Analytical and Bioanalytical Chemistry

https://doi.org/10.1007/s00216-020-02714-5

RESEARCH PAPER

Determination of water content of crude oil by azeotropic

distillation Karl Fischer coulometric titration
Zhilong Zhen 1 & Haifeng Wang 2 & Yuanming Yue 3 & Dongmei Li 3 & Xiaoping Song 2 & Jia Li 2

Received: 5 April 2020 / Revised: 9 May 2020 / Accepted: 14 May 2020

# Springer-Verlag GmbH Germany, part of Springer Nature 2020

Abstract
The determination of water content in crude oil is important for oil transportation, refining, and trade. However, the sensitivity
and accuracy of the conventional azeotropic distillation (AD) method are inadequate. Karl Fischer titration methods may give
false high results because of the reducing sulfur compounds in crude oil. The present study developed an azeotropic distillation
Karl Fischer coulometric titration (AD-KFCT) method which required a modified instrument and a new calibration procedure.
The method was modified to decrease the interference caused by reducing sulfur compounds. A certified reference material for
water content in liquid was used to determine the recovery of water mass achieved using the AD-KFCT method. The effect of the
sample polarity on the method accuracy was assessed. The relative error and relative standard deviations of the water content in
three crude oils containing known amounts of water were −7.5% to 2.9% and 0.4% to 6.0%, respectively. The interference by
reducing sulfur compounds was studied. The crude oil containing 1-propanethiol was measured using a sulfur dioxide-free
anolyte, and the amount of iodine consumed by the distilled 1-propanethiol was determined. The contribution of 1-
propanethiol was then subtracted from the water content measured using the normal Karl Fischer reagent. Finally, the relative
error of the modified water content in the crude oil samples containing 1-propanethiol was −4.4% to 0.7%. Therefore, the
modified AD-KFCT method is accurate and convenient for crude oil.

Keywords Water content . Crude oil . Azeotropic distillation . Karl Fischer coulometric titration

Introduction must be determined accurately to ensure operational safety

Water in crude oil can increase friction in pipelines and thus
increase the energy cost of transportation [1]. It can also dis-
solve salts, which accelerates the corrosion of refining equip-
ment and the scaling of pipelines [1, 2]. Excessive water in
crude oil increases the energy required during distillation and
can cause instability in the refining operation [1]. Therefore,
the excessive water must be removed prior to refining, which
consumes energy and reagents. The water content of crude oil
* Haifeng Wang
wanghf@nim.ac.cn
1
School of Computer, Tonghua Normal University, Tonghua 134002,
China
2
National Institute of Metrology of China, Beijing 100029, China
3
Technical Centre of Harbin Customs of China, Harbin 150008,
China
and economic efficiency.
There are several methods for measuring the water content
of crude oil, including azeotropic distillation (AD) [3], Karl
Fischer titration (KFT) [4], headspace gas chromatography
[5], electric dehydration [6], microwave resonance [7], centri-
fugation [8], electric capacitance [9], terahertz time-domain
spectroscopy [10], and nuclear magnetic resonance [11].
The AD method is convenient and accurate, and is used as
an international standard method [12]. However, water drop-
lets in the inner wall of the condenser cause false low results
[13]. Kopyltsova et al. found that the trap volume and the
water content of the distillation solvent affected the accuracy
of the AD method [14, 15]. The accuracy of the AD method
for crude oil with low water content is unsatisfactory because
of the poor readability of the water volume and the existence
of water-in-oil emulsions in the trap [12]. The AD method is
also time-consuming.
KFT methods, including the Karl Fischer volumetric titra-
tion (KFVT) and Karl Fischer coulometric titration (KFCT),

are used to determine the water content of crude oil using the
stoichiometric ratio of iodine to water (1:1) in the Karl Fischer
reaction [16]. Both KFT methods give reproducible results
and thus are used as international standard methods [17, 18].
Crude oil, particularly heavy crude oil, is poorly soluble in the
anolyte used in Karl Fischer titration, so the anolyte needs to
be renewed often and the electrode needs to be cleaned fre-
quently. Furthermore, reducing compounds such as mercaptan
(RSH) in crude oil can be oxidized by iodine, causing false
high results [19–21]. Margolis et al. developed a modified
KFCT method in which iodine consumed by reducing sulfur
compounds was determined using sulfur dioxide (SO2)-free
reagents, and the contribution of reducing sulfur compounds
was then subtracted from the water content measured using the
normal Karl Fischer reagent [1, 4]. However, this modified
KFCT method with the two-step procedure was time-consum-
ing, and its results were not reproducible. The lack of an ac-
curate and convenient method for crude oil causes inconsis-
tency of water content in international trade [15].
Roberts et al. developed a method in which the mixture of
sample and solvent was distilled and then the mass of water in
the water-solvent azeotrope was determined using the KFVT
[22]. Muroi et al. reported a continuous azeotropic distillation
Karl Fischer volumetric titration method to determine the wa-
ter content of grease [23]. More recently, a continuous
azeotropic distillation Karl Fischer coulometric titration
(AD-KFCT) method was used to determine the water content
of mineral and transformer oils [24–26]. Extracting water
from a viscous sample by azeotropic distillation prevents the
sample from contaminating the electrode. The AD-KFCT
method was found to be more sensitive and had a lower limit
of detection than the conventional AD method [25]. However,
the AD-KFCT method has seldom been used to determine the
water content of crude oil [1].
In the present study, the AD-KFCT method was modified
to measure the water content of crude oil. The recovery of
water mass achieved using the method was determined using
the certified reference material (CRM) for water content in
liquid. The effect of the polarity of the sample on the accuracy
of the method was investigated, and the interference caused by
reducing sulfur compounds was reduced.
Experimental
Materials
Hydranal Coulomat AG-Oven (hereafter “AG-Oven”) anolyte
was purchased from Honeywell (Morris Plains, NJ, USA).
The CRM for the water content in liquid with a certified value
of 1.00 mg·g−1 (GBW 13513) was developed by the National
Institute of Metrology of China (Beijing, China). Xylene, bu-
tanol, anisole, benzyl alcohol, formamide, and 1-propanethiol
Zhen Z. et al.
were purchased from Beijing Chemical Works (Beijing,
China). Chromatographic-grade methanol was purchased
from Merck (Darmstadt, Germany). Imidazole was purchased
from Sigma-Aldrich (St. Louis, MO, USA). Sodium thiosul-
fate and trichloroacetic acid were purchased from Alfa Aesar
Chemicals (Ward Hill, MA, USA). SO2-free anolyte contain-
ing methanol, imidazole, potassium iodide, and trichloroacetic
acid with mass fractions of 79.02%, 9.52%, 3.31%, and
8.15%, respectively, were prepared in the laboratory. A
0.4-mL aliquot of 0.1 mol·L−1 sodium thiosulfate aqueous
solution was added to 1 L of the SO2-free anolyte prior to
usage. Four crude oil samples were from the Western Desert
in Egypt, Castilla in Columbia, Changqing in China, and
Tyumen in Russia. Their API indices were 41.1, 12.7, 39.6,
and 42.3, respectively. Their sulfur content was 14.1, 16.0,
0.90, and 4.74 mg·g−1, respectively.
The test rig for the AD-KFCT method was constructed as
shown in Fig. 1. Nitrogen supplied by a gas cylinder (labelled
1 in Fig. 1) was dried by passing through a molecular sieve
drier (2), and the flow rate was controlled and monitoring
using a mass flow controller and meter (3). The nitrogen
flowed into a distillation flask (4) through a thin Teflon tube.
This home-made glass distillation flask (4), a 12-mL crimped
vial with a septum, had two thin glass tubes for gas inlet and
outlet. The distillation flask was placed in an aluminum block
that was placed in an electric heater (5). The gas outlet tube
was connected to the titration cell (6) of a Karl Fischer coulo-
metric titrator (7) by a thin Teflon tube.
The AD-KFCT method was performed using a DL 39 Karl
Fischer coulometric titrator (labelled 7 in Fig. 1, Mettler-
Toledo, Greifensee, Switzerland) with a diaphragmless elec-
trode. A CS200 gas mass flow controller and meter (3 in Fig.
1, Sevenstar, Beijing, China) was used to regulate the nitrogen
flow rate.
Analytical methods
Xylene was used as the distillation solvent. The distillation
temperature was 100 °C, which is 5 °C higher than the boiling
Fig. 1 Schematic of the AD-KFCT apparatus (1, nitrogen cylinder; 2,
molecular sieve drier; 3, gas mass flow controller and meter; 4,
distillation flask; 5, electric heater; 6, titration cell; 7, Karl Fischer
coulometric titrator)
Determination of water content of crude oil by azeotropic distillation Karl Fischer coulometric titration
point of the water-xylene azeotrope (95 °C). The measurement
procedure was as follows: start the titrator, add 10 mL xylene
to the distillation flask, distill the xylene to anhydrous, deter-
mine the drift over 180 s, add the sample to the distillation
flask, distill the mixed solution and titrate the water-xylene
azeotrope simultaneously, end the titration, and calculate the
water content of the sample. AG-Oven anolyte was used as the
anodic electrolyte. The nitrogen flow rate was 50 mL·min−1.
The extraction and titration times were 60 and 480 s, respec-
tively. After titration terminated, the drift was no more than
5 μg·min−1. The water content of a sample was calculated as
below.
mH2 O;KFCT
x¼
mSample R
where x is the water content of the sample (μg·g−1), mH2O,
KFCT is the water mass measured using the Karl Fischer cou-
lometric titrator (μg), msample is the sample mass (g), and R is
the water mass recovery. R was determined using the GBW
13513.
In the AD-KFCT method, a sample was measured
using both the normal Karl Fischer reagent (AG-Oven)
and the SO2-free anolyte (to reduce the interference
caused by reducing sulfur compounds). The measure-
ment procedure using the SO2-free anolyte was similar
to that using AG-Oven anolyte, but the extraction time
was 360 s, because 1-propanethiol (which was spiked in
the sample) evaporates slowly. When the amount of
iodine consumed by the distilled reducing compounds
had been determined using the SO2-free anolyte, the
contribution of distilled reducing compounds was
subtracted from the water content determined using
AG-Oven anolyte to give the modified water content.
Results
Calibration of AD-KFCT method
GBW 13513 with certified water content of 1.00 mg·g−1 was
measured using the AD-KFCT method. As shown in Fig. 2, at
measured water mass of 20, 30, 50, 90, 180, 370, 575, 760,
and 965 μg, the recoveries of water mass (with relative stan-
dard deviations (RSDs) in parentheses) were 70.4% (1.3%),
77.4% (0.6%), 86.4% (2.4%), 88.6% (1.1%), 92.4% (1.1%),
94.7% (0.4%), 98.4% (0.7%), 97.4% (1.0%), and 97.3%
(0.5%), respectively. It can be seen that the recovery increased
as the water mass increased. When the water mass ranged
from 20 to 965 μg, the RSDs of the recoveries ranged from
0.4% to 2.4% (Fig. 2), indicating good reproducibility. The
limit of detection of the water mass was 12 μg, indicating
good sensitivity.
Fig. 2 Measured water mass vs water mass recovery of GBW 13513 by
AD-KFCT (red solid line is the fitting line)
ð1Þ
The water content of the dried xylene determined using the
KFCT method was 1.2 μg·g−1, and the water content of the
residual solution after distillation, also determined using the
KFCT method, was in the range of 0.7–1.5 μg·g−1. The small
differences between the water content of the dried xylene and
residual solution does not adequately explain the lower water
mass recovery (Fig. 2). When the AD-KFCT was at equilib-
rium, some iodine evaporated along with the carrier gas. The
electrode generated iodine slowly to keep the potential at the
equilibrated value of 100 mV. The drift determined at the
equilibrium was in the range of 2–4 μg·min−1, and was
subtracted from the measured water mass. During the extrac-
tion and the early stage of titration of the AD-KFCT, the water
content of the anolyte was high, so the iodine concentration of
anolyte was much lower than that at the equilibrium. The
iodine evaporation rate was lower than that during the drift
determination, i.e. the actual drift was less than the determined
drift, which results in the lower water mass recovery (Fig. 2).
As the water mass increased, the proportion of the error from
the drift determination to the total water mass decreased, so
the water mass recovery increased (Fig. 2).
A function was developed to fit the measured water mass
data to the water mass recovery data (Eq. 2 and Fig. 2). The
function was as follows:
−mH O;KFCT −mH O;KFCT
2 2
R ¼ −0:7456⋅e 13:23119 −0:12812⋅e 236:15397 þ 0:9813 ð2Þ
where R is the fitted water mass recovery, and mH2O, KFCT is
the measured water mass (μg). After the crude oil was mea-
sured using the AD-KFCT method, mH2O, KFCT was intro-
duced into Eq. 2, and R was calculated. mH2O, KFCT, R, and
msample were introduced into Eq. 1, and then the water content
of the sample (x) was calculated.
The AD-KFCT method reported by Margolis et al. is a
three-step procedure which involves determining the water
mass in the azeotrope using an AD-KFCT, determining the
water content of the dried solvent before distillation using a
KFCT, and determining the water content of the residual so-
lution after distillation using a KFCT [25]. The water content

of the dried solvent and that of the residual solution were
extremely low and therefore difficult to determine accurately.
The mass of the dried solvent or residual solution (~8 g) was
much larger than the mass of the sample (0.1–0.5 g); a small
error in the water content of the dried solvent or residual so-
lution would cause a marked error in the water content of
sample. In our study, once the AD-KFCT method had been
calibrated (i.e. the function fitting the water mass data to the
water mass recovery data was determined), the water content
of a sample could be calculated from the measured water mass
in the azeotrope. This made the method convenient and repro-
ducible. The AD-KFCT method used a simple home-made
glass distillation flask and two thin Teflon transfer lines, and
thus low drift of 2–4 μg·min−1 was achieved, improving the
reproducibility of water content results. Xylene was used as
the solvent instead of toluene, so the distillation process could
be performed at a high temperature (100 °C) to allow a short
distillation time and give good water mass recovery.
Effect of the sample polarity on the accuracy of the
AD-KFCT method
The effect of the sample polarity on the accuracy of the AD-
KFCT method was investigated. For this, anisole, 1-butanol,
benzyl alcohol, and formamide with water content of 0.571,
2.845, 7.616, and 3.009 mg·g−1, respectively, were measured
using the AD-KFCT method. When the water mass in anisole
ranged from 70 to 570 μg, the relative error of water content
ranged from −2.8% to 4.6%. Similarly, when the water mass
in benzyl alcohol ranged from 80 to 1000 μg, the relative error
of water content ranged from −4.4% to 3.9%. When the water
mass in 1-butanol ranged from 50 to 500 μg, the relative error
of water content ranged from −5.9% to 4.4%. This indicated
that the AD-KFCT method was accurate for these three com-
pounds. However, when the water mass in formamide ranged
from 124 to 586 μg, the relative error of water content ranged
from −79% to −47%, indicating that the results were inaccu-
rate and not reproducible.
The boiling points of anisole, benzyl alcohol, 1-butanol,
and formamide are 154, 205, 117, and 210 °C, respectively.
Therefore, these compounds would not evaporate markedly
during distillation at 100 °C. The dielectric constants of xy-
lene, anisole, benzyl alcohol, 1-butanol, and formamide are
2.27, 4.33, 13.0, 17.8, and 110, respectively [27]. The “like
dissolves like” rule states that compounds with the same po-
larity (polar or non-polar) will dissolve in each other. Because
anisole, benzyl alcohol, and 1-butanol are non-polar, their
residual solution is non-polar. The solubility of water in the
non-polar residual solutions at high temperature was very low,
and most of the water in samples evaporated during distilla-
tion. This explained why the water content of anisole, benzyl
alcohol, and 1-butanol was accurate. In contrast, formamide
increased the polarity of the residual solution and the
Zhen Z. et al.
solubility of water in the solution. Therefore, some water in
the sample would have remained in the residual solution, and
the measured water content was lower than the actual value.
Validation of the AD-KFCT method using crude oil
containing a known amount of water
Crude oil samples containing known amounts of water
were prepared using a gravimetric method. The water con-
tent of the dry crude oil was measured using the AD-KFCT
method. Pure water was then added to the dry crude oil.
The mass of crude oil and pure water was weighed using an
electric balance with readability of 0.01 mg. The water
content of the spiked crude oil was calculated from the
mass of the dry crude oil, the mass of pure water, and the
water content of the dry crude oil. Spiked Western Desert,
Castilla, and Changqing crude oil samples with various
water content were prepared and then used to validate the
accuracy of the AD-KFCT method. The mass of crude oil
samples was 0.09 to 0.7 g, and the water mass of each
aliquot ranged from 0.2 to 1.0 mg. As shown in Fig. 3,
the relative error of water content for the Western Desert
crude oil samples was −1.9% to 0.0%. The relative error of
water content in the Castilla and Changqing crude oil sam-
ples was −7.5% to 2.9% and −5.0% to 2.2%, respectively,
which indicated that the AD-KFCT method was accurate.
As shown in Fig. 3, the RSDs of water content of the
Western Desert, Castilla, and Changqing crude oil samples
was 1.6–4.2%, 3.7–6.0%, and 0.4–3.9%, respectively,
which indicated that the AD-KFCT method was
reproducible.
Crude oil mainly contains non-polar hydrocarbons, so the
residual solution of crude oil and xylene has low water solu-
bility. Therefore, the water content of crude oil samples deter-
mined using the AD-KFCT method was accurate. The mea-
sured water content of the crude oil samples was less repro-
ducible than the measured water content of GBW 13513 be-
cause of the inhomogeneity in the water content of crude oil
samples.
Fig. 3 Water content vs relative error of water content of crude oil
Determination of water content of crude oil by azeotropic distillation Karl Fischer coulometric titration
Interference caused by reducing sulfur compounds
The interference with the AD-KFCT results caused by reduc-
ing sulfur compounds was investigated. Aliquots of GBW
13513 were spiked with various amounts of 1-propanethiol.
The mass of 1-propanethiol and GBW 13513 was weighed
using an electric balance with readability of 0.01 mg.
Solutions with water content of ~1.00 mg·g −1 and 1-
propanethiol content between 1 and 10 mg·g−1 were prepared
and measured.
The solutions were measured using the AD-KFCT method
using AG-Oven anolyte. Each sample aliquot was ~0.47 g. As
the 1-propanethiol content increased from 1 to 10 mg·g−1, the
relative error of the water content increased from 1.8% to
21.8% (Fig. 4, squares). The positive errors were attributed
to the side reaction between the distilled 1-propanethiol and
iodine.
The solutions were also measured using the AD-
KFCT method with SO2-free anolyte. Each sample ali-
quot was ~0.47 g. Iodine in the SO2-free anolyte did
not react with water because of the lack of SO2, so
iodine consumption occurred only by the reaction be-
tween the distilled 1-propanethiol and iodine. The mea-
sured water mass was converted into an amount of io-
dine using the stoichiometric ratio of water to iodine
(1:1) for the Karl Fischer reaction [16]. As shown in
Fig. 5, as the amount of 1-propanethiol in the sample
increased from 6.2 to 62 μmol (i.e. the 1-propanethiol
concentration increased from 1 to 10 mg·g−1), and the
amount of iodine increased from 0.95 to 6.6 μmol. The
slope of the straight line fitted to a plot of the amount
of iodine (on the y-axis) against the amount of 1-
propanethiol (on the x-axis) was 0.122, suggesting that
the stoichiometric ratio of iodine to 1-propanethiol was
0.122:1 (Fig. 5, circles). According to ISO 10101, mer-
captans react with iodine and thus produce disulfides
Fig. 4 Mass fraction of 1-propanethiol vs relative error of water content
of GBW 13513 spiked with 1-propanethiol (square, the relative error of
the original measured value using AD-KFCT using AG-Oven anolyte;
circle, the relative error of water content after the modification of
interference caused by distilled 1-propanethiol)
Fig. 5 Amount of 1-propanethiol vs the measured amount of iodine of
GBW 13513 spiked with 1-propanethiol (square, using Oven-KFCT;
circle, using AD-KFCT)
(Eq. 3) [28]. Therefore, the stoichiometric ratio of io-
dine to1-propanethiol should be 0.5:1. The actual stoi-
chiometric ratio for the AD-KFCT method was different
from the theoretical ratio.
2RSH þ I2 →RSSR þ 2HI ð3Þ
where RSH is a mercaptan, I2 is iodine, RSSR is a disul-
fide, and HI is hydrogen iodide.
The solutions were also measured using the oven evapora-
tion Karl Fischer coulometric titration (oven-KFCT) method
using the SO2-free anolyte. The mass of the sample aliquot
was ~0.37 g, and the oven temperature was 100 °C. As the
amount of 1-propanethiol increased from 4.8 to 49 μmol (i.e.
the 1-propanethiol concentration increased from 1 to 10 mg·
g−1), the amount of iodine increased from 3.5 to 26 μmol (Fig.
5, squares). The slope of the straight line fitted to a plot of the
amount of iodine (on the y-axis) against the amount of 1-
propanethiol (on the x-axis) was 0.555 (Fig. 5). The stoichio-
metric ratio of iodine to 1-propanethiol (0.555:1) was close to
the theoretical value (0.5:1), indicating that most of the 1-
propanethiol evaporated and reacted with iodine following
Eq. 3 when the oven-KFCT method was used. For compari-
son, most of the 1-propanethiol remained in the residual solu-
tion when the AD-KFCT method using the SO2-free anolyte
was used, and the stoichiometric ratio (0.122:1) was quite
different from the theoretical value (0.5:1) (Fig. 5, circles)
[28].
When the AD-KFCT method was used, the amount of
iodine consumed by 1-propanethiol was measured using the
SO2-free anolyte, and the contribution of 1-propanethiol was
subtracted from the water content measured using AG-Oven
anolyte. As shown in Fig. 4, with 1-propanethiol concentra-
tion ranging from 1 to 10 mg·g−1, the relative error of the
modified water content ranged from 0.13% to 4.1%, which
indicated that the procedure markedly improved the accuracy
of the measured water content.

Validation of the AD-KFCT method using crude oil
containing 1-propanethiol
Crude oil samples containing 1-propanethiol were measured
to confirm the method successfully decreased the interference
caused by reducing sulfur compounds. Aliquots of Tyumen
crude oil containing 1-propanethiol were spiked with pure
water to give crude oil samples containing 5.0 mg·g−1 1-
propanethiol and water content of 0.50–5.0 mg·g−1. The crude
oil samples were detected using the AD-KFCT method using
AG-Oven and the SO2-free anolyte. The mass of the crude oil
samples was 0.2 to 0.4 g, and the water mass of each aliquot
was in the range of 0.2 to 1.0 mg.
As shown in Fig. 6, at water content of approximately 0.50,
1.0, 1.5, 3.0, and 5.0 mg·g−1, the relative error of water content
measured using AG-Oven anolyte was 6.2%, 6.9%, 4.1%,
0.9%, and 1.4%, respectively (Fig. 6, squares). The amount
of iodine consumed by 1-propanethiol was measured using
the SO2-free anolyte, and the contribution was subtracted from
the water content measured using AG-Oven anolyte. The rel-
ative error of the modified water content was −4.4%, 0.7%,
−0.8%, −1.7%, and −0.8% when the water content was ap-
proximately 0.50, 1.0, 1.5, 3.0, and 5.0 mg·g−1, respectively
(Fig. 6, circles). This indicated that the accuracy of the AD-
KFCT method was improved by eliminating the interference
caused by distilled reducing compounds. It should be noted
that the reproducibility for crude oil containing 1-propanethiol
was worse than the reproducibility for GBW 13513 also con-
taining 1-propanethiol. This could have been caused by the
inhomogeneity of water in the crude oil.
Discussion
Crude oil contains several species of sulfur compounds, in-
cluding hydrogen sulfide (H2S), elemental sulfur, RSH,
thioethers, bisulfides, and thiophenes. H2S and RSH can react
Fig. 6 Water content vs relative error of water content of Tyumen crude
oil containing 1-propanethiol (square, original results using AG-Oven
anolyte; circle, modified results)
Zhen Z. et al.
with iodine to give elemental sulfur and bisulfides, respective-
ly [28]. Therefore, for crude oil containing H2S and RSH, the
KFCT method using direct sample injection gives a false high
result. The relative error in such cases can be greater than
600% [4]. Margolis et al. developed a modified KFCT method
in which the contribution of the reducing sulfur species deter-
mined using the SO2-free anolyte was subtracted from the
water content measured using the normal Karl Fischer anolyte
[4]. This modification improved the accuracy of the KFCT
method for the water content of crude oil, but the method is
laborious and time-consuming.
The modified AD-KFCT method described here can be
used to determine the water content of crude oil using the
strategy described below. First, the crude oil should be mea-
sured using the SO2-free anolyte. If the amount of iodine
consumed by the distilled reducing compounds is very low
(i.e. negligible interference is caused by reducing com-
pounds), the sample can be measured using the normal Karl
Fischer reagent. If the amount of iodine consumed by the
distilled reducing sulfur compounds is not negligible, the con-
tribution made by reducing sulfur compounds should be
subtracted from the water content measured using the normal
Karl Fischer reagent to give the modified water content. The
proportions of H2S and low-molecular mercaptans to total
sulfur compounds are usually low in commercial crude oil.
For example, no distilled reducing sulfur compounds were
found in the four crude oil samples mentioned above using
the AD-KFCT method using the SO2-free anolyte. Therefore,
the AD-KFCT method with the normal Karl Fischer reagent
can generally be used to measure commercial crude oil
independently.
Conclusion
The AD-KFCT method was modified and used to deter-
mine the water content of crude oil samples. Calibration
was performed using a CRM for the water content in
liquid. The results indicated that the measured water con-
tent was accurate for the non-polar samples but inaccurate
and poorly reproducible for polar samples such as form-
amide. Using the AD-KFCT method, the relative error
and the RSDs for the water content of three crude oil
samples were −7.5% to 2.9% and 0.4% to 6.0%, respec-
tively. For crude oil containing 1-propanethiol, the water
content measured using the AD-KFCT method was mod-
ified to decrease the contribution of iodine consumed by
1-propanethiol (a reducing compound), and the relative
error for the modified water content was −4.4% to 0.7%.
The modified AD-KFCT method can be used to determine
the water content of crude oil samples. The method is
convenient and accurate, and reducing sulfur compounds
do not interfere with the results.
Determination of water content of crude oil by azeotropic distillation Karl Fischer coulometric titration
Acknowledgments This study was supported by the National Quality
Infrastructure Program of China (grant no. 2017YFF0205300) and the
Ability Promotion Program of the National Institute of Metrology of
China (grant no. 31-ANL1814).
Compliance with ethical standards
Conflict of interest The authors declare that they have no conflict of
interest.
Ethical approval This article does not contain any studies with human
participants or animals performed by any of the authors.
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