ASTM D4337-89(2003)
(Test Method)Standard Test Methods for Analysis of Linear Detergent Alkylates
Standard Test Methods for Analysis of Linear Detergent Alkylates
SIGNIFICANCE AND USE
These test methods are suitable for setting specifications on linear detergent alkylates and for quality control where these alkylates are manufactured or are used in a manufacturing process.
The gas chromatography test is useful in identifying linear detergent alkylates produced by the various manufacturing processes and for determining the applicability of a linear detergent alkylate to a particular end use. Test conditions have been optimized for resolution of the C-9 to C-15 linear detergent alkylates and the presence of higher or lower chain lengths will be readily apparent but may produce erroneous results. The tetralin structures have not been sufficiently identified to allow determination of tetralins, and small unidentified components are reported as tetralins and unidentifieds.
Some linear detergent alkylates use a manufacturing process with an organic chloride as a precursor. This test may be used to ensure that the chloride content of the alkylate is not excessive for a particular end use.
The platinum-cobalt color test is useful in determining that the color of the linear detergent alkylate will not contribute to the color of the end use product.
The refractive index and specific gravity tests are possible aids in the identification of linear detergent alkylates and in evaluating alkylates for gross contaminants.
The water test is suitable for determining that linear detergent alkylates do not contain amounts of water deleterious to further processing.
FIG. 1 Typical Gas Chromatic Scan of an Alkylate
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: SectionComposition by Gas Chromatography7-15Chlorides16-27Color28-30Refractive Index31-33Specific Gravity34-36Water37-39
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
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:D4337–89(Reapproved 2003)
Standard Test Methods for
Analysis of Linear Detergent Alkylates
This standard is issued under the fixed designation D4337; 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 D1193 Specification for Reagent Water
D1209 Test Method for Color of Clear Liquids (Platinum-
1.1 These test methods cover chemical and physical tests
Cobalt Scale)
applicable to linear detergent alkylates, evaluating those prop-
D1218 Test Method for Refractive Index and Refractive
ertieswhichcharacterizelineardetergentalkylateswithrespect
Dispersion of Hydrocarbon Liquids
to its suitability for desired uses.
D1364 Test Method for Water in Volatile Solvents (Karl
NOTE 1—Linear detergent alkylates comprises linear alkylbenzenes
Fischer Reagent Titration Method)
prepared by varying processes of varying linear alkyl chain length. The
E180 Practice for Determining the Precision of ASTM
alkylate is sulfonated for surfactant use, the largest application being in
Methods for Analysis and Testing of Industrial and Spe-
detergent products. Careful control of linear detergent alkylate character-
cialty Chemicals
istics is desired; during sulfonation, variations of the sulfonate can occur
that may result in either desirable or undesirable end-use properties.
3. Significance and Use
1.2 The test methods appear as follows:
3.1 These test methods are suitable for setting specifications
Section
on linear detergent alkylates and for quality control where
Composition by Gas Chromatography 7-15
Chlorides 16-27 these alkylates are manufactured or are used in a manufactur-
Color 28-30
ing process.
Refractive Index 31-33
3.2 The gas chromatography test is useful in identifying
Specific Gravity 34-36
Water 37-39
linear detergent alkylates produced by the various manufactur-
ing processes and for determining the applicability of a linear
1.3 This standard does not purport to address all of the
detergent alkylate to a particular end use. Test conditions have
safety concerns, if any, associated with its use. It is the
been optimized for resolution of the C-9 to C-15 linear
responsibility of the user of this standard to establish appro-
detergent alkylates and the presence of higher or lower chain
priate safety and health practices and determine the applica-
lengths will be readily apparent but may produce erroneous
bility of regulatory limitations prior to use. Material Safety
results. The tetralin structures have not been sufficiently
Data Sheets are available for reagents and materials. Review
identified to allow determination of tetralins, and small uni-
them for hazards prior to usage. See also Note 1 and Section
dentified components are reported as tetralins and unidenti-
21.
fieds.
3.3 Some linear detergent alkylates use a manufacturing
2. Referenced Documents
process with an organic chloride as a precursor. This test may
2.1 ASTM Standards:
be used to ensure that the chloride content of the alkylate is not
D270 Method of Sampling Petroleum and Petroleum Prod-
excessive for a particular end use.
ucts
3.4 The platinum-cobalt color test is useful in determining
D1122 Test Method for Density or Relative Density of
thatthecolorofthelineardetergentalkylatewillnotcontribute
Engine Coolant Concentrates and Engine Coolants ByThe
to the color of the end use product.
Hydrometer
3.5 The refractive index and specific gravity tests are
possible aids in the identification of linear detergent alkylates
These test methods are under the jurisdiction of ASTM Committee D12 on
and in evaluating alkylates for gross contaminants.
Soaps and other Detergents and are the direct responsibility of Subcommittee
3.6 The water test is suitable for determining that linear
D12.12 on Analysis of Soaps and Synthetic Detergents.
Current edition approved May 26, 1989. Published June 1990. Originally
detergentalkylatesdonotcontainamountsofwaterdeleterious
published as D4337 – 84. Last previous edition D4337 – 84a. DOI: 10.1520/D4337-
to further processing.
89R03.
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 Withdrawn. The last approved version of this historical standard is referenced
the ASTM website. on www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D4337–89 (2003)
FIG. 1 Typical Gas Chromatic Scan of an Alkylate
4. Purity of Reagents isomer distribution before sulfonation. The analyses of stocks
having a chain length distribution above or below the interval
4.1 Purity of Reagents—Reagent grade chemicals shall be
covered in this test method will require a different set of
used in all tests. Unless otherwise indicated, it is intended that
operating conditions. If water, extremely high boiling compo-
all reagents shall conform to the specifications of the Commit-
4 nents, or unusual impurities are present in the linear detergent
tee onAnalytical Reagents of theAmerican Chemical Society,
alkylate, this test would not necessarily detect them and may
where such specifications are available. Other grades may be
produce erroneous results.
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
8. Summary of Test Method
accuracy of the determination.
8.1 A sample is injected by means of a microsyringe into a
4.2 Unless otherwise indicated, references to water shall be
vaporizationchamberofagaschromatograph.Astreamsplitter
understood to meanType III water conforming to Specification
allows the majority of the sample to be vented into the
D1193.
atmosphere through a valve that is incorporated in the vapor-
5. Precautions izationchamber.Asmallportionofthesampleisthensweptby
thecarriergasintoacapillarycolumnthathasbeencoatedwith
5.1 Consult the latest OSHA regulations regarding all re-
5 a thin layer of the stationary phase. A hydrogen flame ioniza-
agents and materials used in these test methods.
tion detector provides a very sensitive means of detecting the
6. Sampling extremely small concentrations of separated vapor components
as they elute from the column. An electrometer-amplifier
6.1 Unless otherwise indicated in a specific test method,
converts the detector signal into a suitable signal that can be
sample the material in accordance with Method D270, with
recorded on a standard strip-chart recorder and integrated by a
special application of Sections 41 and 42 pertaining to indus-
suitable integration device. The concentrations of the compo-
trial aromatic hydrocarbons, Section 12 pertaining to Bottle or
nents are obtained by normalizing the integrated areas, based
Beaker Sampling, and Section 15 pertaining to Tap Sampling.
ontheassumptionthatallcomponentsofthemixtureareeluted
Samples must be taken and stored in amber, screw-cap, glass
under the conditions used.
bottles to protect them from light.
9. Apparatus
COMPOSITION BY GAS CHROMATOGRAPHY
9.1 Gas Chromatograph, with the following characteristics:
7. Scope
9.1.1 Sample Injection Port, operable at 250°C and contain-
7.1 The gas chromatography test was developed to allow ing a stream splitter capable of linearly splitting sample
determination of C-9 through C-15 linear detergent alkylate
injections up to 1000 to 1.
9.1.2 Column Oven, capable of temperature programming
from 120 to 165°C at a rate of 1 or 2°C per min.
Reagent Chemicals, American Chemical Society Specifications, American
9.1.3 Flame Ionization Detector, capable of operating at
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
300°C.
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
9.2 Recorder, 0 to 1 mv range with 0.1 second full scale
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
deflection.
MD.
5 9.3 Integration Device, capable of accurately measuring
Available from Occupational Safety and Health Review Commission, 1825 K
Street, Washington, DC 20006. areas of up to 250 components.
D4337–89 (2003)
9.4 Column, 150 ft (45.7 m) by 0.01 in. (0.25 mm) inside 1 min after the injection of the sample, but it must always be
diameter stainless steel wall; open tubular capillary column closed at exactly the same time after injection.
coated with phenyl methyl silicone DC-550 or other column 12.5 Compare the sample chromatogram with the standard
that will perform required separation as indicated in Fig. 1. chromatogram (Fig. 1) and from the retention times of the
9.5 Syringe, 10-µL capacity with fixed 2-in. (5.1 cm) components identify all straight chain alkyl benzene isomers.
needle. Label all peaks whose identity has been established. Many
unidentified minor peaks will appear as minor constituents of
10. Reagents
the sample and may be attributed to tetralin structures. Include
10.1 Carrier Gas, high-purity nitrogen. these peaks in the calculations and report in a pooled percent-
10.2 Hydrogen, 99.996 mol % pure.
age as tetralins and unknowns.
10.3 Compressed Air.
13. Calculations
11. Calibration
13.1 Calculate the percentage for each component by divid-
11.1 Nocalibrationorcorrectionfactorsarenecessaryasthe
ing the area of each component by the total area of all
response of the flame ionization detector is essentially constant
components and multiplying by 100.
for aromatic hydrocarbons. The individual peak area percent-
13.2 Calculate the total 2-phenyl isomer by summing to-
ages may be regarded as the actual weight percent in the
gether the 2-phenyl isomers for all chain lengths.
sample.
13.3 Calculate the chain length distribution by summing
together all percentages for the identified linear alkyl benzene
12. Procedure
isomers of each chain length.
12.1 Adjust the chromatograph to the following conditions:
13.4 Calculate lights (components eluting before C alkyl
Column temperature, °C (Note 2) 120 programmed to 160 at 1 to 2°C
benzene) by summing together the percentages of all the
per min
components eluting before 5-phenyldecane.
Injection port temperature, °C 250
13.5 Calculate heavies (components eluting after C alkyl
Detector temperature, °C 300
Carrier gas pressure, lbf 60
benzene) by summing together all the percentages of the
Sample size (Note 3), µL 0.5 to 1
components eluting after 2-phenyltetradecane.
Chart speed, cm/min 1
Hydrogen flow (Note 4), mL/min 30 13.6 Calculate tetralins and unknowns by summing together
Air flow (Note 4), mL/min 240
the percentages of all unidentified peaks eluting between the
Range X1
5-phenyldecane peak and the 2-phenyltetradecane peak.
Attenuator setting X4
13.7 Determine the average molecular weight by assuming
Splitter (Note 3) 1000/1
the tetralins and unknowns to have a molecular weight of 244.
NOTE 2—These conditions should give adequate separation. It may be
Theaveragemolecularweightiscalculatedtothethirddecimal
necessarytoadjustconditionsslightlytomeettheseparationcriteriaofthe
sample chromatogram (Fig. 1), depending upon the performance of the place using the following equation:
capillary column.
Average molecular weight 5 [1002~lights (1)
NOTE 3—Sample size and splitter ratio should be adjusted to obtain a
1 heavies!#/[~( C isomers/218!
peak height of 10 to 15 mV for the largest components. 10
NOTE 4—Hydrogen and air flows should be adjusted to give maximum
1 ~( C isomers/232! 1 ~( C isomers/246!
11 12
detector sensitivity. See instructions in instrument instruction manual.
1 ~( C isomers/260! 1 ~( C isomers/274!
13 14
12.2 When a new column is installed, leak-test the plumb-
1 ~( tetralins 1 unknowns/244!#
ing connections by applying the operating carrier gas pressure.
The air and hydrogen connections to the detector should be
14. Report
leak tested periodically. In particular, the hydrogen supply
14.1 Report the components and average molecular weight
should be leak-tested at the cylinder each time the cylinder is
as specified in Table 1. Duplicate runs that agree within the
changed, due to the hazardous nature of hydrogen gas.
checking limits shown in Table 1 are acceptable for averaging
12.3 Wet and rinse the syringe with the sample and draw an
(95 % confidence level).
excessofliquidintothesyringebarrel.Exercisecautionthatall
air bubbles are excluded from the liquid in the syringe.
15. Precision and Bias
Carefully depress the plunger until the exact amount of liquid
15.1 The following criteria should be used for judging the
desired is contained in the syringe.
12.4 Open the split valve and quickly pierce the septum, acceptability of results:
15.1.1 Repeatability (Single Analyst)— The standard devia-
thrusting the needle of the syringe completely into the inlet. In
the same motion quickly and completely depress the plunger. tion of results (each the average of duplicates), obtained by the
same analyst on different days, has been estimated to be the
Immediately withdraw the syringe and start the column oven
temperature program sequence. The split valve may be closed value shown in Table 1 with the indicated degrees of freedom.
Two such results should be considered suspect (95 % confi-
dence level) if they differ by more than the values in Table 1.
Capillary column, Part 009-0354, available from Perkin-Elmer Corporation,
15.1.2 Reproducibility (Multilaboratory)— The standard
Norwalk, CT, has been found satisfactory.
deviation of results (each the average of duplicates), obtained
Microsyringe No. 701, available from Hamilton Co., P. O. Box 307, Whittier,
CA, has been found satisfactory. by analysts in different laboratories, has been estimated to be
D4337–89 (2003)
TABLE 1 Composition by Gas Chromatography Precision Values
Repeatability Reproducibility
Level, Report To, Checking
95 % Confi- 95 % Confi-
Component
Standard Degrees of Standard Degrees of
Area % Area % Limits
dence dence
Deviation Freedom Deviation Freedom
Interval Interval
Lights 0–1 0.01 0.14 0.053 46 0.15 0.099 7 0.33
Total C-10 Isomers 0–1 0.01 0.08 0.021 13 0.06 0.138 6 0.44
5–30 0.1 0.8 0.27 26 0.8 0.37 6 1.3
Total C-11 Isomers 0–3 0.1 0.3 0.07 13 0.2 0.26 6 0.9
20–40 0.1 1.9 0.65 27 1.9 1.05 6 3.6
Total C-12 Isomers 10–45 0.1 1.3 0.34 40 1.0 0.84 6 2.9
Total C-13 Isomers 0–15 0.1 1.1 0.26 26 0.8 0.72 6 2.5
40–60 0.1 2.3 0.40 14 1.2 1.60 6 5.5
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