750 J. Sep. Sci.

2012, 35, 750–757

Abdul Muttaleb Yousef Research Article

Jaber1
Nemr Ahmed Mehanna2
Abdalla Mahmoud Simultaneous liquid–liquid extraction of
Abulkibash1
dibenzyl disulfide, 2,6-di-tert-butyl-p-cresol,
1 Chemistry Department, King
Fahd University of Petroleum &
and 1,2,3-benzotriazole from power
Minerals , Dhahran, Saudi
Arabia
transformer oil prior to GC and HPLC
2 Industrial Support Services
Laboratories, Al-Bassam Group
determination
of Companies , Dammam, Saudi
Arabia 2,6-Di-tert-butyl-p-cresol (DBPC), dibenzyl disulfide (DBDS), and 1,2,3-benzotriazole (BTA)
are additives that may be found concomitantly in the oil matrix of power transformer.
Received June 09, 2011 DBPC and DBDS act as antioxidants while, BTA is a corrosion inhibitor that protects
Revised November 15, 2011 copper conductors inside the transformer unit from corrosion. A powerful analytical method
Accepted December 08, 2011 is, therefore, required to determine these additives at trace levels in the transformer oil.
This work describes a unique single liquid–liquid extraction pretreatment step prior to the
determination of the components by gas chromatography (GC) and high-performance liquid
chromatography (HPLC) techniques. The optimum volume ratio used in the pretreatment
step was determined as 5:2:5 for mineral oil/n-hexane/acetonitrile, respectively. Relatively,
the method is simple and quick with a minimal use of solvents. Analytical results indicate
that the method is relatively sensitive, accurate, and precise for each of the three components
in fresh and used mineral oil. The calibration curves for the three components demonstrate
a significant increase in sensitivities. Detection limits found were, 100 mg L−1 (0.01% w/v),
0.80 mg L−1 , and 2.04 mg L−1 for DBPC, DBDS, and BTA, respectively. The Student’s
t values determined at 95% confidence level indicate that there is no significant difference
between the experimental means obtained by this method and the standard method for each
component.

Keywords: BTA / Corrosive sulfur / DBDS / DBPC / Liquid–liquid extraction

DOI 10.1002/jssc.201100505

1 Introduction 2,6-Di-tert-butyl-p-cresol (DBPC) is a common and useful

primary antioxidant additive that is widely used as a radical
The chemical properties of the mineral insulating oil may trapping agent, thus preventing the degradation of the oil
change as a result of aging or other factors where the dete- [1]. 1,2,3-benzotriazole (BTA) is an additive used as a passi-
rioration products could destroy the insulating property of vator that inhibits the corrosion effects of the organic sulfur
the oil. Moreover, a reaction may occur between corrosive on copper conductors in the transformer unit. Also, many
sulfur compounds, when available in the oil, and the cop- mineral oils have been found to contain dibenzyl disulfide
per conductors inside the transformer unit to form copper (DBDS) [2] which is responsible for the formation of copper
sulfide that eventually deposits on the surface of the insulat- sulfide [3]. DBDS has been used as an antioxidant and as a
ing paper causing shorting faults between the turns of the stabilizer for petroleum distillates and polymers [4] and it has
electric transformer. Mineral insulating oil quality can be im- been found in many samples of the commercially available
proved by using specific additives that retard the deterioration insulating oils as an undeclared artificial antioxidant [5]. It
processes. has been found that BTA can compete with DBDS to form
a layer of stable copper complex [6, 7] on the copper surfaces
inside the transformer unit, thus, the corrosivity associated
with DBDS would be minimized. The resultant effect of these
additives depends primarily on their interrelated actions that
Correspondence: Professor Abdul Muttaleb Yousef Jaber, in turn depend on their concentrations and the operation
KFUPM, Chemistry Department, Dhahran 31261, Saudi Arabia conditions of the power transformer unit. Thus, it is of prime
E-mail: ajaber@philadelphia.edu.jo
importance to determine the concentration of each of these
Abbreviations: BTA, 1,2,3-benzotriazole; DBDS, dibenzyl additives in insulating oil to check its quality.
disulfide; DBPC, 2,6-di-tert-butyl-p-cresol; PCB, polychlori- Most standard methods and methods reported in the
nated biphenyles literature for the determination of oil additives required a


C 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.jss-journal.com
J. Sep. Sci. 2012, 35, 750–757 Sample Preparation 751

pretreatment separation step for each additive from the oil 2 Experimental
matrix prior to its determination by gas chromatography
(GC), or high-performance liquid chromatography (HPLC) 2.1 Equipment and materials
techniques. According to ASTM D 4768 [8], DBPC is sep-
arated by solid-phase extraction, SPE, using an alumina Shimadzu GC, Model 17A, equipped with an FID an ECD,
column prior to its determination by the GC/FID (flame AOC-201 auto injector, and DB-5 column of 30 m, 0.25 mm,
ionization detector) system. To avoid the lengthy sample pre- 1.00 ␮m was used for DBDS and DBPC detection. Agilent
treatment, ASTM D 2668 method has been developed for the HPLC, Model 1200, equipped with ultraviolet (UV) detec-
direct determination of DBPC by using the Fourier transform tor, auto-injector, and ZORBAX Eclipse XDB-C18 column of
infrared (FTIR) technique [9]. Also, DBPC was determined 4.6 × 150 mm, 5 ␮m was used for BTA detection. Screw cap
by HPLC [10], differential pulse voltammetry [11], and micel- glass tubes of 20 mL were used for the liquid–liquid extrac-
lar electrokinetic capillary chromatography [12] techniques tion. The cartridges used for solid phase extraction include:
where the SPE or liquid–liquid extraction pretreatment step silica cartridge (500 mg SampliQ) and alumina cartridge
was conducted prior to their determination. (AccuBond II Alumina N sorbents, with 50–200 ␮m parti-
The need for monitoring the passivator content in the cle size). A vacuum manifold for solid phase extraction from
insulating oil matrix has also been investigated [13]. The pas- Millipore was used.
sivator BTA has been determined using HPLC following an The chemicals used include: DBPC, internal standards
SPE pretreatment step for new and used mineral insulating diphenyl disulfide and diphenoxy benzene, DBDS, BTA
oils according to the IEC-60666 [14] and ASTM WK24216 [15] (Sigma Aldrich, St. Louis, MO, USA); fresh mineral insu-
standard methods. lating oil free of DBPC, DBDS, and BTA (a gift from the Gulf
ASTM D 1275 and IEC-62535 are standard methods, Chemical and Industrial Oils, Dammam, Saudi Arabia); ace-
mainly applied for the determination of organic sulfur com- tonitrile, methanol, and n-hexane (Merck, Kirkland, Québec,
pounds such as DBDS in mineral insulating oils [16–19]. The Canada). All chemicals used were of analytical reagent grade.
results obtained from these methods are interpreted qual- A stock solution of DBDS, DBPC, and BTA was prepared
itatively by visual evaluation of the copper corrosion using by dissolving accurately weighed samples of these materials
ASTM D 130 [20]. In conclusion, neither ASTM D 1275 nor in fresh mineral insulating oil then diluting each with oil as
IEC-62535 standard methods can detect any form of organic needed to give solutions of concentrations in ranges simi-
sulfur compounds if a metal passivator is present in the oil lar to those in mineral oil, namely, 10 000 mg L−1 (1.0% w/v)
matrix. The major challenge to detect DBDS in mineral insu- DBPC and 100 mg L−1 DBDS and BTA. Various working stan-
lating oil using GC is to separate DBDS signal from the oil dards of appropriate DBDS, DBPC, and BTA concentrations
matrix which requires a special pretreatment step. DBDS in were prepared from their stock solutions according to exper-
insulating oil was assessed quantitatively using SPE through imental needs. A stock solution of internal standard mixture
alumina cartridge followed by GC–MS (mass spectrometry) of 0.2% diphenoxy benzene and 5 mg L−1 diphenyl disul-
determination [21]. This method is reported to be highly se- fide was prepared in acetonitrile or methanol. The internal
lective for DBDS and can provide a quantitative conclusion. standards mixture was used for DBDS and DBPC detection
However, using benzene as a desorbent renders the method through GC–ECD–FID. No internal standard was used for
unpopular due to health hazard issues. Moreover, the SPE the determination of BTA using the HPLC method.
is a tedious procedure and adds an extra cost to the method
of analysis. Recently, International Electrotechnical Commis-
sion (IEC) proposed a method for DBDS determination [22] 2.2 Liquid–liquid extraction procedure
based on diluting the oil sample to about 20 times with a
solvent like isooctane prior to its determination by a GC– A 5-mL sample of mineral insulating oil containing DBPC,
ECD (electron capture detector) system. Although the dilution DBDS, and BTA was diluted with a certain volume of n-
helped the reduction of oil matrix from the chromatogram, hexane (between 2 and 5 mL) in a 20 mL screw cap glass
DBDS signal sensitivity was sacrificed due to the high dilu- tube and 5 mL acetonitrile or methanol were added to func-
tion of the oil sample solution. IEC recently issued a standard tion as an extractant for the three components simultane-
(IEC-60296) [23] that forces insulating oil manufacturers to ously. The mixture was shaken vigorously for about 10–15
provide with each oil shipment a document to certify that the s then centrifuged at 2000 rpm (revolutions per minute) for
product does not contain undeclared additives. 1 min.
This article investigates the efficiency of a single liquid– For the DBDS/DBPC determination, 2 mL of the acetoni-
liquid extraction pretreatment step using a nonpolar dilu- trile or the methanol layer was transferred into another tube
ent (n-hexane) for the oil sample and a polar solvent extrac- and mixed with 2 mL of the internal standard stock solution.
tant (acetonitrile or methanol). Thus, DBDS, DBPC, and BTA This mixture was stored for GC–ECD–FID injection.
components are extracted from fresh and in service mineral For the BTA determination, 1 mL of the acetonitrile or
insulating oil samples prior to their determination by either the methanol layer was transferred into another tube, 4 mL
GC or HPLC techniques. of deionized water was added to match the mobile phase


C 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.jss-journal.com
752 A. M. Y. Jaber et al. J. Sep. Sci. 2012, 35, 750–757

matrix (water/acetonitrile, 80:20, v/v). The mixture was fil- DBPC, BTA, and DBDS from a mineral insulating oil sample
tered through a 0.45-␮m syringe filter and stored for HPLC diluted with n-hexane. The layer comprising the three com-
injection. ponents was separated, mixed with internal standard when
necessary, then injected into the GC or HPLC system. The
chromatograms were recorded and the peak of each compo-
2.3 Solid phase extraction nent was used to assess its extraction efficiency. For the sake
of comparison, the known standard methods, ASTM D 4768,
Solid phase extraction trials were tested in this work according IEC-60666, and IEC-62697 standard methods were applied
to literature/standard procedures [8, 14, 21] with some mod- for the determination of DBPC, BTA, and DBDS. According
ifications (instead of their home made clean up columns, to these methods, GC and HPLC techniques were used for
readymade cartridges were used in this study) to examine the determination of DBPC and BTA, respectively, after solid
the efficiency of solid phase extraction and the GC or HPLC phase extraction pretreatment step; while DBDS was deter-
signal sensitivity when each of the three components are in- mined without a pretreatment step but with significant dilu-
dividually injected following the solid phase extraction step. tion with isooctane to minimize the oil matrix background
In all solid phase extraction trials, a mineral insulating oil interference on the GC chromatogram.
sample was diluted with n-hexane or n-heptane and eluted The chromatograms obtained after liquid–liquid extrac-
through an alumina or silica cartridge using an appropriate tion showed that the background signal associated with the
eluent. The sought component (DBDS or DBPC or BTA) was oil matrix was almost eliminated as in the case of literature
washed out from the cartridge using a desorbent that was methods in which solid phase extraction was used [8, 14, 21].
benzene in the case of DBDS and methanol in the case of However, the chromatographic peak of each of the three com-
DBPC and BTA. ponents was drastically enhanced in comparison with that
observed when determined by the standard methods men-
tioned above. The GC signal for DBPC increased almost
3 Results and discussion three times (Figs. 1a and 2) when liquid–liquid pretreatment
extraction step was used. The use of n-hexane in this liquid–
3.1 Assessment of the liquid–liquid extraction liquid extraction pretreatment has decreased the possibility
process for the oil matrix extraction in the extractant (acetonitrile or
methanol) phase. n-Hexane was used earlier as a diluent
The mineral insulating oil matrix usually introduces a high for edible oil samples when the synthetic phenolic antiox-
background effect that obscures the chromatographic signals idants were extracted by acetonitrile polar solvent prior to
of DBDS, DBPC, and BTA when determined by the GC or their determination by micellar electrokinetic capillary chro-
HPLC techniques. According to literature reports [8, 14, 21], matography [12]. The use of n-hexane as a cosolvent in the
SPE as a pretreatment step requires extensive dilution of the extraction was attributed to its role in decreasing the viscosity
oil sample, thus, the results obtained may suffer from low of the oil sample, thereby enhancing the contact between the
sensitivity and poor precision. Consequently, a liquid–liquid oil and acetonitrile phases. When the same liquid–liquid ex-
extraction step was introduced in this work and the results traction pretreatment step was carried out in the absence of
are compared with those obtained from the SPE step. n-hexane, the chromatogram showed a high background con-
In the preliminary liquid–liquid extraction trials, the tribution (Fig. 1b) indicating the presence of oil traces in the
extraction procedure was conducted using a liquid extrac- acetonitrile layer. However, when a sample of this acetonitrile
tant (acetonitrile or methanol) to extract, simultaneously, the layer was shaken with n-hexane (5:2, v/v), a chromatogram

Figure 1. GC–FID signal for mineral insulating oil containing 2000 mg L−1 (0.2%) DBPC after extraction with acetonitrile using (a) oil/n-
hexane/acetonitrile, 5:2:5 and (b) oil/acetonitrile, 5:5.


C 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.jss-journal.com
J. Sep. Sci. 2012, 35, 750–757 Sample Preparation 753

3.2 Optimizing of volume ratios in the liquid–liquid

extraction process

The focus of this work was to introduce a single, easy, and

efficient liquid–liquid extraction step with minimal use of sol-
vents where DBDS, DBPC, and BTA are extracted simultane-
ously from the oil matrix prior to their determination by GC
and HPLC techniques. The extraction efficiency was assessed
by varying the volume ratios: oil/oil diluent/extractant solvent
until the optimum ratio that produced the highest GC/HPLC
signal sensitivity was obtained; this would indicate the high-
est extraction efficiency. Two sets of oil/oil diluent/extractant
solvent volume ratios were studied. In one set the extrac-
Figure 2. GC/ECD signal for mineral insulating oil containing 50 tant solvent was 5 mL acetonitrile while in the other it was
mg L−1 DBDS after extraction with acetonitrile using oil/n-hexane/ 5 mL methanol. The components of each set were as follows:
acetonitrile, 5:2:5.
Y:X:5, where Y (mineral insulating oil) = 2 or 5 mL, and X
(n-hexane) = 2 or 5 mL. Thus, four combinations were pre-
pared for each extractant solvent. A series of solutions (a total
of four solutions for each extractant solvent) comprising vari-
similar to that of Fig. 1a was obtained where the background ous DBDS, DBPC, and BTA concentrations (1–100 mg L−1 for
has almost disappeared. The nonpolar n-hexane solvent may DBDS and BTA and 100–10 000 mg L−1 , i.e., 0.01–1% w/v for
compete with the acetonitrile extractant for the oil matrix, DBPC) dissolved in fresh mineral oil (Y mL) were prepared
thus, it minimizes the extraction of oil into the acetonitrile from each combination. The liquid–liquid extraction was car-
layer. The same argument holds for the solid phase extrac- ried out according to the procedure mentioned above, and a
tion or liquid–liquid extraction of BTA prior to its injection portion of each extract (acetonitrile or methanol layer) was
into the HPLC system. Though DBDS separation from the oil separated, mixed with the internal standard when needed,
matrix was not required when it was determined by the GC– and injected into the GC to determine DBDS, DBPC simul-
ECD system, according to the standard method IEC-62697, taneously where one line is passed into an ECD to determine
a significant dilution of the oil sample prior to GC–ECD de- DBDS while the other line is passed into an FID to deter-
termination was essential. This extensive dilution should be mine DBPC. Another portion of the extractant was injected
responsible for the low chromatographic peak sensitivity and into the HPLC to determine BTA. Furthermore, two more se-
consequently the high limit of detection (LOD) reported there ries of standard solutions were prepared comprising DBDS,
(≤5 mg L−1 ) [22]. DBPC, and BTA with the same range of concentrations but
These preliminary trials indicated that solid-phase extrac- dissolved in pure acetonitrile in one time and in methanol
tion requires various elution steps that may dilute the ana- in the other. Again, a portion of each of these sample solu-
lyte to be determined in the oil sample, thus, decreasing the tions was injected into the GC system and another portion
sensitivity and detection limit of the chromatographic sig- was injected into the HPLC system. Calibration curves were
nal. Furthermore, appreciable quantities of various solvents constructed for each of the three components (DBDS, DBPC,
and time will be consumed compared to the liquid–liquid and BTA) in each of the four series. The extraction efficiency
extraction pretreatment described in this work. For example, for each volume ratio was calculated as the ratio of the slope
according to the IEC-60666 standard method, BTA is deter- of the calibration curve constructed for solutions of a certain
mined in mineral insulating oil by SPE pretreatment where component prepared in this volume ratio to the slope of the
about 40 mL of pentane and 10 mL of methanol are used for calibration curve constructed for the same component in the
one oil sample, while for DBPC, about 6 mL of pentane with extractant solvent (acetonitrile or methanol) only. The extrac-
5 mL of methanol are required for one sample. Furthermore, tion efficiencies calculated as percent extraction are presented
according to the IEC-62697 standard method for the DBDS in Fig. 3.
determination, the oil sample is diluted 20 times with isooc- It is obvious from Fig. 3 that acetonitrile achieved bet-
tane. However, according to this work, only 2 mL hexane (as ter extraction efficiency than methanol for each of the three
diluent) and 5 mL acetonitrile (as extractant) are used for an components in all volume ratios, and the difference in percent
oil sample comprising the three components. Thus, all the extractability was more pronounced with DBDS. This differ-
three species are separated simultaneously from the matrix ence in extractability might be ascribed to the differences
of an oil sample using a single extraction step with only two in solubility of each of the three components in methanol
solvents and a total of 7 mL of solvents. The efficiency of and acetonitrile, thus, the significant difference in the case of
liquid–liquid extraction pretreatment step was assessed for DBDS might be attributed to its higher solubility in acetoni-
each of the three components to optimize the volumes of oil trile compared to that in methanol. Increasing the volume
sample and solvents that give the highest chromatographic of the oil diluent from 2 to 5 mL seems to be of little effect
peak. on the extraction efficiency except for DBPC. This increase


C 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.jss-journal.com
754 A. M. Y. Jaber et al. J. Sep. Sci. 2012, 35, 750–757

Figure 3. Extraction efficiencies for sev-

eral volume ratios (oil/oil diluent/extractant
solvent) using acetonitrile or methanol as
extractants.

caused a decrease in extraction efficiency of about 7–9% for DBDS, and 1–100 mg L−1 BTA solutions prepared in fresh
DBPC in acetonitrile or methanol, however, the decrease in mineral insulating oil and extracted by acetonitrile liquid–
extraction efficiency for the other two components were about liquid extraction using the optimum volume ratio followed
2–3%. This decrease may be attributed to the competition of by injection into the GC–ECD/FID and HPLC/UV systems
acetonitrile and n-hexane for each of the components. The under the optimum operational and instrumental conditions
dramatic increase in the extraction efficiency was observed [8, 14, 21]. Diphenoxy benzene and diphenyl disulfide inter-
when the volume of the oil sample was increased from 2 nal standards were used with DBPC and DBDS, respectively,
to 5 mL, however, the extractant volume was kept the same whereas BTA calibration curve was established using the ex-
(5 mL). Figure 3 shows that the highest extraction efficien- ternal standard calibration method. Although according to the
cies for the three components were achieved when the min- standard method, IEC-60666 [14], it is recommended that the
eral oil/oil diluent/extractant solvent was 5:2:5. Consequently HPLC–UV detector be set at 260–270 nm to measure the ab-
this volume ratio was recommended as the optimum value sorbance of BTA, it was set at 250 nm in this study, especially
for the liquid–liquid extraction step prior to GC and HPLC with used oil, to minimize the chromatographic interference
determination of the three components. The change in the of certain oxidation byproducts (furanic compounds such as
extraction efficiency may be ascribed mainly to the dilution 2-furaldehyde) that form in the oil as a result of oil and in-
factor that takes place when the components transfer from sulating paper degradation and overheating. The maximum
the oil sample into the extractant (acetonitrile or methanol) absorbance wavelength for these furanic compounds falls in
phase and partially due to the solubility of components in the the range of 272–280 nm [24], however, the wavelength of
extractant phase. When the volume ratio increased from 2:5 to maximum absorbance for BTA is 260 nm. The measurement
5:5, the extraction efficiency for BTA increased almost by the at 250 nm gave significant signal sensitivity for BTA and a
same proportion; however, the increase in the extraction effi- minimal absorbance for the furanic compounds. Thus, there
ciency for both DBDS and DBPC was less than that expected was no need for the standard addition method as proposed by
from the change in the volume ratio (Fig. 3). The variation the IEC-60666 standard method [14] when dealing with used
in the extraction efficiency for each of the three components oil.
may be ascribed to their relative solubilities in acetonitrile or Table 1 gives the linearity, slope, and limit of detection
methanol. Since BTA has the relatively highest solubility, it determined according to Miller and Miller [25] for GC and
achieved the highest extraction efficiency in both acetonitrile HPLC calibration graphs for DBPC, DBDS, and BTA fol-
and methanol phases. lowing the liquid–liquid extraction pretreatment described
As Fig. 3 indicates, the extraction efficiency did not reach above. It also provides these values for the literature stan-
100%, hence, in conducting such determinations, standards dard methods in which the pretreatment was only a dilution
and oil sample solutions must undergo the same pretreat- by isooctane as in the case of DBDS or solid phase extrac-
ment before the samples are injected into the GC–ECD–FID tion as in the case of DBPC and BTA [8, 14]. Table 1 shows
and HPLC systems in order to compensate for the difference that higher sensitivities and lower detection limits than those
in the extraction efficiency. of the standard methods were achieved. The sensitivity en-
hancement may be ascribed to the type of column and elu-
ent used. According to the IEC-62697 standard method, a
3.3 Linearity, sensitivity, and limit of detection for significant interference of polychlorinated biphenyles, PCB,
the GC and HPLC calibration curves with DBDS signal was observed, however, this interference
was completely absent when the DB-5 column was used
The linearity was established for concentration ranges of (Fig. 4) under the same conditions and using the same ECD
100–10 000 mg L−1 (0.01–1.00% w/v) DBPC, 1–100 mg L−1 detector.


C 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.jss-journal.com
J. Sep. Sci. 2012, 35, 750–757 Sample Preparation 755

Table 1. Linearity, slope, and limit of detection of the calibration graphs for DBPC, DBDS, and BTA using the liquid–liquid extraction and
the standard methods sample pretreatment prior to the GC and HPLC determination

Regression parameters DBPCb) DBDSc) BTAd)

ASTM D Liquid–liquid IEC- Liquid–liquid IEC- Liquid–liquid

4768 extraction 62697 extraction 60666 extraction

R2a) 0.995 0.999 0.999 0.997 0.997 0.999

Slopea) 0.81 1.84 0.01 0.04 2.53 5.03
LOD 500 mg L−1 (0.05% w/v) 100 mg L−1 (0.01% w/v) 1.80 mg L−1 0.80 mg L−1 5.30 mg L−1 2.04 mg L−1

a) Calibration ranges: 100–10 000 mg L−1 (0.01–1.00% w/v) DBPC and 1–100 mg L−1 DBDS/BTA.
b) Determined by GC/FID.
c) Determined by GC/ECD.
d) Determined by HPLC.

3.4 Accuracy and precision of GC and HPLC

determinations

The accuracy and precision in the determinations of DBPC,

DBDS, and BTA in mineral insulating oil using GC and
HPLC techniques preceded by liquid–liquid extraction pre-
treatment on the one hand and those for the standard meth-
ods on the other hand have been estimated for fresh and aged
mineral insulating oil samples. The results are presented in
Tables 2 (DBDS), 3 (DBPC), and 4 (BTA). The percentage
recoveries (the ratio of the quantity found by experiment for
a certain component to the quantity added to the oil sample)
for DBDS were in the range of 98.9–102.3% with percent
Figure 4. The GC/ECD signal of 1 mg L−1 polychlorinated relative standard deviations (RSDs) of 0.45–6.28 for various
biphenyles, PCB, and 10 mg L−1 DBDS in acetonitrile using DB-5 DBDS concentration ranges (1–150 mg L−1 DBDS). The two-
column.
sided t-test was used to investigate whether the means differ

Table 2. Accuracy and precision for DBDS determination in mineral insulating oils using the liquid–liquid extraction and the standard
pretreatment methods prior to the GC determination

Quantity added Liquid–liquid extraction IEC-62697 Student’s t-test ASTM D1275 B ASTM D 130a)
DBDS (mg L−1 )
Quantity found Recovery Quantity found Recovery two-sided Corrosive–
DBDS (mg L−1 ) (%) DBDS (mg L−1 ) (%) (n = 3) noncorrosive

1.00 1.02 102.3 Not detected - - None corrosive Degree of corrosion is 1a

Percentage RSD 6.28 -
10.00 10.07 100.7 10.33 103.3 1.24 None corrosive Degree of corrosion is 1b
Percentage RSD 1.84 2.99
20.00 20.33 101.7 19.66 98.3 2.90 None corrosive Degree of corrosion is 3b
Percentage RSD 0.85 1.85
50.00 49.93 99.9 50.44 100.9 1.74 Corrosive Degree of corrosion is 4a
Percentage RSD 0.61 0.79
100.00 99.27 99.3 99.99 100.0 1.98 Corrosive Degree of corrosion is 4b
Percentage RSD 0.63 0.11
150.00b) 148.32 98.9 149.58 99.7 2.56 None corrosive Degree of corrosion is 1b
Percentage RSD 0.45 0.36

a) Qualitative visual corrosion classification as per ASTM D 130.

b) The oil sample was passivated with 30 mg L−1 BTA.


C 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.jss-journal.com
756 A. M. Y. Jaber et al. J. Sep. Sci. 2012, 35, 750–757

Table 3. Accuracy and precision for DBPC determination in mineral insulating oils using the liquid–liquid extraction and the standard
pretreatment methods prior to GC determination

Quantity added Liquid–liquid extraction ASTM D 4768 Student t-test

DBPC (% w/v)
Quantity found Quantity found two-sided
DBPC (% w/v) Recovery (%) DBPC (% w/v) Recovery (%) (n = 3)

0.01 0.010 110.0 Not detected - -

Percentage RSD 5.41 -
0.05 0.049 98.0 0.052 104.0 0.46
Percentage RSD 2.97 3.85
0.10 0.101 101.0 0.102 102.0 0.36
Percentage RSD 4.48 6.51
0.20 0.204 102.0 0.209 104.7 0.57
Percentage RSD 4.16 5.26
0.30 0.296 98.8 0.304 101.3 2.14
Percentage RSD 0.51 1.97
0.30a) 0.301 100.3 0.308 102.8 2.63
Percentage RSD 0.99 1.23

a) 0.30% w/v DBPC spiked in aged oil matrix.

significantly from zero. Student’s t values for three replicates taining DBDS as high as 150 mg L−1 was passivated with
of measurements made on each sample at 95% confidence 30 mg L−1 BTA, the ASTM D 1275 method gave a result of
level indicate that no significant difference existed between noncorrosivity of the oil, a conclusion that gives a false indi-
the experimental means obtained from this GC–ECD follow- cation to the presence of DBDS. The percent recoveries for
ing the liquid–liquid extraction pretreatment and the IEC- DBPC were in the range of 98–110% for concentration ranges
62697 standard method (Table 2). Table 2 shows also that of 100–3000 mg L−1 (0.01–0.30% w/v). Student’s t values in-
the IEC-62697 standard method did not detect DBDS at 1 dicate that no significant difference existed between the ex-
mg L−1 level. This may be ascribed to the need for an oil perimental means obtained from this GC–FID following the
sample dilution of about 20 times to facilitate its elution liquid–liquid extraction pretreatment and the ASTM D 4768
through the GC column. The ASTM D1275 B did not de- standard method (Table 3). It is obvious from Table 3 that
tect the presence of DBDS even at concentrations of about 100 mg L−1 (0.01% w/v) DBPC was not detectable when the
20 mg L−1 DBDS. Furthermore, when an oil sample con- standard method was used. The percent recoveries for BTA

Table 4. Accuracy and precision for the BTA determination in mineral insulating oils using the liquid–liquid extraction and the standard
pretreatment methods prior to GC determination

BTA Quantity Liquid–liquid extraction IEC-60666 Student t-test ASTM D1275 B ASTM D 130a)
added (mg L−1 )
Quantity found Quantity found two-sided Corrosive–
BTA (mg L−1 ) Recovery (%) BTA (mg L−1 ) Recovery (%) (n = 3) noncorrosive

2.00b) 2.08 104.2 Not detected - - Corrosive Degree of corrosion is 4a

Percentage RSD 1.69 -
10.00b) 9.99 99.9 10.04 100.4 0.77 None corrosive Degree of corrosion is 3b
Percentage RSD 0.80 0.89
30.00b) 30.03 100.1 29.91 99.7 0.51 None corrosive Degree of corrosion is 2b
Percentage RSD 0.36 1.32
50.00b) 50.25 100.5 49.95 99.9 1.38 None corrosive Degree of corrosion is 1a
Percentage RSD 0.57 0.50
50.00c),b) 50.02 100.0 49.38 98.8 3.06 None corrosive Degree of corrosion is 1b
Percentage RSD 0.29 0.67
100.00c) 100.01 100.0 98.76 98.8 4.16 - -
Percentage RSD 0.18 0.50

a) Qualitative visual corrosion classification as per ASTM D 130.

b) The oil sample was spiked with 50 mg L−1 DBDS.
c) Aged oil matrix contained 1000 ␮g L−1 2-furaldehyde.


C 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.jss-journal.com
J. Sep. Sci. 2012, 35, 750–757 Sample Preparation 757

were in the range of 99.9–104.2% for concentration ranges of King Fahd University of Petroleum & Minerals, the Industrial
2–100 mg L−1 BTA. Student’s t values indicated no significant Support Services Laboratories, and Gulf Chemical and Industrial
difference existed between the experimental means obtained Oils are thanked for the support of this research project.
from this HPLC/UV following the liquid–liquid extraction
The authors have declared no conflict of interest.
pretreatment and the IEC-60666 standard method (Table 4).
The percent recovery was about 100% when the liquid–liquid
extraction pretreatment for an aged oil sample containing 5 References
100 mg L−1 BTA and spiked with 1000 ␮g L−1 2-furaldehyde
was tested (Table 4). The method is accurate, precise, and can [1] Ito, T., Morishima, Y., IEEJ Trans. 2009, 4, 422–424.
be used successfully for different mineral insulating oil ma- [2] Kawarai, H., Fujita, Y., Tanimura, J., Toyama, S., Yamada,
trices used for power transformers. Consequently, the liquid– N., Nagao, E., IEEE 2009, 16, 1430–1433.
liquid extraction pretreatment facilitates the removal of the [3] Amimoto, T., Nagao, E., Tanimura, J., Toyama, S.,
oil matrix, preconcentrates the analyte (DBDS, DBPC, and Yamada, N., IEEE Trans. 2008, 16, 257–264.
BTA), and reduces the analysis time of the three components [4] Scott, G., Atmospheric Oxidation and Antioxidants,
that may need to be tested together to judge the quality and Elsevier, Amsterdam, London, New York 1965.
characteristics of the mineral insulating oil when fresh or [5] Maina, R., Scatiggio, F., Kapila, S., Tumiatti, V., Tumiatti,
used. Thus, DBDS, the antioxidant and corrosive component M., Pompili, M., Dibenzyl disulfide (DBDS) as corrosive
at the same time can be detected and controlled even at con- sulfur contaminant in used and unused mineral insulat-
ing oils, published on CIGRE SC2 web site, 2006.
centrations as low as 1 mg L−1 and in the presence of the BTA
passivator. These findings would help studying the kinetics [6] Wiklund, P., Levin, M., Pahlavanpour, B., IEEE 2007, 23,
1–14.
of copper corrosion in the transformer where the concentra-
tions of DBDS, DBPC, and BTA should be smaller than the [7] Shin, J., Hong, J., Trans. Elect. Electron. Mater. 2010, 11,
288–291.
levels detected by the standards; a study that is currently under
investigation. [8] J. ASTM D 4768-03, J. ASTM Int. 2008, 10.03.
[9] J. ASTM D 2668-07, J. ASTM Int. 2008, 10.03.
[10] Lamarre, A., Gendron, C., IEEE Trans. 1995, 2, 413–417.
4 Concluding remarks [11] Foley, L., Kimmerle, F. M., Anal. Chem. 1979, 51, 818–822.
[12] Zamarreño, M. M., González-Maza, I., Sánchez-Pérez, A.,
This work describes an efficient single and fast pretreatment Carabias Martı́nez, R., Food Chem. 2007, 100, 1722–1727.
step for fresh and used transformer oil samples with minimal
[13] Augusta, M., Martins, G., Gomes, A., Pahlavanpour, B.,
consumption of solvents for the simultaneous liquid–liquid IEEE 2009, 25, 23–27.
extraction of three important mineral insulating oil additives,
[14] IEC-60666, IEC, 2nd Ed., 2010, 22–30.
namely, DBDS, DPBC, and BTA to facilitate their determina-
[15] J. ASTM WK 24216, J. ASTM Int. 2009 (a draft under
tion by GC and HPLC techniques. DBDS and DBPC are de-
development).
termined simultaneously by GC/ECD/FID technique while
[16] CIGRE WG A2-32, Copper sulfide in transformer insula-
BTA is determined by HPLC technique. Comparison of the
tion, Final report—Boucher 378, 2009, 1–35.
results of this method for each of the three components to
[17] IEC-62535, IEC, 1st Ed., 2008, 6–13.
those obtained by the standard methods revealed that this
method provides better sensitivity and lower detection lim- [18] ASTM D1275-06, J. ASTM Int. 2006, 10.03.
its as a result of the preconcentration and removal of the [19] Grant, D. H., IEEE Electrical Institution Conference,
mineral insulating oil matrix that may interfere with the de- Canada, June 2009, pp. 489–490.
termination of the components. Determining relatively low [20] J. ASTM D 130-04, J. ASTM Int. 2006, 5.01.
concentrations of these three components would help study- [21] Toyama, S., Tanimura, J., Yamada, N., Nagao, E., IEEE
ing their interaction effects in the mineral insulating oil and Trans. 2009, 16, 509–515.
its corrosion and passivation actions under the transformer [22] IEC-62697-1, IEC, 1st Ed., 2010, 10–27.
operational conditions. Traditionally this interaction effect is [23] IEC-60296, IEC, 3rd Ed., 2003, 6–7.
studied indirectly by investigating the copper sulfide forma- [24] J. ASTM D 5837-99, J. ASTM Int. 2005, 10.03.
tion. Currently, the corrosion process is being investigated [25] Miller, J. C., Miller, J. N., Statistics and Chemometrics
via the depletion of the DBDS concentration in the mineral for Analytical Chemistry, Pearson, Harlow 2005, 5th Ed.,
insulating oil. pp. 121, 39.


C 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.jss-journal.com