Designation: D4928 − 11

Manual of Petroleum Measurement Standards (MPMS), Chapter 10.9

Designation: 386/99

Standard Test Method for

Water in Crude Oils by Coulometric Karl Fischer Titration1
This standard is issued under the fixed designation D4928; 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.
This standard has been approved for use by agencies of the Department of Defense.

1. Scope* D4057 Practice for Manual Sampling of Petroleum and

1.1 This test method covers the determination of water in Petroleum Products
the range from 0.02 to 5 mass or volume % in crude oils. D4177 Practice for Automatic Sampling of Petroleum and
Mercaptan (RSH) and sulfide (S− or H2S) as sulfur are known Petroleum Products
to interfere with this test method, but at levels of less than D5854 Practice for Mixing and Handling of Liquid Samples
500 µg/g (ppm), the interference from these compounds is of Petroleum and Petroleum Products
insignificant (see Section 5). E203 Test Method for Water Using Volumetric Karl Fischer
Titration
1.2 This test method can be used to determine water in the
0.005 to 0.02 mass % range, but the effects of the mercaptan 2.2 API Standards:3
and sulfide interference at these levels has not been deter- MPMS Chapter 8.1 Practice for Manual Sampling of Petro-
mined. leum and Petroleum Products (ASTM Practice D4057)
MPMS Chapter 8.2 Practice for Automatic Sampling of
1.3 This test method is intended for use with standard Petroleum and Petroleum Products (ASTM Practice
commercially available coulometric Karl Fischer reagent. D4177)
1.4 The values stated in SI units are to be regarded as MPMS Chapter 8.3 Practice for Mixing and Handling of
standard. No other units of measurement are included in this Liquid Samples of Petroleum and Petroleum Products
standard. (ASTM Practice D5854)
1.5 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the 3. Summary of Test Method
responsibility of the user of this standard to establish appro- 3.1 After homogenizing the crude oil with a mixer, an
priate safety and health practices and determine the applica- aliquot is injected into the titration vessel of a Karl Fischer
bility of regulatory limitations prior to use. For specific hazard apparatus in which iodine for the Karl Fischer reaction is
statements, see Section 7. generated coulometrically at the anode. When all the water has
been titrated, excess iodine is detected by an electrometric
2. Referenced Documents end-point detector and the titration is terminated. Based on the
2.1 ASTM Standards:2 stoichiometry of the reaction, one mole of iodine reacts with
D1193 Specification for Reagent Water one mole of water, thus the quantity of water is proportional to
the total integrated current according to Faraday’s Law.
3.2 The precision of this test method is critically dependent
1
This test method is under the jurisdiction of ASTM Committee D02 on on the effectiveness of the homogenization step. The efficiency
Petroleum Products and Lubricants and the API Committee on Petroleum Measure- of the mixer used to achieve a homogeneous sample is
ment and is the direct responsibility of Subcommittee D02.02 /COMQ on Hydro-
carbon Measurement for Custody Transfer (Joint ASTM-API). determined by the procedure given in Practice D5854 (API
Current edition approved June 1, 2011. Published August 2011. Originally MPMS Chapter 8.3).
approved in 1989. Last previous edition approved in 2010 as D4928–00 (2010).
DOI: 10.1520/D4928-11.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
3
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM Published as Manual of Petroleum Standards. Available from American
Standards volume information, refer to the standard’s Document Summary page on Petroleum Institute (API), 1220 L. St., NW, Washington, DC 20005-4070, http://
the ASTM website. www.api.org.

*A Summary of Changes section appears at the end of this standard

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D4928 − 11
3.3 Two procedures are provided for the determination of inserted through the inlet port septum. This syringe is used in
water in crude oils. In one procedure, a weighed aliquot of the calibration step (Section 10). It should be of suitable
sample is injected into the titration vessel and the mass % of graduations for readings to the nearest 0.1 µL or better.
water is determined. The other procedure provides for the 6.3.1.2 Syringes, 250 µL, 500 µL, and 1000 µL (1 mL), for
direct determination of the volume % of water in the crude oil crude oil samples. For the volumetric determination procedure,
by measuring the volume of crude oil injected into the titration the syringes should be accurate to 5 µL, 10 µL, and 20 µL
vessel. (0.02 mL), respectively.
4. Significance and Use 7. Reagents and Materials
4.1 A knowledge of the water content of crude oil is 7.1 Purity of Reagents—Reagent grade chemicals shall be
important in the refining, purchase, sale, or transfer of crude used in all tests. Unless otherwise indicated, it is intended that
oils. all reagents shall conform to the specifications of the Commit-
tee on Analytical Reagents of the American Chemical Society,
5. Interferences
where such specifications are available.4 Other grades may be
5.1 A number of substances and classes of compounds used, provided it is first ascertained that the reagent is of
associated with condensation or oxidation-reduction reactions sufficiently high purity to permit its use without lessening the
interfere in the determination of water by Karl Fischer. In crude accuracy of the determination.
oils, the most common interferences are mercaptans and
7.2 Purity of Water—Unless otherwise indicated, references
sulfides (not total sulfur). At levels of less than 500 µg/g (ppm)
to water shall be understood to mean reagent water as defined
(as sulfur), the interference from these compounds is insignifi-
by Type IV of Specification D1193.
cant. Most crude oils, including crude oils classified as “sour
crude,” have mercaptan and sulfide levels of less than 500 µg/g 7.3 Xylene, reagent grade. Less than 0.05 % water.
(ppm) as sulfur. For more information on substances that (Warning—Flammable. Vapor harmful.)
interfere in the determination of water by Karl Fischer titration 7.4 Karl Fischer Reagent—Standard commercially avail-
method (see Test Method E203). able reagents for coulometric Karl Fischer titrations.
5.2 The significance of the mercaptan and sulfide interfer- 7.4.1 Anode Solution, shall be 6 parts of commercial Karl
ence on the Karl Fischer titration for water levels in the 0.005 Fischer anode solution with 4 parts of reagent grade xylene.
to 0.02 mass % range has not been determined experimentally. Fresh Karl Fischer anode solution shall be used. Anode
At these low water levels, however, the interference may be solution shall not be used past its expiration date. Anode
significant for mercaptan and sulfide levels of less than solution should be replaced after 7 days in the titration vessel.
500 µg/g (ppm) (as sulfur). (Warning—Flammable, toxic by inhalation and if swallowed,
avoid contact with skin.)
6. Apparatus
NOTE 1—Other proportions of anode solution and xylene can be used
6.1 Karl Fischer Apparatus, using electrometric end-point. and should be determined for a particular reagent and apparatus. The
Presently there are available on the market a number of precision and bias were established using the designated anode solution
commercial coulometric Karl Fischer titration assemblies. and xylene.
Instructions for operation of these devices are provided by the 7.4.2 Cathode Solution, use standard commercially avail-
manufacturer and not described herein. able Karl Fischer cathode solution. Cathode solution shall not
6.2 Mixer, to homogenize the crude sample. be used after the expiration date and should be replaced after 7
6.2.1 Non-Aerating, High-Speed, Shear Mixer—The mixer days in the titration vessel. (Warning—Flammable, can be
shall be capable of meeting the homogenization efficiency test fatal if inhaled, swallowed, or absorbed through skin. Possible
described in Practice D5854 (API MPMS Chapter 8.3). The cancer hazard.)
sample size is limited to that suggested by the manufacturer for 8. Sampling and Test Specimens
the size of the mixing probe.
6.2.2 Circulating sample mixers, such as those used with 8.1 Sampling is defined as all the steps required to obtain an
automatic crude oil sampling receivers, are acceptable provid- aliquot representative of the contents of any pipe, tank, or other
ing they comply with the principles of Practice D5854 (API system and to place the sample into a container for analysis by
MPMS Chapter 8.3). a laboratory or test facility. The laboratory sample container
and sample volume shall be of sufficient dimensions and
6.3 Syringes: volume to allow mixing as described in 8.4.
6.3.1 Samples are most easily added to the titration vessel
by means of accurate glass syringes with LUER fittings and 8.2 Laboratory Sample—The sample of crude oil presented
hypodermic needles of suitable length. The bores of the to the laboratory or test facility for analysis by this test method.
needles used should be kept as small as possible but large
enough to avoid problems arising from back pressure and 4
Reagent Chemicals, American Chemical Society Specifications, American
blocking while sampling. Suggested syringe sizes are as Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
listed by the American Chemical Society, see Annual Standards for Laboratory
follows: Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
6.3.1.1 Syringe, 10 µL with a needle long enough to dip and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
below the surface of the anode solution in the cell when MD.

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D4928 − 11
TABLE 1 Approximate Test Specimen Size Based on Expected 9.2 Seal all joints and connections to the vessel to prevent
Water Content atmospheric moisture from entering the apparatus.
Expected Water Sample Size,
Water Titrated, µg 9.3 Add to the anode (outer) compartment the mixture of
Content, % g or mL
0.02–0.1 1.0 200–1000 xylene and Karl Fischer anode solutions which has been found
0.1–0.5 0.5 500–2500 suitable for the particular reagent and apparatus being used.
0.5–5.0 0.25 1250–12500
Add the solutions to the level recommended by the manufac-
turer.
9.4 Add to the cathode (inner) compartment the Karl Fis-
cher cathode solution to a level 2 to 3 mm below the level of
Only representative samples obtained as specified in Practice the solution in the anode compartment.
D4057 (API MPMS Chapter 8.1) and Practice D4177 (API
MPMS Chapter 8.2) shall be used to obtain the laboratory 9.5 Turn on the apparatus and start the magnetic stirrer for
sample. a smooth stirring action. Allow the residual moisture in the
titration vessel to be titrated until the end-point is reached.
NOTE 2—Examples of laboratory samples include sample bottles from
manual sampling, receptacles from automatic crude oil samplers, and NOTE 3—High background current for a prolonged period can be due to
storage containers holding a crude oil from a previous analysis. moisture on the inside walls of the titration vessel. Gentle shaking of the
vessel (or more vigorous stirring action) will wash the inside with
8.3 Test Specimen—The sample aliquot obtained from the electrolyte. Keep the titrator on to allow stabilization to a low background
laboratory sample for analysis by this test method. Once current.
drawn, the entire portion of the test specimen will be used in
the analysis. Mix the laboratory sample properly as described 10. Standardization
in 8.4 before drawing the test specimen.
10.1 In principle, standardization is not necessary since the
8.4 Mix the laboratory sample of crude oil immediately water titrated is a direct function of the coulombs of electricity
(within 15 min) before drawing the test specimen to ensure consumed. However, reagent performance deteriorates with
complete homogeneity. Mix the sample at room temperature use and shall be regularly monitored by accurately injecting
(15 to 25°C) or less in the laboratory sample container and 10 µL of pure water. Suggested intervals are initially with fresh
record the temperature of the sample in degrees Celsius reagent and then after every ten determinations (see Section
immediately before mixing. The type of mixer depends on the 11.1.3). If the result is outside 10 000 6 200 µg, replace both
quantity of crude oil in the laboratory sample container. Before the anode and cathode solutions.
any unknown mixer is used, the specifications for the homog-
enization test, Practice D5854 (API MPMS Chapter 8.3), shall 11. Procedure
be met. Reevaluate the mixer for any changes in the type of
crude, volume of crude in the container, the shape of the 11.1 Mass Determination of Sample Size:
container, or the mixing conditions (such as mixing speed and 11.1.1 Add fresh solvents to the anode and cathode com-
time of mixing). partments of the titration vessel and bring the solvent to
end-point conditions as described in Section 9.
8.5 For small laboratory sample containers and volumes, 50
11.1.2 Add an aliquot of the crude oil test specimen to the
to 500 mL, a non-aerating, high-speed, shear mixer is required.
titration vessel immediately after the mixing step described in
Use the mixing time, mixing speed, and height of the mixer
8.4 using the following method.
probe above the bottom of the container found to be satisfac-
tory in Practice D5854 (API MPMS Chapter 8.3). For larger 11.1.2.1 Starting with a clean, dry syringe of suitable
containers and volumes, appropriate mixing conditions shall be capacity (see Table 1 and Note 4), withdraw at least three
defined by following a set of procedures similar to those portions of the sample and discard to waste. Immediately
outlined in Practice D5854 (API MPMS Chapter 8.3) and withdraw a further portion of sample, clean the needle with a
Practice D4177 (API MPMS Chapter 8.2) but modified for paper tissue, and weigh the syringe and contents to the nearest
application to the larger containers and volumes. Clean and dry 0.1 mg. Insert the needle through the inlet port septum, start the
the mixer between samples. titration and with the tip of the needle just below the liquid
surface, inject the sample. Withdraw the syringe and reweigh
8.6 Record the temperature of the sample in degrees Celsius the syringe to the nearest 0.1 mg. After the end-point is
immediately after homogenization. The rise in temperature reached, record the titrated water from the digital readout on
between this reading and the initial reading before mixing (8.4) the instrument.
is not to exceed 10°C, otherwise loss of water can occur or the
emulsion can become unstable. NOTE 4—If the concentration of water in the sample is completely
unknown, it is advisable to start with a small trial portion of sample to
8.7 Select the test specimen size as indicated in Table 1 avoid excessive titration time and depletion of the reagents. Further
based on the expected water content. adjustment of the aliquot size can then be made as necessary.
11.1.2.2 When the background current or titration rate
9. Preparation of Apparatus returns to a stable reading at the end of the titration as
9.1 Follow the manufacturer’s directions for preparation discussed in 9.5, additional samples can be added in accor-
and operation of the titration apparatus. dance with 11.1.2.1.

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D4928 − 11
11.1.3 Replace the solutions when one of the following TABLE 2 Precision Intervals
occurs and then repeat the preparation of the apparatus as in % Water Repeatability (r) Reproducibility (R)
Section 9. (Mass or Volume) Mass Volume Mass Volume
11.1.3.1 Persistently high and unstable background current. 0.01 0.002 0.003 0.005 0.005
0.02 0.003 0.004 0.008 0.008
11.1.3.2 Phase separation in the anode compartment or 0.05 0.005 0.008 0.014 0.015
crude oil coating the electrodes. 0.1 0.01 0.01 0.02 0.02
11.1.3.3 The total crude content added to the titration vessel 0.3 0.02 0.03 0.05 0.05
0.5 0.03 0.04 0.07 0.07
exceeds one quarter of the volume of solution in the anode 0.7 0.03 0.04 0.08 0.09
compartment. 1.0 0.04 0.06 0.11 0.11
1.5 0.05 0.07 0.14 0.15
11.1.3.4 The solutions in the titration vessel are greater than 2.0 0.06 0.09 0.17 0.18
one week old. 2.5 0.07 0.10 0.19 0.21
11.1.3.5 The instrument displays error messages that di- 3.0 0.08 0.12 0.22 0.23
3.5 0.09 0.13 0.24 0.26
rectly or indirectly suggest replacement of the electrodes—see 4.0 0.10 0.14 0.26 0.28
the instrument operating manual. 4.5 0.11 0.15 0.29 0.31
11.1.3.6 The result from a 10-µL injection of water is 5.0 0.12 0.16 0.31 0.33

outside 10 000 6 200 µg.

11.1.4 Thoroughly clean the anode and cathode compart-
ments with xylene if the vessel becomes contaminated with
W1
crude. Never use acetone or similar ketones. Water, mass % 5 3 100 (1)
W2
NOTE 5—Clogging of the frit separating the vessel compartments will
also cause instrument malfunction. where:
W1 = mass of water titrated, µg and
11.1.5 For crudes too viscous to draw into a syringe, add the W2 = mass of sample used, µg.
sample to a clean, dry dropper bottle and weigh the bottle and
crude. Quickly transfer the required amount of sample to the 12.2 Calculate the volume % water in a crude oil sample as
titration vessel with the dropper. Reweigh the bottle. Titrate the follows:
sample as in 11.2. V1
Water content, volume % 5 3 100 (2)
11.2 Volume Determination of Sample Size: V2
11.2.1 This procedure is applicable only when conditions where:
warrant, that is, when the vapor pressure and viscosity of the V1 = volume of water titrated, µL
crude permit an accurate determination of the volume of the
W1
crude oil. Viscous crudes are difficult to measure accurately 5
1000
with a syringe.
, where W1 is as defined in 12.1, and
11.2.2 Take care in filling the syringe to reduce the forma- V2 = volume of sample used, µL.
tion of gas bubbles.
NOTE 6—The presence of gas bubbles in the syringe can be a source of 13. Report
interference. The tendency of the crude to form gas bubbles is a function 13.1 When determining % water by mass, report the water
of the crude type and corresponding vapor pressure.
content to the nearest 0.01 mass %.
11.2.3 The referee procedure for determination of water in 13.2 When determining % water by volume, report the
crude oil by coulometric Karl Fischer titration is the mass water content to the nearest 0.01 volume %.
measurement of the crude oil in 11.1.
11.2.4 The basic steps are the same as those for mass 14. Precision and Bias
determination (see 11.1) with the following exception. With a
14.1 The precision of this test method as determined by the
clean, dry syringe of suitable capacity (see Table 1), withdraw
statistical examination of interlaboratory test results is as
at least three portions of sample and discard to waste. Imme-
follows:5
diately withdraw a further portion of sample, expel any gas in
14.1.1 Repeatability—The difference between successive
the syringe, clean the needle with a paper tissue, and record the
results obtained by the same operator with the same apparatus
volume in the syringe to the nearest 1 or 10 µL as appropriate
under constant operating conditions on identical test material
(see 6.3.1.2). Insert the needle through the port inlet septum,
would, in the long run, in the normal and correct operation of
start the titration, and with the tip of the needle just below the
the test method, exceed the following values only in one case
liquid surface, inject the entire contents of the syringe. After
in twenty (see Table 2).
the end-point is reached, record from the digital readout on the
14.1.1.1 For determinations of water by mass,
instrument the micrograms titrated.
r 5 0.040 ~ X 2/3 ! (3)
12. Calculation
12.1 Calculate the mass % water in a crude oil sample as 5
Supporting data have been filed at ASTM International Headquarters and may
follows: be obtained by requesting Research Report RR:D02-1246.

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D4928 − 11
where: where:
X = sample mean from 0.02 to 5 mass %. X = sample mean from 0.02 to 5 volume %.
14.1.1.2 For determinations of water by volume, 14.2 Bias:
14.2.1 No significant difference was found between the
r 5 0.056 ~ X 2/3 ! (4)
average water content obtained by this test method and the
where: expected water content (based on the amount of added water)
X = sample mean from 0.02 to 5 volume %. for the crude oil samples analyzed in the round robin used to
evaluate the precision of this test method.5
14.1.2 Reproducibility—The difference between two single 14.2.2 The interference from mercaptan sulfur follows the
and independent results obtained by different operators work- theoretical stoichiometry of 1 to 0.28, that is 1000 µg/g (ppm)
ing in different laboratories on identical test material would, in of mercaptan sulfur can generate a response equivalent to
the long run, exceed the following values only in one case in 280 µg/g (ppm) water by this test method. The interference
twenty (see Table 2). from H2S sulfur follows the stoichiometry of 1 to 0.56, that is
14.1.2.1 For determinations of water by mass, 1000 µg/g (ppm) of hydrogen sulfide sulfur can generate a
R 5 0.105 ~ X 2/3 response equivalent to 560 µg/g (ppm) water by this test
! (5)
method. The validity of correcting measured water contents for
where: known mercaptan/sulfide levels has not yet been determined.
X = sample mean from 0.02 to 5 mass %.
15. Keywords
14.1.2.2 For determinations of water by volume, 15.1 coulometric; crude oils; homogenization; Karl Fischer;
R 5 0.112 ~ X 2/3
! (6) shear mixer; titration; water; water in crude oils

SUMMARY OF CHANGES

Subcommittee D02.02.08 has identified the location of selected changes to this standard since the last issue
(D4928–00 (2010)) that may impact the use of this standard.

(1) Corrected the description for V1 in Eq 2 in 12.2.

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