septum,
same analyst on different days, has been estimated to be the
thrusting the needle of the syringe completely into the inlet. In
value shown in Table 1 with the indicated degrees of freedom.
the same motion quickly and completely depress the plunger.
Two such results should be considered suspect (95 % confi-
Immediately withdraw the syringe and start the column oven
dence level) if they differ by more than the values in Table 1.
temperature program sequence. The split valve may be closed
15.1.2 Reproducibility (Multilaboratory)— The standard
1 min after the injection of the sample, but it must always be
deviation of results (each the average of duplicates), obtained
closed at exactly the same time after injection.
by analysts in different laboratories, has been estimated to be
12.5 Compare the sample chromatogram with the standard
the value shown in Table 1 with the indicated degrees of
chromatogram (Fig. 1) and from the retention times of the
freedom. Two such results should be considered suspect (95 %
components identify all straight chain alkyl benzene isomers.
confidence level) if they differ by more than the values shown
in Table 1 (Note 5).
NOTE 5—The preceding precision estimates are based on an interlabo-
Microsyringe No. 701, available from Hamilton Co., P. O. Box 307, Whittier,
CA, has been found satisfactory. ratory study of six samples of linear detergent alkylates. A total of eight
...
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