ASTM D6304-07

Standard Test Method for Determination of Water in Petroleum Products, Lubricating Oils, and Additives by Coulometric Karl Fischer Titration (Withdrawn 2016)

SIGNIFICANCE AND USE
A knowledge of the water content of lubricating oils, additives, and similar products is important in the manufacturing, purchase, sale, or transfer of such petroleum products to help in predicting their quality and performance characteristics.
For lubricating oils, the presence of moisture could lead to premature corrosion and wear, an increase in the debris load resulting in diminished lubrication and premature plugging of filters, an impedance in the effect of additives, and undesirable support of deleterious bacterial growth.
SCOPE
1.1 This test method covers the direct determination of water in the range of 10 to 25 000 mg/kg entrained water in petroleum products and hydrocarbons using automated instrumentation. This test method also covers the indirect analysis of water thermally removed from samples and swept with dry inert gas into the Karl Fischer titration cell. Mercaptan, sulfide (S  or H2S), sulfur, and other compounds are known to interfere with this test method (see Section 5).
1.2 This test method is intended for use with commercially available coulometric Karl Fischer reagents and for the determination of water in additives, lube oils, base oils, automatic transmission fluids, hydrocarbon solvents, and other petroleum products. By proper choice of the sample size, this test method may be used for the determination of water from mg/kg to percent level concentrations.
1.3 The values stated in SI units are to be regarded as standard. No other units of measurements are included in this standard.
This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
WITHDRAWN RATIONALE
This test method covers the direct determination of water in the range of 10 to 25 000 mg/kg entrained water in petroleum products and hydrocarbons using automated instrumentation. This test method also covers the indirect analysis of water thermally removed from samples and swept with dry inert gas into the Karl Fischer titration cell. Mercaptan, sulfide (S− or H2S), sulfur, and other compounds are known to interfere with this test method.
Formerly under the jurisdiction of Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants, this test method was withdrawn in April 2016 in accordance with section 10.5.3.1 of the Regulations Governing ASTM Technical Committees, which requires that standards shall be updated by the end of the eighth year since the last approval date.

General Information

• Status: Historical
• Publication Date: 14-Jul-2007
• Withdrawal Date: 04-Apr-2016
• ICS: 71.040.50 - Physicochemical methods of analysis
• ICS: 75.080 - Petroleum products in general
• ICS: 75.100 - Lubricants, industrial oils and related products
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.02.10 - Sediment and Water (API MPMS Chapter 10.0)

Relations

• Replaces: ASTM D6304-04ae1 - Standard Test Method for Determination of Water in Petroleum Products, Lubricating Oils, and Additives by Coulometric Karl Fisher Titration
• Effective Date: 15-Jul-2007
• Referred By: ASTM D6448-16(2022) - Standard Specification for Industrial Burner Fuels from Used Lubricating Oils
• Effective Date: 15-Jul-2007
• Referred By: ASTM D4814-23 - Standard Specification for Automotive Spark-Ignition Engine Fuel
• Effective Date: 15-Jul-2007
• Referred By: ASTM D8279-23 - Standard Test Method for Determination of Timing-Chain Wear in a Turbocharged, Direct-Injection, Spark-Ignition, Four-Cylinder Engine
• Effective Date: 15-Jul-2007
• Referred By: ASTM D8185-18 - Standard Guide for In-Service Lubricant Viscosity Measurement
• Effective Date: 15-Jul-2007
• Referred By: ASTM D7590-22 - Standard Guide for Measurement of Remaining Primary Antioxidant Content In In-Service Industrial Lubricating Oils by Linear Sweep Voltammetry
• Effective Date: 15-Jul-2007
• Referred By: ASTM D6710-21 - Standard Guide for Evaluation of Hydrocarbon-Based Quench Oil
• Effective Date: 15-Jul-2007
• Referred By: ASTM D4304-22 - Standard Specification for Mineral and Synthetic Lubricating Oil Used in Steam or Gas Turbines
• Effective Date: 15-Jul-2007
• Referred By: ASTM D8323-20 - Standard Guide for Management of In-Service Phosphate Ester-based Fluids for Steam Turbine Electro-Hydraulic Control (EHC) Systems
• Effective Date: 15-Jul-2007
• Referred By: ASTM D8235-21 - Standard Specification for Ethyl Tertiary-Butyl Ether (ETBE) for Blending with Gasolines for Use as Automotive Spark-Ignition Engine Fuel
• Effective Date: 15-Jul-2007
• Referred By: ASTM D4378-22 - Standard Practice for In-Service Monitoring of Mineral Turbine Oils for Steam, Gas, and Combined Cycle Turbines
• Effective Date: 15-Jul-2007
• Referred By: ASTM D7720-21 - Standard Guide for Statistically Evaluating Measurand Alarm Limits when Using Oil Analysis to Monitor Equipment and Oil for Fitness and Contamination
• Effective Date: 15-Jul-2007
• Referred By: ASTM D7754-19 - Standard Test Method for Determination of Trace Oxygenates in Automotive Spark-Ignition Engine Fuel by Multidimensional Gas Chromatography
• Effective Date: 15-Jul-2007
• Referred By: ASTM D7973-19 - Standard Guide for Monitoring Failure Mode Progression in Plain Bearings
• Effective Date: 15-Jul-2007
• Referred By: ASTM D4054-23 - Standard Practice for Evaluation of New Aviation Turbine Fuels and Fuel Additives
• Effective Date: 15-Jul-2007

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D6304 − 07
StandardTest Method for
Determination of Water in Petroleum Products, Lubricating
1
Oils, and Additives by Coulometric Karl Fischer Titration
This standard is issued under the fixed designation D6304; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber 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* ucts by Hydrometer Method
D4052Test Method for Density, Relative Density, and API
1.1 This test method covers the direct determination of
Gravity of Liquids by Digital Density Meter
water in the range of 10 to 25 000 mg/kg entrained water in
D4057Practice for Manual Sampling of Petroleum and
petroleum products and hydrocarbons using automated instru-
Petroleum Products
mentation.Thistestmethodalsocoverstheindirectanalysisof
D4177Practice for Automatic Sampling of Petroleum and
water thermally removed from samples and swept with dry
Petroleum Products
inert gas into the Karl Fischer titration cell. Mercaptan, sulfide
− D5854Practice for Mixing and Handling of Liquid Samples
(S or H S), sulfur, and other compounds are known to
2
of Petroleum and Petroleum Products
interfere with this test method (see Section 5).
E203Test Method for Water Using Volumetric Karl Fischer
1.2 This test method is intended for use with commercially
Titration
available coulometric Karl Fischer reagents and for the deter-
mination of water in additives, lube oils, base oils, automatic
3. Summary of Test Method
transmissionfluids,hydrocarbonsolvents,andotherpetroleum
3.1 An aliquot is injected into the titration vessel of a
products.Byproperchoiceofthesamplesize,thistestmethod
coulometricKarlFischerapparatusinwhichiodinefortheKarl
may be used for the determination of water from mg/kg to
Fisher reaction is generated coulometrically at the anode.
percent level concentrations.
When all of the water has been titrated, excess iodine is
1.3 The values stated in SI units are to be regarded as
detectedbyanelectrometricendpointdetectorandthetitration
standard. No other units of measurement are included in this
isterminated.Basedonthestoichiometryofthereaction,1mol
standard.
ofiodinereactswith1molofwater;thus,thequantityofwater
1.4 This standard does not purport to address all of the is proportional to the total integrated current according to
safety concerns, if any, associated with its use. It is the Faraday’s Law.
responsibility of the user of this standard to establish appro-
3.2 The sample injection can be done either by mass or
priate safety and health practices and determine the applica-
volume.
bility of regulatory limitations prior to use.
3.3 The viscous samples can be analyzed by using a water
vaporizer accessory that heats the sample in the evaporation
2. Referenced Documents
chamber, and the vaporized water is carried into the Karl
2
2.1 ASTM Standards:
Fischer titration cell by a dry inert carrier gas.
D1193Specification for Reagent Water
D1298Test Method for Density, Relative Density, or API
4. Significance and Use
Gravity of Crude Petroleum and Liquid Petroleum Prod-
4.1 A knowledge of the water content of lubricating oils,
additives, and similar products is important in the
manufacturing, purchase, sale, or transfer of such petroleum
1
This test method is under the jurisdiction of ASTM Committee D02 on
products to help in predicting their quality and performance
Petroleum Products, Liquid Fuels, and Lubricantsand is the direct responsibility of
Subcommittee D02.02.10 on Sediment and Water (API MPMS Chapter 10.0).
characteristics.
Current edition approved July 15, 2007. Published August 2007. Originally
ε1
4.2 For lubricating oils, the presence of moisture could lead
approved in 1998. Last previous edition approved in 2004 as D6304–04a . DOI:
10.1520/D6304-07.
toprematurecorrosionandwear,anincreaseinthedebrisload
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
resulting in diminished lubrication and premature plugging of
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
filters, an impedance in the effect of additives, and undesirable
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. support of deleterious bacterial growth.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
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D6304 − 07
TABLE 1 Test Sample Size Based on Expected Water Content
capacities: 250 µL accurate to the nearest
...

This document is not anASTM standard and is intended only to provide the user of anASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately,ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
An American National Standard Designation: D6304 – 07
´1
Designation:D 6304–04a
Standard Test Method for
Determination of Water in Petroleum Products, Lubricating
1
Oils, and Additives by Coulometric Karl Fischer Titration
This standard is issued under the fixed designation D6304; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
1
superscript epsilon (´) indicates an editorial change since the last revision or reapproval. ´ NOTE—Editorial changes were made
throughout in March 2005.
1. Scope*
1.1 This test method covers the direct determination of water in the range of 10 to 25 000 mg/kg entrained water in petroleum
products and hydrocarbons using automated instrumentation.This test method also covers the indirect analysis of water thermally
−
removed from samples and swept with dry inert gas into the Karl Fischer titration cell. Mercaptan, sulfide (S or H S), sulfur, and
2
other compounds are known to interfere with this test method (see Section 5).
1.2 This test method is intended for use with commercially available coulometric Karl Fischer reagents and for the
determination of water in additives, lube oils, base oils, automatic transmission fluids, hydrocarbon solvents, and other petroleum
products. By proper choice of the sample size, this test method may be used for the determination of water from mg/kg to percent
level concentrations.
1.3Values stated in SI units are to be regarded as the standard.
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory
limitations prior to use.
2. Referenced Documents
2
2.1 ASTM Standards:
D1193 Specification for Reagent Water
D1298 TestMethodforDensity,RelativeDensity(SpecificGravity),orAPIGravityofCrudePetroleumandLiquidPetroleum
Products by Hydrometer Method
D4052 Test Method for Density and Relative Density of Liquids by Digital Density Meter Test Method for Density, Relative
Density, and API Gravity of Liquids by Digital Density Meter
D4057 Practice for Manual Sampling of Petroleum and Petroleum Products
D4177 Practice for Automatic Sampling of Petroleum and Petroleum Products
D5854 Practice for Mixing and Handling of Liquid Samples of Petroleum and Petroleum Products
E203 Test Method for Water Using Volumetric Karl Fischer Titration
3. Summary of Test Method
3.1 An aliquot is injected into the titration vessel of a coulometric Karl Fischer apparatus in which iodine for the Karl Fisher
reaction is generated coulometrically at the anode. When all of the water has been titrated, excess iodine is detected by an
electrometric end point detector and the titration is terminated. Based on the stoichiometry of the reaction, 1 mol of iodine reacts
with 1 mol of water; thus, the quantity of water is proportional to the total integrated current according to Faraday’s Law.
3.2 The sample injection can be done either by mass or volume.
3.3 Theviscoussamplescanbeanalyzedbyusingawatervaporizeraccessorythatheatsthesampleintheevaporationchamber,
and the vaporized water is carried into the Karl Fischer titration cell by a dry inert carrier gas.
4. Significance and Use
4.1 A knowledge of the water content of lubricating oils, additives, and similar products is important in the manufacturing,
1
This test method is under the jurisdiction ofASTM Committee D02 on Petroleum Products and Lubricants and is the direct responsibility of Subcommittee D02.02.0B
on Static Petroleum Measurement.Sampling, Sediment, Water.
Current edition approved May 1, 2004.July 15, 2007. Published June 2004.August 2007. Originally approved in 1998. Last previous edition approved in 2004 as D
´1
6304–04D6304–04a . . DOI: 10.1520/D6304-07.
2
ForreferencedASTMstandards,visittheASTMwebsite,www.astm.org,[e-mail] Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
*A Summary of Changes section appears at the end of this standard.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
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