ASTM E611-08(2015)e1

Standard Test Methods for Low Concentrations of Diethlyene Glycol in Ethylene Glycol by Gas Chromatography (Withdrawn 2020)

SIGNIFICANCE AND USE
3.1 Either test method may be used to determine the concentrations of diethylene glycol in ethylene glycol. The concentrations of the components are obtained by a normalization technique, based on the assumption that all components are eluted under the conditions used. If all components should not be eluted, the calculated concentrations will be erroneously high, with the major component showing the most significant absolute error. Since water is not detected by these procedures, the results are on a water-free basis. Water may be determined in accordance with the applicable sections of Test Methods E202 and the gas chromatographic results corrected for the water concentration.  
3.2 Both test methods are currently in industrial use. Test Method A is the simpler of the two test methods because it does not require the preparation of derivatives prior to gas chromatographic analysis. The results obtained by Test Method A are slightly more accurate than those obtained by Test Method B. With respect to precision there is no significant difference between the two test methods. Test Method B has been reported to be suitable also for the analysis of a wide variety of glycol ethers, but this use is beyond the scope of this standard.
SCOPE
1.1 These test methods are intended primarily for the analysis of mixtures of ethylene and diethylene glycols in which the diethylene glycol concentration is 0.1 % or less. Both test methods should be applicable to higher concentrations of diethylene glycol, but precision and bias estimates have been obtained only for 0.05 to 0.1 % diethylene glycol.
Note 1: Test Methods E202 describe another gas chromatographic test method applicable to mixtures of ethylene, diethylene, and triethylene glycols and mixtures of propylene, dipropylene, and tripropylene glycols in which one of the glycols is the principal component and the other two are present in concentrations of 0.1 to 1 % each.
Note 2: Test Method E2409 describes another gas chromatographic test method for the determination of glycol impurities in mono-, di-, tri- and tetraethylene glycol (MEG, DEG, TEG and TeEG) in the range of 5 to 3000 μg/g.  
1.2 The two test methods are given as follows:    
Sections  
Test Method A—Nonderivative Method  
5 to 13  
Test Method B—Derivative Method  
14 to 22  
1.3 Review the current Safety Data Sheets (SDS) for detailed information concerning toxicity, first aid procedures, and safety precautions for chemicals used in this standard.  
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard with the exception of foot-pound units for apparatus descriptions.  
1.5 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. For a specific warning statement, see 15.1.5.
WITHDRAWN RATIONALE
These test methods are intended primarily for the analysis of mixtures of ethylene and diethylene glycols in which the diethylene glycol concentration is 0.1 % or less. Both test methods should be applicable to higher concentrations of diethylene glycol, but precision and bias estimates have been obtained only for 0.05 to 0.1 % diethylene glycol.
Formerly under the jurisdiction of Committee D16 on Aromatic, Industrial, Specialty and Related Chemicals, these test methods were withdrawn in October 2020 and replaced by Test Method D8311 for Impurities in Monoethylene Glycol by Gas Chromatography with Normalization.1

General Information

• Status: Withdrawn
• Publication Date: 31-May-2015
• ICS: 71.080.60 - Alcohols. Ethers
• Technical Committee: D16 - Aromatic, Industrial, Specialty and Related Chemicals
• Drafting Committee: D16.14 - Alcohols & Glycols

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
´1
Designation: E611 − 08 (Reapproved 2015)
Standard Test Methods for
Low Concentrations of Diethlyene Glycol in Ethylene Glycol
by Gas Chromatography
This standard is issued under the fixed designation E611; 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.
ε NOTE—Editorial change was made in Subsection 1.3 in May 2016.
1. Scope* ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom-
1.1 These test methods are intended primarily for the
mendations issued by the World Trade Organization Technical
analysis of mixtures of ethylene and diethylene glycols in
Barriers to Trade (TBT) Committee.
which the diethylene glycol concentration is 0.1 % or less.
Both test methods should be applicable to higher concentra-
2. Referenced Documents
tions of diethylene glycol, but precision and bias estimates
2.1 ASTM Standards:
have been obtained only for 0.05 to 0.1 % diethylene glycol.
D1193 Specification for Reagent Water
NOTE1—TestMethodsE202describeanothergaschromatographictest
method applicable to mixtures of ethylene, diethylene, and triethylene E180 Practice for Determining the Precision of ASTM
glycols and mixtures of propylene, dipropylene, and tripropylene glycols
Methods for Analysis and Testing of Industrial and Spe-
in which one of the glycols is the principal component and the other two 3
cialty Chemicals (Withdrawn 2009)
are present in concentrations of 0.1 to 1 % each.
E202 Test Methods for Analysis of Ethylene Glycols and
NOTE 2—Test Method E2409 describes another gas chromatographic
Propylene Glycols
test method for the determination of glycol impurities in mono-, di-, tri-
and tetraethylene glycol (MEG, DEG, TEG and TeEG) in the range of 5
E2409 TestMethodforGlycolImpuritiesinMono-,Di-,Tri-
to 3000 µg/g.
and Tetraethylene Glycol and in Mono- and Dipropylene
Glycol(Gas Chromatographic Method)
1.2 The two test methods are given as follows:
2.2 Other Document:
Sections
Test Method A—Nonderivative Method 5 to 13
Manufacturers’ instruction manuals of gas chromatograph
Test Method B—Derivative Method 14 to 22
1.3 Review the current Safety Data Sheets (SDS) for de- 3. Significance and Use
tailed information concerning toxicity, first aid procedures, and
3.1 Either test method may be used to determine the
safety precautions for chemicals used in this standard.
concentrations of diethylene glycol in ethylene glycol. The
1.4 The values stated in SI units are to be regarded as concentrations of the components are obtained by a normal-
standard. No other units of measurement are included in this ization technique, based on the assumption that all components
standard with the exception of foot-pound units for apparatus are eluted under the conditions used. If all components should
descriptions. not be eluted, the calculated concentrations will be erroneously
high, with the major component showing the most significant
1.5 This standard does not purport to address all of the
absolute error. Since water is not detected by these procedures,
safety concerns, if any, associated with its use. It is the
the results are on a water-free basis. Water may be determined
responsibility of the user of this standard to establish appro-
in accordance with the applicable sections of Test Methods
priate safety, health, and environmental practices and deter-
E202 and the gas chromatographic results corrected for the
mine the applicability of regulatory limitations prior to use.
water concentration.
For a specific warning statement, see 15.1.5.
1.6 This international standard was developed in accor-
3.2 Both test methods are currently in industrial use. Test
dance with internationally recognized principles on standard- MethodAisthesimplerofthetwotestmethodsbecauseitdoes
1 2
These test methods are under the jurisdiction of ASTM Committee D16 on For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Aromatic, Industrial, Specialty and Related Chemicals and are the direct responsi- contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
bility of Subcommittee D16.14 on Alcohols & Glycols. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved June 1, 2015. Published June 2015. Originally the ASTM website.
approved in 1977. Last previous edition approved in 2008 as E611 – 08. DOI: The last approved version of this historical standard is referenced on
10.1520/E0611-08R15E01. www.astm.org.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
ϵ1
E611 − 08 (2015)
TABLE 1 Instrument Parameters, Method A—Nonderivative
A
Instrument Varian Aerograph. Model 204, equipped with flame ionization detectors
Strip-chart recorder 0-1 mV range
Chart speed ⁄2 in. (12.7 mm)/min
Column 50 in. (1270 mm) of ⁄16-in. (4.8-mm) outside diameter copper or
stainless steel tubing packed with 10 % polyethylene glycol.
20 000 molecular weight, on Chromosorb G, DMCS, 60/80 mesh
Column temperature 168°C
Carrier gas helium at 100 mL/min
Hydrogen flow rate 40 mL/min
Air flow rate 400 mL/min
Injection port temperature 210°C
Detector block temperature 168°C
Sample size 2µL
Injection time 28 s
A
The parameters in this table apply to a Varian Aerograph, Model 204, manufactured by Varian Div., 611 Hansen Way, Palo Alto, CA 94303. Any similar instrument may
be used for this method with appropriate modifications of the parameters.
not require the preparation of derivatives prior to gas chro- 6.1.1 Sample Injection Port, with heater characteristics
matographic analysis. The results obtained by Test Method A necessary for operation at 210°C.
are slightly more accurate than those obtained by Test Method 6.1.2 Column Oven, capable of isothermal operation at
B. With respect to precision there is no significant difference 168°C.
between the two test methods. Test Method B has been 6.1.3 Detector, of conventional flame ionization type, ca-
reported to be suitable also for the analysis of a wide variety of pable of operating at 168°C. A conventional thermal conduc-
glycol ethers, but this use is beyond the scope of this standard. tivity detector can be used, but sensitivity will be reduced and
water may be detected as a peak eluting with the pressure peak
4. Purity of Reagents
due to sample injection, depending upon the concentration of
water. The precision and bias statements in Section 13 are for
4.1 Reagent grade chemicals shall be used in all tests.
flame ionization detectors.
Unless otherwise indicated, it is intended that all reagents shall
6.1.4 Recorder, 0 to 1-mV range, that 1-s full scale deflec-
conform to the specifications of the Committee on Analytical
tion with a chart speed of approximately 1.3 cm/min or other
Reagents of the American Chemical Society, where such
convenient speed that will produce a satisfactory
specifications are available. Other grades may be used, pro-
chromatogram, and an attenuator switch to change the recorder
vided it is first ascertained that the reagent is of sufficiently
range as required to keep the chromatogram on scale.
high purity to permit its use without lessening the accuracy of
the determination.
NOTE 3—On instruments using electronic integration the attenuation
feature is not required.
4.2 Unless otherwise indicated, references to water shall be
understood to mean Type II or III reagent water conforming to
6.1.5 Column, 50 in. long, ⁄16 in. in outside diameter with a
Specification D1193.
wall thickness of 0.030 in. for copper or 0.020 in. for stainless
steel construction; packed with 10 % polyethylene glycol on
orange calcinated diatomite with dimethyldichlorosilane,
TEST METHOD A—NONDERIVATIVE METHOD
DMCS, 60/80 mesh.
6.1.6 Microsyringe, 10-µL capacity.
5. Summary of Test Method
6.1.7 Copper or Stainless Steel Tubing, ⁄16 in. in outside
5.1 The sample is injected into a gas chromatographic
diameter with a wall thickness of 0.030 in. for copper or 0.020
column. The components are separated as they pass through
in. for stainless steel.
the column with helium carrier gas, their presence in the
NOTE 4—The copper tubing should be sealed, refrigeration grade. If the
effluent is detected by a flame ionization detector, and recorded
seal has been broken, clean the copper tubing with an acetone wash and
as a chromatogram. The areas under the peaks due to the
dry with nitrogen before filling. Stainless steel tubing should be pre-
sample components are corrected by applying appropriate
washed with successive volumes of 10 % HCl, distilled water, acetone,
calibration factors to obtain the composition of the sample on
methylene chloride, and dried with nitrogen.
a weight percentage basis.
7. Reagents and Materials
6. Apparatus
7.1 Air, compressed.
6.1 Gas Chromatographic Instrument having the following
7.2 Orange Calcinated Diatomite with
minimal characteristics (see Table 1).
Dimethyldichlorosilane, 60/80 mesh.
7.3 Ethylene Glycol and Diethylene Glycol—See Section 9
Reagent Chemicals, American Chemical Society Specifications, Am. Chemical
for purity requirements.
Soc., Washington, DC. For suggestions on the testing of reagents not listed by the
American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH
7.4 Helium (He).
Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmacopeial Convention, Inc. (USP), Rockville, MD. 7.5 Hydrogen (H ).
ϵ1
E611 − 08 (2015)
7.6 Methylene Chloride (Dichloromethane) (CH Cl ). percentages in the standard mixture and the average area
2 2
percentages, calculate the factor for diethylene glycol as
7.7 Polyethylene Glycol, 20 000 molecular weight.
describedin11.1.1.Assumeacalibrationfactorofunityforthe
ethylene glycol in the base ethylene glycol standard mixture.
8. Preparation of Chromatographic Column
9.3 Calibration Method 2:
8.1 Dissolve 20 g of the polyethylene glycol in approxi-
9.3.1 For routine analyses, high-purity, commercial grades
mately 200 mLof CH Cl with gentle warming to aid solution.
2 2
of each glycol may be used. If the gas chromatographic
Add 180 g of orange calcinated diatamite with
analysis as described in Section 10 indicates that the concen-
dimethyldichlorosilane, DMCS, and sufficient CH Cl to form
2 2
tration of the ethylene glycol in the diethylene glycol to be
a slurry, and mix well, making certain that all particles are
added to the base ethylene glycol in the standard mixture does
wetted. Evaporate the CH Cl by heating gently over a steam
2 2
not exceed 0.2 area %, the concentration of the impurity is
bath in a fume hood until the mixture is dry. Frequent stirring
insignificantattheconcentrationlevelsincludedinthescopeof
of the slurry during the drying operation is necessary to obtain
this test method. The base ethylene glycol should contain less
a uniform coating. The use of a vacuum rotary evaporator will
than 0.05 area % diethylene glycol.
shorten the time required for drying.
9.3.2 Prepare a standard mixture of the glycols whose
8.2 Screen the dried packing through a 50-mesh (300-µm
composition approximates that of the glycol to be analyzed.
screen opening) and an 80-mesh (180-µm screen opening)
The composition of the standard mixture should be known to
screen to remove any lumps and fines. Fill a 127-cm section
the nearest 0.001 %. Correct the composition for any water
1.4-cm outside diameter copper or stainless steel tubing with
present using the equation in 11.2.4. Determine the water
the screened packing retained on the 80-mesh screen. Gently
content as described in the applicable section of Test Methods
vibrate the tubing during packing to ensure uniform packing.
E202. If the concentrations of the ethylene glycol in the
Useborosilicateglasswoolforplugsintheendsofthecolumn.
diethylene glycol added to the base ethylene glycol in the
Columns packed using vacuum or by blowing the packing into
standardmixturedoesnotexceed0.2area %,theconcentration
the tubing are generally unsatisfactory.
of the impurity is insignificant at the concentration levels
8.3 Conditionthecolumnpriortousebyplacingthecolumn
included in the scope of this method. The base ethylene glycol
in the chromatograph in accordance with 10.1, but do not
should contain less than 0.1 area % diethylene glycol.
connect the column to the detector. Pass helium through the
9.3.3 Obtain at least two chromatograms of the standard
column at 100 mL/min during the conditioning.
mixture and of the base ethylene glycol in accordance with
10.2 and calculate the average area percent for each of the
9. Calibration Factors
glycols present in accordance with 11.2.1. Do not include any
areas associated with the pressure peak in calculating the area
9.1 Inordertoobtainthecompositionofthesampleinterms
percentages.Usingthemasspercentofdiethyleneglycoladded
of mass percent, multiply the areas associated with the com-
to the ethylene glycol and the average area percentages for the
ponents by an appropriate calibration factor. These factors are
glycolscalculatethecalibrationfactorforthediethyleneglycol
obtained from mixtures of known composition, and should be
in accordance with 11.1.2. Assume the calibration factor of
determined for each apparatus. The calibration factors may be
unityfortheethyleneglycolinthebaseethyleneglycolandthe
obtained using standards prepared from “hearts cuts” from the
standard mixture.
distillation of each of the glycols, or from commercial grades
of each glycol as described in the following test methods. For
10. Procedure
highest accuracy, use glycols obtained from “hearts cuts.”
10.1 Mount the column in the chromatograph, and adjust
Check the calibration factors periodically or whenever there is
the operating conditions in accordance with the parameters
evidence of a change in the column or instrument.
given in Table 1 (see Note 5). Allow sufficient time for the
9.2 Calibration Method 1:
instrument to reach equilibrium as indicated by a stable base
9.2.1 Purify the commercial grade of each glycol needed by
line on the chart at the maximum sensitivity setting to be used.
careful fractionation in glass at reduced pressure, discarding
NOTE 5—The instrument parameters given in Table 1 were developed
the first 30 % and retaining the next 30 % as the “hearts cuts.”
for the indicated instrument. The use of other instruments will probably
Analyze these fractions as described in Section 1
...