Designation: D4768 − 11

Standard Test Method for

Analysis of 2,6-Ditertiary-Butyl Para-Cresol and 2,6-
Ditertiary-Butyl Phenol in Insulating Liquids by Gas
Chromatography1
This standard is issued under the fixed designation D4768; 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 4. Significance and Use

1.1 This test method covers the determination by gas 4.1 In new electrical insulating oil, this test method provides
chromatography of 2,6-ditertiary-butyl para-cresol and 2,6- a quantitative measure of the amounts of 2,6-ditertiary-butyl
ditertiary-butyl phenol in new and used insulating liquids at para-cresol and 2,6-ditertiary-butyl phenol that have been
concentrations up to 0.5 %. It includes the determination in added to the oil. In a used oil, the test measures the amount of
Type I and II insulating mineral oils as specified in Specifica- these inhibitors remaining in the oil. This test method is
tion D3487, but has also been used to measure these inhibitors suitable for manufacturing control, specification acceptance,
in other insulating liquids, such as esters and high fire-point and service evaluation.
hydrocarbons. 4.2 This test method is used to separate, identify, and
1.2 This standard does not purport to address all of the quantify the inhibitors with minimal interference and matrix
safety concerns, if any, associated with its use. It is the effects.
responsibility of the user of this standard to establish appro- 4.3 This test method has also been used successfully to
priate safety and health practices and determine the applica- determine the inhibitor concentrations in other insulating
bility of regulatory limitations prior to use. liquids such as esters and high-temperature hydrocarbons.
2. Referenced Documents
5. Apparatus
2.1 ASTM Standards:2
D923 Practices for Sampling Electrical Insulating Liquids 5.1 Gas Chromatograph, equipped with oven temperature
D3487 Specification for Mineral Insulating Oil Used in control constant to 1°C and with heated injector port.
Electrical Apparatus 5.1.1 Means to Record the Chromatogram, such as a pen
D5222 Specification for High Fire-Point Mineral Electrical recorder or a digital integrator to determine peak areas, is
Insulating Oils recommended. An automated sample injector may be used.
E260 Practice for Packed Column Gas Chromatography 5.2 Flame Ionization Detector, with appropriate hydrogen/
3. Summary of Test Method air gas flows, is preferred over a thermal conductivity detector
to provide maximum sensitivity.
3.1 The test specimen is placed onto a column containing
activated alumina and extracted to remove interfering sub- 5.3 Column, a suitable stainless steel or glass column
stances. The inhibitors are then eluted from the column with packed with a nonpolar silicone on an appropriate support or
suitable solvent and analyzed by gas chromatography. The equivalent capillary column.
inhibitor type and quantity are determined by comparison of NOTE 1—A 3 % OV-13 on 100/120 Mesh Supelcoport,4 1.83 m (6 ft)
each component with a working standard tested under similar long, 3.2 mm (0.125 in.) in outside diameter has been used successfully.
conditions. A SPB-14 30 m by 0.53 mm 1µm film column has also been used
successfully.
1
This test method is under the jurisdiction of ASTM Committee D27 on 5.3.1 Condition columns in accordance with manufacturer’s
Electrical Insulating Liquids and Gases and is the direct responsibility of Subcom- recommendations. Disconnect columns from detector prior to
mittee D27.03 on Analytical Tests. conditioning and reconnect after conditioning.
Current edition approved Aug. 1, 2011. Published September 2011. Originally
approved in 1988 as D4768 – 88. Last previous edition approved in 2003 as 5.4 Precision Syringe, glass, 10.0 µL.
D4768 – 03. DOI: 10.1520/D4768-11.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
3
Standards volume information, refer to the standard’s Document Summary page on Registered trademark of Ohio Valley Specialty Co.
4
the ASTM website. Registered trademark of Supelco, Inc.

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 D4768 − 11
5.5 Volumetric Glassware, appropriate for making dilutions. 7.3.1 Prepare a check standard containing 0.30 % (w/w)
5.6 Pipets, Pasteur, disposable, 146 by 7.5 mm. DBP and 0.30 % (w/w) DBPC in methanol. Dilute 0.25 mL of
check standard to 5.0 mL with methanol.
5.7 Analytical Balance. 7.3.2 Prepare a working standard in accordance with 7.4,
5.8 Automatic Pipetter, 1 mL calibrated, adjustable. using the 0.30 % (w/w) oil standard and the cleanup column
5.9 Oven, capable of maintaining a temperature of 325 6 whose efficiency is to be determined. Inject a volume of this
5°C for conditioning extraction columns. working standard into the gas chromatograph.
7.3.3 Inject a volume (equal to that used in 7.3.2) of the
5.10 Desiccator.
diluted check standard into the chromatograph using the same
6. Reagents and Materials chromatographic conditions used to analyze the working stan-
dards.
6.1 Purity of Reagents—Use reagent grade chemicals in all 7.3.4 Calculate the extraction efficiency for both DBP and
tests. Unless otherwise indicated, it is intended that all reagents DBPC as follows:
shall conform to the specifications of the Committee on
Analytical Reagents of the American Chemical Society, where AI
such specifications are available. 5 Other grades may be used, C I 3 W 0.30
3 100 5
AI 3 CC 3 VC 3 DC
5 extraction efficiency, %
provided it is first ascertained that the reagent is of sufficient AC A C 3 C I 3 W 0.30
purity to permit its use without lessening the accuracy of the CC 3 VC 3 DC
determination. where:
6.2 2,6-ditertiary-butyl phenol (DBP). AI = area (or height) of 0.30 % working standard,
6.3 2,6-ditertiary-butyl para-cresol (DBPC— )—Also 6 AC = area (or height) of 0.30 % check standard,
known as butylated hydroxytoluene (BHT). CI = known concentration of working standard,
CC = known concentration of check standard,
6.4 Glass Wool. DC = relative density (specific gravity) of methanol used
6.5 Aluminum Oxide (Alumina), acid powder, ACS, Brock- in check standard preparation, and
man Activity Grade 1, for chromatography. 7 W0.30 = weight of 0.30 % working standard as recorded in
7.4.1.
6.6 Hexane or Heptane, ACS reagent grade. VC = volume of check standard diluted to 5 mL in 7.3.1
6.7 Methanol, anhydrous, ACS reagent grade. (=0.25 mL)
6.8 Mineral Oil, inhibitor-free, transformer grade. 7.3.5 The minimum acceptable extraction efficiency is 70 %
for DBPC and 60 % for DBP. If the prepared columns do not
7. Calibration and Standardization achieve this level of efficiency, make and test new cleanup
7.1 Cleanup Column Preparation—Prepare cleanup col- columns until acceptable extraction efficiency is achieved. If
umns by inserting a small glass wool plug into the wide end of unable to obtain this, purchase a new lot of acid powder
a Pasteur pipet and tamping down to the narrow end. Fill alumina or verify that extraction columns are being activated
column to a height of approximately 35 mm (1.5 in.) with properly as in 7.1.
alumina and place a second glass wool plug on top of 7.4 Working Standard Preparation :
adsorbent. Activate column by placing in 325°C oven for a
7.4.1 Accurately weigh a cleanup column to 0.001 g. Pipet
minimum of 12 h. Cool in a desiccator prior to use. After
0.25 mL of the 0 % standard solution onto the top of the
column has cooled, purge column with approximately 2 mL
cleanup column. Weigh the cleanup column to 0.001 g. Record
hexane or heptane. Do not allow column to dry out prior to use.
the difference as W0 %. Repeat for the remaining standard
7.2 Standard Solution Preparation—Standard solutions are solutions utilizing different cleanup columns and recording
prepared containing both DBP and DBPC from inhibitor-free weights as W0.040 % , W0.080 %, W0.15 %, W0.30 % and W0.40 %,
mineral oil. Prepare oil solutions of 0, 0.040, 0.080, 0.15, 0.30, respectively.
and 0.40 % (w/w) of both DBP and DBPC. Determine the 7.4.2 To remove nonpolar interferences, wash the standard
relative density (specific gravity) of the oil used in standard solutions with approximately 5 mL of hexane or heptane,
solution preparation (DI) to 0.001. collecting the eluate in a waste container. Remove as much of
7.3 Column Extraction Effıciency—Verify by the following the solvent as possible by using pipet bulb pressure, but do not
procedure that the extraction efficiency of the prepared col- allow the column to dry out.
umns is acceptable. 7.4.3 Elute the inhibitors from the column with three
washes consisting of 1 mL of methanol each, collecting the
eluate in a clean 5 mL volumetric flask. Dilute to 5 mL with
5
Reagent Chemicals, American Chemical Society Specifications, American methanol and mix well. These are the working standards.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see “Reagent Chemicals and Standards,” 7.5 Working Standard Chromatography—Inject a volume of
by Joseph Rosin, D. Van Nostrand Co., Inc., New York, NY and the“ United States
the working standard solution into the equilibrated chromato-
Pharmacopeia.
6
Registered Trademark of Rhone-Poulenc, Inc. graph as described in Section 8. Recommended injection
7
Available from J.T. Baker Chemical Co., Phillipsburg, NJ 08865. volumes are 2 to 10 µL, depending on individual detector

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 D4768 − 11
response. Measure the response, Ax, (peak height or area in columns. The same “batch” should be interpreted to mean the
integrator counts) for each peak (excluding the solvent front). same lot number of alumina, preparation date, and conditioning
7.5.1 Perform separate linear regression analyses of the time.
responses resulting from both DBPC and DBP working stan- 9.1.2 To remove nonpolar interferences, wash the test speci-
dards by plotting Si versus area, Ax (or height) where: men with approximately 5 mL of hexane or heptane, collecting
Concentration of Working Standard, weight % the eluate in a waste container. Remove as much of the solvent
Si 5 as possible by using pipet bulb pressure, but do not allow the
Mass of Working Standard Used ~ 7.4.1!
column to dry out.
where: 9.1.3 Elute the inhibitor(s) from the column with three
Si = weight normalized, %. washes consisting of 1 mL of methanol each, collecting the
7.5.1.1 If the correlation coefficient for the regression analy- eluate in a clean 5-mL volumetric container. Dilute to 5 mL
ses (7.5.1) is less than 0.995, prepare new working standards volume with methanol and mix well.
(7.4), repeat the chromatographic measurements (7.5) and 9.2 Test Specimen Chromatography—Inject a volume of test
perform the data analysis (7.5.1) on the new results alone. If specimen into the chromatograph under the same chromato-
the situation is not improved, repeat the procedure using graphic conditions used to analyze the working standard(s).
working standards made from newly prepared standard solu-
tions (7.2). 10. Calculation
10.1 Identify the type(s) of inhibitors present by comparing
8. Chromatograph Operating Conditions the retention time obtained from the test specimens to those
8.1 General—The characteristics of individual chromato- obtained for the working standards.
graphs and columns differ. Choose particular operating condi- 10.2 Using the results of the regression analyses (7.5.1),
tions to give a complete separation and good quantification of determine the uncorrected weight percent (Cu) of the inhibitor
the peaks obtained. Temperatures and flow rates with which in the test specimens. Calculate the inhibitor content(s) as
satisfactory separations have been obtained are listed in 8.2 follows:
through 8.5.
C 5 Cu 3 Wx
8.2 Packed or Capillary Column Temperature—A column
oven temperature held isothermally at 150°C for 5 min where:
followed by temperature ramping at 20°C/min to 250°C and a C = weight of inhibitor in test specimen, %,
hold period at that temperature for 2 min gives satisfactory Cu = weight normalized, obtained from regression analy-
results. Although the inhibitors are resolved by the isothermal ses of working standards, %, and
portion of the run, higher temperatures are required to purge Wx = mass of 0.25 mL test specimen as recorded in 9.1.1.
the column of interfering substances for successive runs.
8.3 Detector Temperature—A detector temperature of 11. Report
300°C has been found to be satisfactory.
11.1 Report the following information:
8.4 Injector Port Temperature—An injector port tempera- 11.1.1 Type and amount of each inhibitor found, and
ture of 275°C has been found to be satisfactory. 11.1.2 Total amount of inhibitor as the sum of the individual
8.5 Carrier Gas—A carrier gas of high purity helium at a inhibitors found.
flow of 20 to 40 mL/min gives satisfactory results for packed
columns. 12. Precision and Bias
12.1 The single operator coefficient of variation has been
9. Procedure found not to exceed 11 % for inhibitor content between 0.06
9.1 Test Specimen Preparation: and 0.45 %. Therefore, the results of two tests conducted on the
9.1.1 Accurately weigh a cleanup column to 0.001 g. Pipet same sample by the same operator using the same equipment
0.25 mL of the test specimen onto the top of the cleanup should not differ from each other by more than 30.8 % of the
column. Weigh the cleanup column to 0.001 g. Record the average of the two tests.
difference as Wx.
9.1.1.1 Due to variances between different batches of alu- 13. Keywords
mina, care must be taken to prepare both the working standards 13.1 2,6-ditertiary-butyl para-cresol; 2,6-ditertiary-butyl
and test specimens by using the same batch of cleanup phenol; dbp; dbpc; inhibitor; mineral oil; transformer oil

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 D4768 − 11
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