Designation: D 2668 – 07
Standard Test Method for
2,6-di-tert-Butyl-p-Cresol and 2,6-di-tert-Butyl Phenol in Electrical
Insulating Oil by Infrared Absorption1
This standard is issued under the fixed designation D 2668; 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.
1. Scope* duces pronounced increases in absorbance at 2.72 µm (3650
1.1 This test method covers the determination of the weight cm−1), and 11.63 µm (860 cm−1). 2,6 ditertiary-butyl phenol
percent of 2,6-ditertiary-butyl paracresol (DBPC) and 2,6- produces pronounced increases in absorbance at 2.72 µm (3650
ditertiary-butyl phenol (DBP) in new or used electrical insu- cm−1) and 13.42 µm (745 cm−1).
lating oil in concentrations up to 0.5 % by measuring its 3.3 When making this test on other than a highly oxidized
absorbance at the specified wavelengths in the infrared spec- oil or when using a double-beam spectrophotometer, it has
trum. been found convenient to obtain the spectrum between 2.5 µm
1.2 This standard does not purport to address all of the (4000 cm−1) and 2.9 µm (3450 cm−1) because the instrument is
safety concerns, if any, associated with its use. It is the compensated for the presence of moisture and the band is not
responsibility of the user of this standard to establish appro- influenced by intermolecular forces (associations). However,
priate safety and health practices and determine the applica- when testing a highly oxidized oil or when using a single-beam
bility of regulatory limitations prior to use. instrument better results may be obtained if the scan is made
between 10.90 µm (918 cm−1) and 14.00 µm (714 cm−1).
2. Referenced Documents 3.4 Increased absorption at 11.63 µm (860 cm−1) or 13.42
2.1 ASTM Standards: 2 µm (745 cm−1) or both, will identify the inhibitor as 2,6-
D 923 Practices for Sampling Electrical Insulating Liquids ditertiary-butyl paracresol or 2,6-ditertiary-butyl phenol re-
D 2144 Practices for Examination of Electrical Insulating spectively (Note 1).
Oils by Infrared Absorption NOTE 1—The absorbance at 745 cm−1 for 2,6-ditertiary-butyl phenol
D 3487 Specification for Mineral Insulating Oil Used in and at 860 cm−1 for 2,6-ditertiary-butyl paracresol for equal concentra-
Electrical Apparatus tions will be in the approximate ratio of 2.6 to 1.
3. Significance and Use 4. Apparatus
3.1 The quantitative determination of 2,6-ditertiary-butyl 4.1 With equipment description referring to compliance, the
paracresol and 2,6-ditertiary-butyl phenol in a new electrical equipment shall be in accordance with Section 6 of Test
insulating oil measures the amount of this material that has Methods D 2144. Accordingly, the use of Fourier-transform
been added to the oil as protection against oxidation. In a used rapid scan infrared (FTIR) spectrophotometers is permitted by
oil it measures the amount remaining after oxidation has reference to that test method.
reduced its concentration. The test is also suitable for manu-
facturing control and specification acceptance. 5. Sampling
3.2 When an infrared spectrum is obtained of an electrical 5.1 Obtain the sample in accordance with Practices D 923.
insulating oil inhibited with either of these compounds there is
6. Calibration and Standardization
an increase in absorbance of the spectrum at several wave-
lengths (or wavenumbers). 2,6 ditertiary-butyl paracresol pro- 6.1 When the manufacturer of the oil is known and the base
oil is available, use it to prepare the standards. For oils of
unknown origin, use base oils which meet the requirements of
Specification D 3487. Some base oils may provide a better
1
This test method is under the jurisdiction of ASTM Committee D27 on match than others and therefore it is desirable to have several
Electrical Insulating Liquids and Gases and is the direct responsibility of Subcom-
mittee D27.03 on Analytical Tests. available.
Current edition approved Dec. 1, 2007. Published January 2008. Originally 6.2 Prepare standards containing between 0.05 and 0.4
approved in 1967. Last previous edition approved in 2002 as D 2668 – 02e1 . weight percent of 2,6-ditertiary-butyl paracresol or 2,6-
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
ditertiary-butyl phenol dissolved in an uninhibited base oil.
Standards volume information, refer to the standard’s Document Summary page on Alternatively, the range of prepared standards may be in-
the ASTM website. creased to 0.5 weight percent if certain oils to be investigated
*A Summary of Changes section appears at the end of this standard.
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D 2668 – 07
are believed to contain greater amounts of inhibitor. Obtain a
spectrum, at the desired band, of each standard in accordance
with Test Methods D 2144. Cells with a standard path length of
0.3 to 1.0 mm are recommended. Other path lengths may be
found more suitable for different instruments or particular
wave lengths. Other sample path lengths may be used provided
the instrument sensitivity can be adjusted to compensate for
this change. The dip in the curve for the inhibited oil should
provide a distinctive increase in the absorbance at the critical
wavelength or frequency (Note 3). Repeat the procedure on
each of the standards making at least three scans on each
standard. (See Note 2) Record all settings of the spectropho-
tometer used in obtaining the respective spectra (Note 4).
NOTE 2—The current method precision is based on manually deter-
mined results where exactly three scans were determined for each
standard. Newer instruments are capable of automatically performing
scans much more rapidly, which can reduce the variability of results
determined. In such cases, it is recommended that the number of scans be
increased to statistically compensate for any outliers. Laboratories will
need to determine the minimum number of scans that should be used in
their instrument standardization and test specimen analyses to satisfy their
testing needs.
NOTE 3—Where desired, a chart having a non-linear wavelength scale
as the abscissa may be used.
NOTE 4—In making these tests, transmission-scaled charts may be
used, but in this case special rulers and nomographs or logarithmic tables
will be necessary for determining the intensity measurements. Alterna-
tively, instrument software capable of recording all settings of the
spectrophotometer used in obtaining the respective spectra, may be used.
FIG. 1 Spectrum of an Electrical Insulating Oil Inhibited with 2,6-
6.3 The quantitative determination is made from the follow- Ditertiary-Butyl
ing equation which is derived from Beer’s law: Paracresol Showing Location Points Ao and A
Absorbance 5 A 2 Ao
where:
Ao = absorbance units of base oil, and ating a standard calibration curve, follow manufacturer’s
A = absorbance units of oil containing 2,6-ditertiary-butyl instructions. Perform at least three scans for each standard
paracresol or 2,6-ditertiary-butyl phenol. analyzed across the calibration range of interest (see Note 2).
6.4 Manual Plotting Routine for Generating Calibration Develop a calibration curve which has a minimum correlation
Curve—Designate the point of maximum absorbance of the value of 0.99 to ensure the linearity of the calibration curve.
absorbance band as Point A. Draw a tangent to the spectrum 6.5 When frequent determinations are made on a routine
curve and a second line through Point A perpendicular to the basis, periodic checks of one or more standards are recom-
absorbance lines, as shown in Fig. 1. Designate the intersection mended, since the characteristics of electronics components in
of these two lines as Point Ao. Read the values of absorbance spectrophotometers change with time. If the absorbance of the
at these points on the charts of the three scans made on each standards differ from the calibration curve by more than the
test specimen to the nearest 0.001 absorbance unit (with the aid limits given in 8.2, a new curve should be obtained. Some
of a reading glass) and subtract the values of Ao from those of laboratories have developed tighter limits than these. A new
A. When the average of the three values for each of the curve should also be obtained whenever there is a change in
specially prepared test specimens is plotted against the con- operating conditions, such as a change in light source, scan
centration, a straight line is obtained. The best straight line speed, and so forth.
through the calibration data points should be drawn or deter-
NOTE 5—It is recommended that the solutions of known concentration
mined by linear regression analysis. This is the calibration be stored in amber-colored bottles for a period not to exceed one year in
curve from which the unknown concentration of the 2,6- order to facilitate a quick check of the characteristics of the spectropho-
ditertiary-butyl paracresol or 2,6-ditertiary-butyl phenol in a tometer in relation to the calibration curve.
test specimen may be determined. One such calibration curve
is shown as Fig. 2. Fig. 3 and Fig. 4 illustrate sections of 7. Procedure
differential scans. Figs. 5-7 show FTIR scans of uninhibited, a 7.1 Using the quantitative scan mode, make at least three
similar oil with 0.55 % DBPC and the resulting FTIR differ- scans (see Note 2) of the test specimen on which the determi-
ential scan. nation of the 2,6-ditertiary-butyl paracresol or 2,6-ditertiary-
6.4.1 Automatic Plotting Routine for Generating Calibra- butyl phenol content is to be made, at the desired band. Do this
tion Curve—For instruments capable of automatically gener- in accordance with Test Methods D 2144, except that cells
2
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D 2668 – 07
FIG. 2 Calibration Curve for Determining the Percent by Weight of 2,6-Ditertiary-Butyl
Paracresol in Electrical Insulating Oil
FIG. 3 Section of Differential Scan-A
having path lengths as specified in 6.2 are preferred. Use the specimen performed manually or the average of the same
same cell that was used in obtaining the spectra for the number of scans used to standardize the instrument for the test
calibration curve. For the Differential Method, fill the reference specimen, if performed automatically.
cell with an appropriate base oil free of oxidation inhibitors. 7.3 Manually Determined Results—Read the values of ab-
Use a spectrophotometer which meets the requirements speci- sorbance at points Ao and A on each of the three spectra to the
fied in Section 6 of Test Methods D 2144 and instrumental nearest 0.001 absorbance unit; obtain the differences and
conditions identical to those used in obtaining the spectra for
average them. Using this average value, determine the concen-
the calibration curve. In particular, it should be noted that
tration from the calibration curve.
Fourier-transform rapid scan infrared spectrophotometers may
also be used and in some cases are preferred for the measure- 7.4 Automatically Determined Results—Using the average
ment. value of the absorbance difference between A and Ao that is
7.2 For routine tests, a single scan of the test specimen is determined automatically by the instrument for the same
adequate as long as the instrument is capable of meeting the number of scans performed on the test specimen as for the
criteria of 8.2 using single scans to replace average values. For standards, determine the concentration of the test specimen
referee purposes, use the average of three scans of the test from the calibration curve.
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D 2668 – 07
FIG. 4 Section of Differential Scan-B
FIG. 5 Example of a FTIR Scan of an Uninhibited Transformer Oil
8. Precision and Bias 8.3 Reproducibility—The difference between two determi-
8.1 Checking Limits of Range (A − Ao)—Determine the nations for DBPC and DBP, each obtained from the average of
highest and lowest values of A − Ao resulting from the three or three scans determined manually, obtained by different opera-
more scans and subtract one from the other. If the resulting tors in different laboratories on identical test material would, in
quantity exceeds 0.010, reject the results as excessively vari- the long run, in the normal and correct operation of the test
able and repeat the test. method, exceed the value of 0.04 % by only one case in twenty.
8.2 Repeatability—The difference between two determina- 8.4 No statement is made about bias of this test method for
tions for DBPC and DBP, each obtained from the average of measuring ditertiary-butyl paracresol or ditertiary-butyl phenol
three scans determined manually, obtained by the same opera- as it has not been determined.
tor with the same apparatus under constant operating condi-
tions on identical test material would, in the long run, in the 9. Keywords
normal and correct operation of the test method, exceed the 9.1 2,6-ditertiary-butyl paracresol; 2,6-ditertiary-butyl phe-
value of 0.04 % by only one case in twenty. nol; electrical insulating oil; infrared absorption
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D 2668 – 07
FIG. 6 Example of a FTIR Scan on a Transformer Oil with 0.55 % DBPC
FIG. 7 Example of the Differential Scan Showing 0.542 % WT % DBPC Inhibitor
SUMMARY OF CHANGES
Committee D27 has identified the location of selected changes to this standard since the last issue
(D 2668–02e1) that may impact the use of this standard.
(1) The absorption band for DBP has been changed from 750 (2) FTIR references and Figs. 5-7 were added.
cm-1(13.33 µm) to 745 cm-1(13.42 µm).
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D 2668 – 07
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