NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.

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Designation: D4377 − 00 (Reapproved 2011)

Manual of Petroleum Measurement Standards (MPMS), Chapter 10.7

Designation: 356/99

Standard Test Method for

Water in Crude Oils by Potentiometric Karl Fischer Titration1
This standard is issued under the fixed designation D4377; 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 U.S. Department of Defense.

1. Scope 2.2 API Standards:3

1.1 This test method covers the determination of water in MPMS Chapter 8.1 Manual Sampling of Petroleum and
the range from 0.02 to 2 % in crude oils. Mercaptan and sulfide Petroleum Products (ASTM Practice D4057)
(S− or H2S) sulfur are known to interfere with this test method MPMS Chapter 8.2 Automatic Sampling of Petroleum and
(see Section 5). Petroleum Products (ASTM Practice D4177)
MPMS Chapter 10.2 Determination of Water in Crude Oil by
1.2 This test method is intended for use with standard Karl Distillation (ASTM Test Method D4006)
Fischer reagent or pyridine-free Karl Fischer reagents.

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1.3 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this
3. Summary of Test Method
3.1 After homogenizing the crude oil with a mixer, an
standard.
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1.4 This standard does not purport to address all of the
aliquot of the crude, in a mixed solvent, is titrated to an
electrometric end-point using Karl Fischer reagent.

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safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- 4. Significance and Use
priate safety and health practices and determine the applica- 4.1 A knowledge of the water content of crude oil is
bility of regulatory limitations prior to use. Specific precau- important in the refining, purchase, sale, or transfer of crude
tionary statements are given in Section 7. ASTM D4377-00(2011)
oils.
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2. Referenced Documents 5. Interferences
2.1 ASTM Standards:2 5.1 A number of substances and class of compounds asso-
D1193 Specification for Reagent Water ciated with condensation or oxidation-reduction reactions in-
D4006 Test Method for Water in Crude Oil by Distillation terfere in the determination of water by Karl Fischer. In crude
D4057 Practice for Manual Sampling of Petroleum and oils, the most common interferences are mercaptans and
Petroleum Products sulfides. At levels of less than 500 µg/g (ppm) (as sulfur) the
D4177 Practice for Automatic Sampling of Petroleum and interference from these compounds is insignificant. For more
Petroleum Products information on substances that interfere in the determination of
E203 Test Method for Water Using Volumetric Karl Fischer water using the (Karl Fischer reagent) titration method see Test
Titration Method E203.

1
This test method is under the jurisdiction of ASTM Committee D02 on 6. Apparatus
Petroleum Products, Liquid Fuels, and Lubricants and the API Committee on
Petroleum Measurement, and is the direct responsibility of Subcommittee D02.02
6.1 Karl Fischer Apparatus, using electrometric end-point.
/COMQ on Hydrocarbon Measurement for Custody Transfer (Joint ASTM-API). A suggested assembly of the apparatus is described in Annex
Current edition approved June 1, 2011. Published August 2011. Originally A2.
approved in 1984. Last previous edition approved in 2006 as D4377–00(2006).
DOI: 10.1520/D4377-00R11.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
3
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Published as Manual of Petroleum Measurement Standards. Available from
Standards volume information, refer to the standard’s Document Summary page on American Petroleum Institute (API), 1220 L. St., NW, Washington, DC 20005-4070,
the ASTM website. http://api-ec.api.org.

© Jointly copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, USA and the American Petroleum Institute (API), 1220 L Street NW, Washington DC 20005, USA

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 D4377 − 00 (2011)
6.1.1 Presently there is available on the market commercial 7.4.2 Pyridine-Free Karl Fischer (one-component) reagent
Karl Fischer titration assemblies, some of which automatically diluted with xylene—Dilute three parts pyridine-free Karl
stop the titration at the end-point. Instructions for operation of Fischer (one-component) reagent6 (1 mL = 5 mg water) to 1
these devices are provided by the manufacturer and not part xylene. Fresh Karl Fischer reagent must be used.
described herein. This test method is not intended for use with (Warning—See 7.4.1) Must be used with solvent in 7.6.2.
coulometric Karl Fischer titrators. 7.5 Methanol (anhydrous), Maximum 0.1 % water but pref-
6.2 Mixer, to homogenize the crude sample. erably less than 0.05 % water. (Warning—Flammable. Vapor
6.2.1 Non-Aerating, High-Speed, Shear Mixer,4capable of harmful. May be fatal or cause blindness if swallowed or
meeting the homogenization efficiency test described in Annex inhaled. Cannot be made nonpoisonous.)
A1. The sample size is limited to that suggested by the 7.6 Sample Solvent—Use 7.6.1 for standard Karl Fischer
manufacturer for the size of the probe. reagent containing pyridine and 7.6.2 for pyridine-free Karl
6.3 Syringes: Fischer reagent.
6.3.1 Samples and base liquid are most easily added to the 7.6.1 Sample Solvent—Mix 40 mL of 1-ethylpiperidine, 20
titration vessel by means of accurate glass syringes with LUER mL of methanol, and 40 mL of Karl Fischer reagent in a
fittings and hypodermic needles of suitable length. The bores sealable glass bottle. Allow this mixture to sit overnight before
of the needles used should be kept as small as possible, but adding 200 mL of xylene. Additional methanol may be
large enough to avoid problems arising from back pressure/ required in some cases for the proper function of the elec-
blocking whilst sampling. Suggested syringe sizes are as trodes. (Warning—see 7.3.)
follows: 7.6.2 Sample Solvent for Pyridine-Free Reagents—Mix 3
6.3.1.1 Syringe, 10 µL, with a needle long enough to dip parts chloroform to 1 part pyridine-free solvent using solvent
below the surface of the base solution in the cell during the part of two-component reagent6 (contains SO2 and odorless
standardization procedure (see Section 9). amine dissolved in methanol) and store in a sealable glass
6.3.1.2 Syringes, 2.5 mL, 5 mL, and 10 mL for crude oil bottle. An evaluation of a number of crude oils has demon-
samples (see Section 10). strated that xylene can be substituted for chloroform with no

7. Reagents and Materials

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6.3.1.3 Syringe, 20 mL or larger for sample solvent. apparent change in accuracy of this test method. (Warning—
Flammable. Vapor harmful.) (Also, see 7.4.1.)

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7.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
7.7 Xylene, reagent grade. Less than 0.05 % water.
7.8 Chloroform, reagent grade. (Warning—Harmful if in-

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all reagents shall conform to the specifications of the Commit- haled or swallowed. Carcinogen (animal positive). Skin and
tee on Analytical Reagents of the American Chemical Society, eye irritant. May produce toxic vapors if burned.
where such specifications are available.5 Other grades may be 8. Sampling and Test Samples
used, provided it is first ascertained that the reagent is of
ASTM D4377-00(2011)
sufficiently high purity to permit its use without lessening the 8.1 Sampling, is defined as all the steps required to obtain an
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accuracy of the determination. aliquot representative of the contents of any pipe, tank, or other
system, and to place the sample into the laboratory test
7.2 Purity of Water—Unless otherwise indicated, references container. The laboratory test container and sample volume
to water shall be understood to mean reagent water as defined shall be of sufficient dimensions and volume to allow mixing as
by Type IV of Specification D1193. described in 8.1.2.1.
7.3 1-Ethylpiperidine (99 + percent). (Warning—Irritant. 8.1.1 Laboratory Sample—Only representative samples ob-
Flammable.) tained as specified in Practice D4057 (API MPMS Chapter 8.1)
7.4 Karl Fischer Reagents, Standard reagent containing and Practice D4177 (API MPMS Chapter 8.2) shall be used for
pyridine (7.4.1) or pyridine-free reagent (7.4.2). this test method.
7.4.1 Karl Fischer Reagent Ethylene Glycol Monomethyl 8.1.2 Test Samples—The following sample handling proce-
Ether Solution, stabilized, containing pyridine, (1 mL = 5 mg dure shall apply in addition to those covered in 8.1.1.
of water)—Fresh Karl Fischer reagent must be used. Must be 8.1.2.1 Mix the test sample of crude oil immediately (within
used with solvent in 7.6.1. (Warning—Combustible. Harmful 15 min) before analysis to insure complete homogeneity. Mix
if swallowed, inhaled, or absorbed through the skin.) the test sample at room temperature (25°C) in the original
container.
4
The following mixers were used in a cooperative program and have been found NOTE 1—The sample should be mixed at room temperature (25°C) or
satisfactory for samples under 300 mL; Ultra Turrax Model TP 18/10, available less. Mixing of the sample should not increase the temperature of the
from Tekmar Co., P. O. Box 37202, Cincinnati, OH 45222; Brinkman Polytron sample more than 10°C, or a loss of water may occur. The type of mixer
Model PT 35, Available from Brinkman Instruments Inc., Cantiagu Road, Westbury, depends on the quantity of crude. Before any unknown mixer is used, the
NY 11590; and Kraft Apparatus Model S-25, SGA, Bloomfield, NJ.
5
Reagent Chemicals, American Chemical Society Specifications, American
6
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not Pyridine-free Karl Fischer reagent and two-component solvent used in the
listed by the American Chemical Society, see Annual Standards for Laboratory cooperative program and found to be satisfactory are available from Crescent
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia Chemical Co., Inc., 1324 Motor Parkway, Hauppauge, NY 11788 under the name of
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, Hydranal a registered trademark of Riedel Dehaen—Composite 5 and Hydranal—
MD. solvent.

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 D4377 − 00 (2011)
TABLE 1 Test Sample—% Water Content Based on Sample Size immediately. Remove any solvent from the needle by wiping
Expected Water Sample Size, with a paper tissue and reweigh the syringe to 0.1 mg. Titrate
Content, % g the water with Karl Fischer reagent as in 9.3.1.
0–0.3 5
0.3–1 2 9.4 Calculate the water equivalence of the Karl Fischer
1–2 1
reagent as follows:
F 5 W/T (1)
specifications for the homogenization test, Annex A1, must be met. The where:
mixer must be re-evaluated for any changes in the type of crude, quantity
of crude, or shape of the sample container. F = water equivalence of the Karl Fischer reagent, mg/mL,
(1) For small sample volumes, 50 to 500 mL, a non- W = water added, mg, and
aerating, high speed, shear mixer is required. Use the mixing T = reagent required for titration of the added water, mL.
time, mixing speed, and height above the bottom of the 9.5 Duplicate values of water equivalence should agree
container found to be satisfactory to Annex A1. Clean and dry within 2 % relative. If the variation between the two titrations
the mixer between samples. is greater than 2 % relative, discard the contents of the titration
8.1.2.2 The test sample size is selected as indicated in Table vessel. Introduce a further portion of sample solvent into the
1 based on the expected water content. vessel and repeat the standardization procedure. If the titrations
for two further portions of distilled water still vary by more
9. Calibration and Standardization than 2 %, it is likely that either the Karl Fischer reagent or the
9.1 Standardize the Karl Fischer reagent at least once daily. sample solvent, or both, have aged. Replace these with fresh
reagents and repeat the procedure for calibration and standard-
9.2 Add enough solvent to the clean, dry titration vessel to ization.
cover the electrodes. The volume of solvent depends on the
size of the titration vessel. Seal all openings to the vessel and 9.6 Determine and record the mean water equivalence
start the magnetic stirrer for a smooth stirring action. Turn on value.
the indicating circuit and adjust the potentiometer to give a
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reference point with approximately 1 µA of current flowing.
Add Karl Fischer reagent in suitable amounts to the solvent to
10. Procedure
10.1 Add the fresh sample solvent to the titration vessel and

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cause the needle to deflect from the reference point. At first the
needle will deflect due to local concentration of the unreacted
bring the solvent to end-point conditions as described in 9.2.
10.2 Add the crude to the titration vessel immediately after
reagent about the electrodes but will fall back to near the
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reference point. As the end-point is approached, the needle will
fall back more slowly after each addition of Karl Fischer
the mixing step described in 8.1.2.1 using one of the following
methods:
10.2.1 Starting with a clean, dry syringe (10 or 5 mL), rinse
reagent. The end-point is reached when, after the addition of a the syringe two times with the sample and discharge to waste.
ASTM
single drop of reagent, the needle remains deflected D4377-00(2011)
at least 1 Withdraw the required amount of sample and discharge any air
µA from the reference point for at least 30 s. Swirl the titration
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vessel to dry the inside walls of the vessel. Add more Karl
bubbles. Weigh the syringe to the nearest 0.1 mg. Inject the
sample into the titration vessel, clean the needle with a paper
Fischer reagent, if needed, until a steady end-point is reached tissue, and reweigh the syringe. Titrate the sample until a
for at least 30 s. steady end-point for at least 30 s is reached and record the
9.3 Standardize the Karl Fischer reagent with distilled water volume of Karl Fischer reagent to the nearest 0.01 mL (see
by one of the following methods: Note 2 and Note 4).
9.3.1 From a water filled weighing pipet or syringe previ-
NOTE 4—The solvent should be changed when the sample content
ously weighed to the nearest 0.1 mg, add 1 drop of distilled exceeds 2 g of crude per 15 mL of solvent or when 4 mL of titrant per 15
water (about 20 mg) to the sample solvent at end-point mL of solvent has been added to the titration vessel.
conditions and reweigh the syringe. Record the weight of the 10.2.2 For viscous crudes, add the sample to a clean, dry
water added. Titrate the water with Karl Fischer reagent added dropper bottle and weigh the bottle and crude. Quickly transfer
from the buret until a steady end point is reached for at least 30 the required amount of sample to the titration vessel with the
s. Record to the nearest 0.01 mL the volume of the Karl Fischer dropper. Reweigh the bottle. Titrate the sample as in 10.2.1.
reagent needed to reach the end-point.
NOTE 5—After adding the sample do not shake the cell.
NOTE 2—After adding water do not shake the cell.
NOTE 3—When wiping the needle exercise care, so not to siphon liquid
through the tip of the needle.
11. Calculations
9.3.2 Fill a 10-µL syringe with water taking care to elimi- 11.1 Calculate the water content of the sample as follows:
nate air bubbles, wipe the needle with a paper tissue to remove water, mass % 5 CF/W ~ 10! (2)
any residual water from the needle and accurately determine
where:
the weight of syringe plus water to 0.1 mg. Add the contents of
the syringe to the sample solvent in the cell which has been C = Karl Fischer reagent required to titrate the sample, mL,
adjusted to the end point ensuring that the tip of the needle is F = water equivalence of Karl Fischer reagent, mg/mL,
W = sample used, g, and
below the surface of the sample solvent. Reseal the vessel