ASTM Standards

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles
for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D445 − 19a British Standard 2000: Part 71: Section 1: 1996
Designation: 71 Section 1/97
Standard Test Method for

Kinematic Viscosity of Transparent and Opaque Liquids
(and Calculation of Dynamic Viscosity)1
This standard is issued under the fixed designation D445; 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* 1.5 WARNING—Mercury has been designated by many

1.1 This test method specifies a procedure for the determi- regulatory agencies as a hazardous substance that can cause
nation of the kinematic viscosity, ν, of liquid petroleum serious medical issues. Mercury, or its vapor, has been dem-
products, both transparent and opaque, by measuring the time onstrated to be hazardous to health and corrosive to materials.
for a volume of liquid to flow under gravity through a Use Caution when handling mercury and mercury-containing
calibrated glass capillary viscometer. The dynamic viscosity, η, products. See the applicable product Safety Data Sheet (SDS)
can be obtained by multiplying the kinematic viscosity, ν, by for additional information. The potential exists that selling
the density, ρ, of the liquid. mercury or mercury-containing products, or both, is prohibited
by local or national law. Users must determine legality of sales
NOTE 1—For the measurement of the kinematic viscosity and viscosity in their location.
of bitumens, see also Test Methods D2170 and D2171.
NOTE 2—ISO 3104 corresponds to Test Method D445 – 03. 1.6 This standard does not purport to address all of the
1.2 The result obtained from this test method is dependent safety concerns, if any, associated with its use. It is the
upon the behavior of the sample and is intended for application responsibility of the user of this standard to establish appro-
to liquids for which primarily the shear stress and shear rates priate safety, health, and environmental practices and deter-
are proportional (Newtonian flow behavior). If, however, the mine the applicability of regulatory limitations prior to use.
viscosity varies significantly with the rate of shear, different 1.7 This international standard was developed in accor-
results may be obtained from viscometers of different capillary dance with internationally recognized principles on standard-
diameters. The procedure and precision values for residual fuel ization established in the Decision on Principles for the
oils, which under some conditions exhibit non-Newtonian Development of International Standards, Guides and Recom-
behavior, have been included. mendations issued by the World Trade Organization Technical
1.3 The range of kinematic viscosities covered by this test Barriers to Trade (TBT) Committee.
method is from 0.2 mm2/s to 300 000 mm2/s (see Table A1.1)
at all temperatures (see 6.3 and 6.4). The precision has only 2. Referenced Documents
been determined for those materials, kinematic viscosity 2.1 ASTM Standards:2
ranges and temperatures as shown in the footnotes to the D396 Specification for Fuel Oils
precision section. D446 Specifications and Operating Instructions for Glass
1.4 The values stated in SI units are to be regarded as Capillary Kinematic Viscometers
standard. The SI unit used in this test method for kinematic D1193 Specification for Reagent Water
viscosity is mm2/s, and the SI unit used in this test method for D1217 Test Method for Density and Relative Density (Spe-
dynamic viscosity is mPa·s. For user reference, 1 mm2/s = cific Gravity) of Liquids by Bingham Pycnometer
10-6 m2/s = 1 cSt and 1 mPa·s = 1 cP = 0.001 Pa·s. D1480 Test Method for Density and Relative Density (Spe-
cific Gravity) of Viscous Materials by Bingham Pycnom-
1
This test method is under the jurisdiction of ASTM Committee D02 on eter
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
Subcommittee D02.07 on Flow Properties.
Current edition approved Dec. 1, 2019. Published January 2020. Originally
2
approved in 1937. Last previous edition approved in 2018 as D445 – 19. DOI: For referenced ASTM standards, visit the ASTM website, www.astm.org, or
10.1520/D0445-19A. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
In the IP, this test method is under the jurisdiction of the Standardization Standards volume information, refer to the standard’s Document Summary page on
Committee. the ASTM website.
*A Summary of Changes section appears at the end of this standard

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D445 − 19a
D1481 Test Method for Density and Relative Density (Spe- 2.3 NIST Standards:4
cific Gravity) of Viscous Materials by Lipkin Bicapillary NIST Technical Note 1297 Guideline for Evaluating and
Pycnometer Expressing the Uncertainty of NIST Measurement Re-
D2162 Practice for Basic Calibration of Master Viscometers sults5
and Viscosity Oil Standards NIST GMP 11 Good Measurement Practice for Assignment
D2170 Test Method for Kinematic Viscosity of Asphalts and Adjustment of Calibration Intervals for Laboratory
D2171 Test Method for Viscosity of Asphalts by Vacuum Standards6
Capillary Viscometer NIST Special Publication 811 Guide for the Use of the
D6071 Test Method for Low Level Sodium in High Purity International System of Units (SI)7
NIST Special Publication 1088 Maintenance and Validation
Water by Graphite Furnace Atomic Absorption Spectros-
of Liquid-in-Glass Thermometers8
copy
D6074 Guide for Characterizing Hydrocarbon Lubricant 3. Terminology
Base Oils
D6299 Practice for Applying Statistical Quality Assurance 3.1 See also International Vocabulary of Metrology.9
and Control Charting Techniques to Evaluate Analytical 3.2 Definitions:
Measurement System Performance 3.2.1 digital contact thermometer (DCT), n—an electronic
D6300 Practice for Determination of Precision and Bias device consisting of a digital display and associated tempera-
Data for Use in Test Methods for Petroleum Products and ture sensing probe.
Lubricants 3.2.1.1 Discussion—This device consists of a temperature
D6617 Practice for Laboratory Bias Detection Using Single sensor connected to a measuring instrument; this instrument
Test Result from Standard Material measures the temperature-dependent quantity of the sensor,
D6708 Practice for Statistical Assessment and Improvement computes the temperature from the measured quantity, and
provides a digital output. This digital output goes to a digital
of Expected Agreement Between Two Test Methods that
display and/or recording device that may be internal or external
Purport to Measure the Same Property of a Material
to the device. These devices are sometimes referred to as
D7962 Practice for Determination of Minimum Immersion
“digital thermometers.”
Depth and Assessment of Temperature Sensor Measure- 3.2.1.2 Discussion—PET is an acronym for portable elec-
ment Drift tronic thermometers, a subset of digital contact thermometers
E1 Specification for ASTM Liquid-in-Glass Thermometers (DCT).
E77 Test Method for Inspection and Verification of Ther-
mometers 3.3 Definitions of Terms Specific to This Standard:
3.3.1 automated viscometer, n—apparatus which, in part or
E563 Practice for Preparation and Use of an Ice-Point Bath
in whole, has mechanized one or more of the procedural steps
as a Reference Temperature
indicated in Section 11 or 12 without changing the principle or
E644 Test Methods for Testing Industrial Resistance Ther-
technique of the basic manual apparatus. The essential ele-
mometers ments of the apparatus in respect to dimensions, design, and
E1750 Guide for Use of Water Triple Point Cells operational characteristics are the same as those of the manual
E2593 Guide for Accuracy Verification of Industrial Plati- method.
num Resistance Thermometers 3.3.1.1 Discussion—Automated viscometers have the capa-
E2877 Guide for Digital Contact Thermometers bility to mimic some operation of the test method while
2.2 ISO Standards:3 reducing or removing the need for manual intervention or
ISO 3104 Petroleum products—Transparent and opaque interpretation. Apparatus which determine kinematic viscosity
liquids—Determination of kinematic viscosity and calcu- by physical techniques that are different than those used in this
lation of dynamic viscosity test method are not considered to be Automated Viscometers.
ISO 3105 Glass capillary kinematic viscometers— 3.3.2 density, n—the mass per unit volume of a substance at
Specification and operating instructions a given temperature.
ISO 3696 Water for analytical laboratory use—Specification 3.3.3 dynamic viscosity, η, n—the ratio between the applied
and test methods shear stress and rate of shear of a material.
ISO 5725 Accuracy (trueness and precision) of measurement 3.3.3.1 Discussion—It is sometimes called the coefficient of
methods and results
ISO 9000 Quality management and quality assurance
standards—Guidelines for selection and use 4
Available from National Institute of Standards and Technology (NIST), 100
ISO 17025 General requirements for the competence of Bureau Dr., Stop 3460, Gaithersburg, MD 20899-3460.
5
http://physics.nist.gov/cuu/Uncertainty/bibliography.html
testing and calibration laboratories 6
http://ts.nist.gov/WeightsAndMeasures/upload/GMP_11_Mar_2003.pdf
7
http://www.nist.gov/pml/pubs/sp811/index.cfm
8
http://www.nist.gov/pml/pubs/sp1088/index.cfm
9
International Vocabulary of Metrology — Basic and General Concepts and
3
Available from American National Standards Institute (ANSI), 25 W. 43rd St., Associated Terms (VIM), 3rd ed., 2008, http://www.bipm.org/en/publications/
4th Floor, New York, NY 10036, http://www.ansi.org. guides/vim.html.
2
D445 − 19a
dynamic viscosity or absolute viscosity. Dynamic viscosity is a these requirements. It is not intended to restrict this test method
measure of resistance to flow or deformation which constitutes to the use of only those viscometers listed in Table A1.1.
a material’s ability to transfer momentum in response to steady Annex A1 gives further guidance.
or time-dependent external shear forces. Dynamic viscosity has 6.1.2 Automated Viscometers—Automated apparatus may
the dimension of mass divided by length and time and its SI be used as long as they mimic the physical conditions,
unit is pascal times second (Pa·s). Among the transport operations, or processes of the manual apparatus. Any
properties for heat, mass, and momentum transfer, dynamic viscometer, temperature measuring device, temperature
viscosity is the momentum conductivity. control, temperature-controlled bath, or timing device incorpo-
3.3.4 kinematic viscosity, ν, n—the ratio of the dynamic rated in the automated apparatus shall conform to the specifi-
viscosity (η) to the density (ρ) of a material at the same cation for these components as stated in Section 6 of this test
temperature and pressure. method. Flow times of less than 200 s are permitted, however,
3.3.4.1 Discussion—Kinematic viscosity is the ratio be- a kinetic energy correction shall be applied in accordance with
tween momentum transport and momentum storage. Such Section 7 on Kinematic Viscosity Calculation of Specifications
ratios are called diffusivities with dimensions of length squared D446. The kinetic energy correction shall not exceed 3.0 % of
divided by time and the SI unit is metre squared divided by the measured viscosity. The automated apparatus shall be
second (m2/s). Among the transport properties for heat, mass, capable of determining kinematic viscosity of a certified
and momentum transfer, kinematic viscosity is the momentum viscosity reference standard within the limits stated in 9.2.1
diffusivity. and Section 17. The precision has been determined for auto-
3.3.4.2 Discussion—Formerly, kinematic viscosity was de- mated viscometers tested on the sample types listed in 17.3.1
fined specifically for viscometers covered by this test method and is no worse than the manual apparatus (that is, exhibits the
as the resistance to flow under gravity. More generally, it is the same or less variability).
ratio between momentum transport and momentum storage.
3.3.4.3 Discussion—For gravity-driven flow under a given NOTE 3—Precision and bias of kinematic viscosity measurements for
hydrostatic head, the pressure head of a liquid is proportional flow times as low as 10 s have been determined for automated instruments
tested with the sample types listed in 17.3.1.
to its density, ρ, if the density of air is negligible compared to
that of the liquid. For any particular viscometer covered by this 6.2 Viscometer Holders—Use viscometer holders to enable
test method, the time of flow of a fixed volume of liquid is all viscometers which have the upper meniscus directly above
directly proportional to its kinematic viscosity, ν, where the lower meniscus to be suspended vertically within 1° in all
ν = η ⁄ρ, and η is the dynamic viscosity. directions. Those viscometers whose upper meniscus is offset
from directly above the lower meniscus shall be suspended
4. Summary of Test Method vertically within 0.3° in all directions (see Specifications D446
4.1 The time is measured for a fixed volume of liquid to and ISO 3105).
flow under gravity through the capillary of a calibrated 6.2.1 Viscometers shall be mounted in the constant tempera-
viscometer under a reproducible driving head and at a closely ture bath in the same manner as when calibrated and stated on
controlled and known temperature. The kinematic viscosity the certificate of calibration. See Specifications D446, see
(determined value) is the product of the measured flow time Operating Instructions in Annexes A1–A3. For those viscom-
and the calibration constant of the viscometer. Two such eters which have Tube L (see Specifications D446) held
determinations are needed from which to calculate a kinematic vertical, vertical alignment shall be confirmed by using (1) a
viscosity result that is the average of two acceptable deter- holder ensured to hold Tube L vertical, or (2) a bubble level
mined values. mounted on a rod designed to fit into Tube L, or (3) a plumb
line suspended from the center of Tube L, or (4) other internal
5. Significance and Use means of support provided in the constant temperature bath.
5.1 Many petroleum products, and some non-petroleum 6.3 Temperature-Controlled Bath—Use a transparent liquid
materials, are used as lubricants, and the correct operation of bath of sufficient depth such, that at no time during the
the equipment depends upon the appropriate viscosity of the measurement of flow time, any portion of the sample in the
liquid being used. In addition, the viscosity of many petroleum viscometer is less than 20 mm below the surface of the bath
fuels is important for the estimation of optimum storage, liquid or less than 20 mm above the bottom of the bath.
handling, and operational conditions. Thus, the accurate deter-
mination of viscosity is essential to many product specifica- 6.3.1 Temperature Control—For each series of flow time
tions. measurements, the temperature control of the bath liquid shall
be such that within the range from 15 °C to 100 °C, the
6. Apparatus temperature of the bath medium does not vary by more than
60.02 °C of the selected temperature over the length of the
6.1 Viscometers—Use only calibrated viscometers of the
viscometer, or between the position of each viscometer, or at
glass capillary type, capable of being used to determine
the location of the thermometer. For temperatures outside this
kinematic viscosity within the limits of the precision given in
range, the deviation from the desired temperature must not
the precision section.
exceed 60.05 °C.
6.1.1 Viscometers listed in Table A1.1, whose specifications
meet those given in Specifications D446 and in ISO 3105 meet 6.4 Temperature Measuring Devices:
3
D445 − 19a
6.4.1 Liquid-in-glass Thermometers—Use calibrated ther- NOTE 5—With respect to DCT probe immersion depth, a procedure is
mometers noted in Annex A2. Devices with a nominal tem- available in Test Methods E644, Section 7, for determining the minimum
depth. With respect to an ice bath, Practice E563 provides guidance on the
perature range from 0 °C to 100 °C will have an accuracy after preparation of an ice bath, however, variance from the specific steps is
correction of 60.02 °C or better. When the nominal tempera- permitted provided preparation is consistent as it is being used to track
ture range is outside the 0 °C to 100 °C range, they will have change in calibration.
an accuracy after correction of 60.05 °C or better. 6.4.2.1 Verify the calibration at least annually. The probe
6.4.1.1 If calibrated liquid-in-glass thermometers are used, shall be recalibrated when the check value differs by more than
the use of two thermometers is recommended. When the 0.01 °C from the last probe calibration. Verification can be
temperature range is from 0 °C to 100 °C, the two accomplished with the use of a water triple point cell, an ice
thermometers, with corrections applied, shall agree within bath, or other suitable constant temperature device which has a
0.04 °C. When the temperature range is outside 0 °C to 100 °C, known temperature value of suitable precision. See Practice
the two thermometers, with corrections applied, shall agree to E563 and Guides E1750 and E2593 for more information
within 0.1 °C. regarding checking calibrations.
6.4.2 Digital contact thermometer meeting the following 6.4.2.2 In the case of constant temperature baths used in
requirements: instruments for automatic viscosity determinations, the user is
Criteria Minimum Requirements to contact the instrument manufacturer for the correct DCT that
Nominal temperature –80 °C to 0 °C has performance equivalence to that described here.
rangesA
0 °C to 100 °C 6.4.3 Outside the range from 0 °C to 100 °C, use either
calibrated liquid-in-glass thermometers of an accuracy after
Above 100 °C correction of 60.05 °C or better, or any other thermometric
Display resolution, 0.01 °C device of equal or better accuracy. When two temperature
minimum measuring devices are used in the same bath, they shall agree
Accuracy,B 0 °C to 100 °C: ±20 mK (±0.02 °C) within 60.1 °C.
minimum
–80 °C to 0 °C and above 100 °C: 6.4.4 Temperature Device Placement:
±50 mK (±0.05 °C) 6.4.4.1 Liquid-in-glass Thermometer, shall be suspended
Sensor type RTD, such as a PRT or thermistor vertically and positioned so that the top of the liquid column is
Immersion depthC 40 mm minimum by Practice D7962 just below the surface of the bath fluid. See Fig. 1.
Measurement driftD less than 20 mK (0.02 °C) per year 6.4.4.2 DCT Probe, shall be immersed by more than its
Response timeE less than or equal to 8 s
Temperature calibration When the ‘range-of-use’ is less than 30 minimum immersion depth in a constant temperature bath so
data degrees Celsius, then at least 2 data that the center of the probe’s sensing region is at the same level
points are required.
as the lower half of the working capillary provided the probe’s
When the ‘range-of-use’ is 30 degrees minimum immersion depth is met and is no less than indicated
or greater and less than 90 degrees, on calibration certificate. See Fig. 1. The end of the probe
then at least 3 data points are required.
sheath shall not extend past the bottom of the viscometer. It is
When the ‘range-of-use’ is 90 degrees preferable for the center of the sensing element to be located at
or greater, then at least 4 data points the same level as the lower half of the working capillary as
are required.
long as the minimum immersion requirements are met.
In all cases the calibration data is to be 6.4.5 When using liquid-in-glass thermometers, such as
included in calibration report. those in Table A2.1, use a magnifying device to read the
Temperature calibration The DCT shall have a report of tem-
thermometer to the nearest 1⁄5 division (for example, 0.01 °C or
report perature calibration traceable to a na- 0.02 °F) to ensure that the required test temperature and
tional calibration or metrology standards temperature control capabilities are met (see 10.1). It is
body issued by a competent calibration
laboratory with demonstrated compe- recommended that thermometer readings (and any corrections
tency in temperature calibration. An ISO supplied on the certificates of calibrations for the thermom-
17025 accredited laboratory with tem- eters) be recorded on a periodic basis to demonstrate compli-
perature calibration in its accreditation
scope would meet this requirement. ance with the test method requirements. This information can
be quite useful, especially when investigating issues or causes
A
A device’s minimum and maximum temperature may be different than the values relating to testing accuracy and precision.
shown provided the calibration requirements are met.
B
Accuracy is the total combined accuracy of the DCT unit which includes the 6.5 Timing Device—Use any timing device, spring-wound
display, electronics, and sensor probe with correction factors.
C
or digital, that is capable of taking readings with a discrimi-
Minimum probe immersion depth as determined by Practice D7962, or an
equivalent procedure, and is to be equal to or less than the value in the table. This
nation of 0.1 s or better and has an accuracy within 60.07 %
is the minimum immersion needed to obtain an accurate temperature measure- (see Annex A3) of the reading when tested over the minimum
ment thus the actual immersion will likely exceed this minimum. and maximum intervals of expected flow times.
D
Drift is the difference between the corrected DCT temperature and a reference.
E
Response Time—The time for a DCT to respond to a step change in temperature. 6.5.1 Timing devices powered by alternating electric current
This parameter is determined by the DCT provider following the procedure in may be used if the current frequency is controlled to an
Section 9 of Test Methods E644 or an equivalent method. accuracy of 0.05 % or better. Alternating currents, as provided
NOTE 4—See Guide E2877 for additional information regarding DCT by some public power systems, are intermittently rather than
parameters. continuously controlled. When used to actuate electrical timing
4
D445 − 19a
FIG. 1 Temperature Probe Immersion in Constant Temperature Bath
devices, such control can cause large errors in kinematic ardous in contact with organic materials. If used, wear a full
viscosity flow time measurements. face-shield and full-length protective clothing including suit-
6.6 Ultrasonic Bath, Unheated—(optional), with an operat- able gloves. Avoid breathing vapor. Dispose of used chromic
ing frequency between 25 kHz to 60 kHz and a typical power acid carefully as it remains hazardous. Nonchromium-
output of ≤100 W, of suitable dimensions to hold container(s) containing, strongly oxidizing acid cleaning solutions are also
placed inside of bath, for use in effectively dissipating and highly corrosive and potentially hazardous in contact with
removing air or gas bubbles that can be entrained in viscous organic materials, but do not contain chromium which has
sample types prior to analysis. It is permissible to use ultra- special disposal problems.)
sonic baths with operating frequencies and power outputs 7.2 Sample Solvent, completely miscible with the sample.
outside this range, however it is the responsibility of the Filter before use.
laboratory to conduct a data comparison study to confirm that 7.2.1 For most samples, a volatile petroleum spirit or
results determined with and without the use of such ultrasonic naphtha is suitable. For residual fuels, a prewash with an
baths does not materially impact results. aromatic solvent such as toluene or xylene may be necessary to
7. Reagents and Materials remove asphaltenic material.
7.1 Chromic Acid Cleaning Solution, or a nonchromium- 7.3 Drying Solvent, a volatile solvent miscible with the
containing, strongly oxidizing acid cleaning solution. sample solvent (see 7.2) and water (see 7.4). Filter before use.
(Warning—Chromic acid is a health hazard. It is toxic, a 7.3.1 Acetone is suitable. (Warning—Extremely flam-
recognized carcinogen, highly corrosive, and potentially haz- mable.)
5
D445 − 19a
7.4 Water, deionized or distilled and conforming to Speci- together with the instrument constant. Where the acceleration
fication D1193 or Grade 3 of ISO 3696. Filter before use. of gravity, g, differs by more than 0.1 %, correct the calibration
constant as follows:
8. Certified Viscosity Reference Standards C 2 5 ~ g 2 /g 1 ! 3 C 1 (1)
8.1 Certified viscosity reference standards shall be certified
where the subscripts 1 and 2 indicate, respectively, the
by a laboratory that has been shown to meet the requirements
standardization laboratory and the testing laboratory.
of ISO 17025 by independent assessment. Viscosity standards
shall be traceable to master viscometer procedures described in
10. General Procedure for Kinematic Viscosity
Practice D2162.
10.1 Adjust and maintain the viscometer bath at the required
8.2 The uncertainty of the certified viscosity reference
test temperature within the limits given in 6.3.1, taking account
standard shall be stated for each certified value (k = 2, 95 %
of the conditions given in Annex A2 and of the corrections
confidence). See ISO 5725 or NIST 1297.
supplied on the certificates of calibration for the thermometers.
10.1.1 Thermometers shall be held in an upright position
9. Calibration and Verification
under the same conditions of immersion as when calibrated.
9.1 Viscometers—Use only calibrated viscometers, 10.1.2 In order to obtain the most reliable temperature
thermometers, and timers as described in Section 6. measurement, it is recommended that two thermometers with
9.2 Certified Viscosity Reference Standards (Table A1.2)— valid calibration certificates be used (see 6.4).
These are for use as confirmatory checks on the procedure in 10.1.3 They should be viewed with a lens assembly giving
the laboratory. approximately five times magnification and be arranged to
9.2.1 If the determined kinematic viscosity does not agree eliminate parallax errors.
within the acceptable tolerance band, as calculated from Annex 10.2 Select a clean, dry, calibrated viscometer having a
A4, of the certified value, recheck each step in the procedure, range covering the estimated kinematic viscosity (that is, a
including thermometer and viscometer calibration, to locate the wide capillary for a very viscous liquid and a narrower
source of error. Annex A1 gives details of standards available. capillary for a more fluid liquid). The flow time for manual
NOTE 6—In previous issues of Test Method D445, limits of 60.35 % of viscometers shall not be less than 200 s or the longer time
the certified value have been used. The data to support the limit of noted in Specifications D446. Flow times of less than 200 s are
60.35 % cannot be verified. Annex A4 provides instructions on how to permitted for automated viscometers, provided they meet the
determine the tolerance band. The tolerance band combines both the requirements of 6.1.2.
uncertainty of the certified viscosity reference standard as well as the
uncertainty of the laboratory using the certified viscosity reference 10.2.1 The specific details of operation vary for the different
standard. types of viscometers listed in Table A1.1. The operating
9.2.1.1 As an alternative to the calculation in Annex A4, the instructions for the different types of viscometers are given in
approximate tolerance bands in Table 1 may be used. Specifications D446.
9.2.2 The most common sources of error are caused by 10.2.2 When the test temperature is below the ambient dew
particles of dust lodged in the capillary bore and temperature point, the use of loosely-packed drying tubes affixed to the
measurement errors. It must be appreciated that a correct result open ends of the viscometer is permitted but not mandatory.
obtained on a standard oil does not preclude the possibility of These are designed to prevent water condensation. It is
a counterbalancing combination of the possible sources of essential that they do not set up a pressure differential and
error. affect the rate of flow. Before the first use of drying tubes, it is
recommended that a certified viscosity reference standard is
9.3 The calibration constant, C, is dependent upon the used to verify the correct use of the viscometer with and
gravitational acceleration at the place of calibration and this without drying tubes in order to ensure that there is no
must, therefore, be supplied by the standardization laboratory restriction in the flow. When the test temperature is below the
dew point, fill the viscometer in the normal manner as required
in 11.1. It is recommended to charge the viscometer outside the
bath. To ensure that moisture does not condense or freeze on
TABLE 1 Approximate Tolerance Bands the walls of the capillary, draw the test portion into the working
NOTE 1—The tolerance bands were determined using Practice D6617. capillary and timing bulb, place rubber stoppers into the tubes
The calculation is documented in Research Report RR:D02-1498.A to hold the test portion in place, and insert the viscometer into
Viscosity of Reference Material,
Tolerance Band
the bath. After insertion, allow the viscometer to reach bath
mm2/s temperature, and the remove the stoppers. When performing
< 10 ±0.30 % manual viscosity determinations, do not use those viscometers
10 to 100 ±0.32 %
100 to 1000 ±0.36 % which cannot be removed from the constant temperature bath
1000 to 10 000 ±0.42 % for charging the sample portion.
10 000 to 100 000 ±0.54 %
> 100 000 ±0.73 %
10.2.3 Viscometers used for silicone fluids, fluorocarbons,
A
and other liquids which are difficult to remove by the use of a
Supporting data have been filed at ASTM International Headquarters and may be
obtained by requesting Research Report RR:D02-1498. cleaning agent, shall be reserved for the exclusive use of those
fluids except during their calibration. Subject such viscometers
6
D445 − 19a
to calibration checks at frequent intervals. The solvent wash- 11.2.1 Repeat the procedure described in 11.2 to make a
ings from these viscometers shall not be used for the cleaning second measurement of flow time. Record both measurements.
of other viscometers. 11.2.2 From the two measurements of flow time, calculate
two determined values of kinematic viscosity.
11. Procedure for Transparent Liquids 11.2.3 If the two determined values of kinematic viscosity
11.1 Although not mandatory, for some transparent liquid calculated from the flow time measurements agree within the
sample types such as viscous oils that are prone to having stated determinability figure (see 17.1.1) for the product, use
entrained air or gas bubbles present in the sample, the use of an the average of these determined values to calculate the kine-
ultrasonic bath (see 6.6) without the heater turned on (if so matic viscosity result to be reported. Record the result. If not,
equipped) has been found effective in homogenizing and repeat the measurements of flow times after a thorough
dissipating bubbles typically within 5 min prior to taking a test cleaning and drying of the viscometers and filtering (where
specimen for analysis, with no material impact on results. required, see 11.1) of the sample until the calculated kinematic
Charge the viscometer in the manner dictated by the design of viscosity determinations agree with the stated determinability.
the instrument, this operation being in conformity with that 11.2.4 If the material or temperature, or both, is not listed in
employed when the instrument was calibrated. If the sample is 17.1.1, use 1.5 % as an estimate of the determinability.
thought or known to contain fibers or solid particles, filter
through a 75 µm screen, either prior to or during charging (see 12. Procedure for Residual Fuel Oils and Opaque
Specifications D446). Liquids
NOTE 7—To minimize the potential of particles passing through the 12.1 For steam-refined cylinder oils and black lubricating
filter from aggregating, it is recommended that the time lapse between oils, proceed to 12.2 ensuring a thoroughly representative
filtering and charging be kept to a minimum. sample is used. The kinematic viscosity of residual fuel oils
11.1.1 In general, the viscometers used for transparent and similar waxy products can be affected by the previous
liquids are of the type listed in Table A1.1; however, for the thermal history and the following procedure described in
manual measurement of kinematic viscosity of jet fuels at 12.1.1 to 12.1.8 shall be followed to minimize this.
–20 °C only suspended-level type viscometers as noted in 12.1.1 In general, the viscometers used for opaque liquids
Table A1.1 shall be used. The suspended level type viscometer are of the reverse-flow type listed in Table A1.1, C.
types used for jet fuel do not require a correction to the 12.1.2 Heat the sample in the original container at a
calibration constant for the test temperature being used. temperature between 60 °C and 65 °C for 1 h.
11.1.2 With certain products which exhibit gel-like 12.1.3 Place the BS/IP/RF U-tube reverse-flow, or Zeitfuchs
behavior, exercise care that flow time measurements are made Cross-arm, or Lantz-Zeitfuchs type reverse-flow viscometer
at sufficiently high temperatures for such materials to flow for the samples to be tested in the viscometer bath(s) at the
freely, so that similar kinematic viscosity results are obtained required test temperature. If the viscometers are to be charged
in viscometers of different capillary diameters. prior to insertion in the viscometer bath, for example, Cannon
11.1.3 Allow the charged viscometer to remain in the bath Fenske Opaque, see 12.2.1.
long enough to reach the test temperature. Where one bath is 12.1.4 Upon completion of step 12.1.2, vigorously stir each
used to accommodate several viscometers, never add or sample for approximately 20 s with a glass or steel rod of
withdraw, or clean a viscometer while any other viscometer is sufficient length to reach the bottom of the container. For
in use for measuring a flow time. samples of a very waxy nature or oils of high kinematic
11.1.4 Because this time will vary for different instruments, viscosity, it may be necessary to increase the heating tempera-
for different temperatures, and for different kinematic ture above 65 °C to achieve proper mixing. The sample should
viscosities, establish a safe equilibrium time by trial. be sufficiently fluid for ease of stirring and shaking.
11.1.4.1 Thirty minutes should be sufficient except for the 12.1.5 Remove the stirring rod and inspect for sludge or
highest kinematic viscosities, however a minimum of 30 min is wax adhering to the rod. Continue stirring until there is no
specifically required for manual analysis of jet fuels at −20 °C. sludge or wax adhering to the rod.
11.1.5 Where the design of the viscometer requires it, adjust 12.1.6 Recap the container tightly and shake vigorously for
the volume of the sample to the mark after the sample has 1 min to complete the mixing. To protect the integrity of the
reached temperature equilibrium. sample should a repeat analysis be required, pour sufficient
11.2 Use suction (if the sample contains no volatile con- sample to fill two flasks and loosely stopper. (Each flask should
stituents) or pressure to adjust the head level of the test sample hold sufficient sample to fill two viscometers in order to obtain
to a position in the capillary arm of the instrument about 7 mm two determinations. The second flask is required to carry out a
above the first timing mark, unless any other value is stated in repeat analysis.) If a repeat analysis is not a consideration the
the operating instructions for the viscometer. With the sample next steps can be performed using the original container,
flowing freely, measure, in seconds to within 0.1 s, the time loosely capped.
required for the meniscus to pass from the first to the second 12.1.7 Heat the first sample flask or sample container
timing mark. If this flow time is less than the specified between 100 °C and 105 °C for 30 min.
minimum (see 10.2), select a viscometer with a capillary of 12.1.8 Remove the first sample flask or sample container
smaller diameter and repeat the operation. from the heat, close tightly, and shake vigorously for 60 s.
7
D445 − 19a
12.2 Two determinations of the kinematic viscosity of the with the sample solvent, followed by the drying solvent (see
test material are required. For those viscometers that require a 7.3). Dry the tube by passing a slow stream of filtered dry air
complete cleaning after each flow time measurement, two through the viscometer for 2 min or until the last trace of
viscometers must be used. These two determinations are used solvent is removed.
to calculate one result. Charge two viscometers in the manner 13.2 If periodic verification of the viscometer calibration
dictated by the design of the instrument. For example, for the using certified viscosity reference standards (see 9.2) is outside
Lantz-Zeitfuchs Cross-arm or the BS/IP/RF U-tube reverse- of the acceptable tolerance band, the viscometer may need to
flow viscometers for opaque liquids, filter the sample through be cleaned. Clean the viscometer with the cleaning solution
a 75 µm filter into two viscometers previously placed in the (Warning—see 7.1), for several hours to remove residual
bath. For samples subjected to heat treatment, use a preheated traces of organic deposits, rinse thoroughly with water (7.4)
filter to prevent the sample coagulating during the filtration. and drying solvent (see 7.3), and dry with filtered dry air or a
12.2.1 Viscometers which are charged before being inserted vacuum line. Remove any inorganic deposits by hydrochloric
into the bath may need to be preheated in an oven prior to acid treatment before the use of cleaning acid, particularly if
charging the sample. This is to ensure that the sample will not the presence of barium salts is suspected. (Warning—It is
be cooled below test temperature. essential that alkaline cleaning solutions are not used as
12.2.2 After 10 min, adjust the volume of the sample (where changes in the viscometer calibration can occur.)
the design of the viscometer requires) to coincide with the
filling marks as in the viscometer specifications (see Specifi- 14. Calculation
cations D446).
12.2.3 Allow the charged viscometers enough time to reach 14.1 Calculate each of the determined kinematic viscosity
the test temperature (see 12.2.1). Where one bath is used to values, ν1 and ν2, from the measured flow times, t1 and t2, and
accommodate several viscometers, never add or withdraw, or the viscometer constant, C, by means of the following equa-
clean a viscometer while any other viscometer is in use for tion:
measuring flow time. ν 1,2 5 C·t 1,2 (2)
12.3 With the sample flowing freely, measure in seconds to where:
within 0.1 s, the time required for the advancing ring of contact ν1,2 = determined kinematic viscosity values for ν1 and ν2,
to pass from the first timing mark to the second. Record the respectively, mm2/s,
measurement. C = calibration constant of the viscometer, mm2/s2, and
12.3.1 In the case of samples requiring heat treatment t1,2 = measured flow times for t1 and t2, respectively, s.
described in 12.1 through 12.1.8, complete the measurements Calculate the kinematic viscosity result, ν, as an average of
of flow time within 1 h of completing 12.1.8. Record the ν1 and ν2 (see 11.2.3 and 12.4.1).
measured flow times.
14.2 Calculate the dynamic viscosity, η, from the calculated
12.4 Calculate kinematic viscosity, ν, in millimetres squared kinematic viscosity, ν, and the density, ρ, by means of the
per second, from each measured flow time. Regard these as two following equation:
determined values of kinematic viscosity.
12.4.1 For residual fuel oils, if the two determined values of η 5 ν 3 ρ 3 1023 (3)
kinematic viscosity agree within the stated determinability where:
figure (see 17.1.1), use the average of these determined values η = dynamic viscosity, mPa·s,
to calculate the kinematic viscosity result to be reported. This ρ = density, kg/m3, at the same temperature used for the
constitutes one analysis. Record the result. If a second value determination of the kinematic viscosity, and
(repeat) is required, then repeat the analysis after thorough ν = kinematic viscosity, mm2/s.
cleaning and drying of the viscometers starting from sample
preparation steps 12.1.6 using the second flask. If the original 14.2.1 The density of the sample can be determined at the
container has been conditioned using steps 12.1.2 to 12.1.8, test temperature of the kinematic viscosity determination by an
then this is not suitable for a repeat analysis. If the calculated appropriate method such as Test Method D1217, D1480, or
kinematic viscosities do not agree, repeat the measurements of D1481.
flow times after thorough cleaning and drying of the viscom-
15. Expression of Results
eters and filtering of the sample. If the material or temperature,
or both, is not listed in 17.1.1, for temperatures between 15 °C 15.1 Report the test results for the kinematic or dynamic
and 100 °C use as an estimate of the determinability 1.0 %, and viscosity, or both, to four significant figures, together with the
1.5 % for temperatures outside this range; it must be realized test temperature.
that these materials can be non-Newtonian, and can contain
solids which can come out of solution as the flow time is being 16. Report
measured. 16.1 Report the following information:
16.1.1 Type and identification of the product tested,
13. Cleaning of Viscometer 16.1.2 Reference to this test method or a corresponding
13.1 Between successive determinations of kinematic international standard,
viscosity, clean the viscometer thoroughly by several rinsings 16.1.3 Result of the test (see Section 15),
8
D445 − 19a
16.1.4 Any deviation, by agreement or otherwise, from the Additives at 100 °C14 0.00106 y1.1
procedure specified, Gas oils at 40 °C15 0.0013 (y+1)
Jet fuels at –20 °C16 0.007608 y
16.1.5 Date of the test, and Kerosine, diesel fuels, 0.0037 y (0.37 %)
16.1.6 Name and address of the test laboratory. biodiesel fuels, and biodiesel
fuel blends at 40 °C17
17. Precision and Bias where: y is the average of determined values being com-
17.1 Comparison of Determined Values: pared.
17.1.1 Determinability (d)—The difference between succes- 17.1.2 The determinability for used (in-service) formulated
sive determined values obtained by the same operator in the oils has not been determined, however use a limit of 1.0 % (see
same laboratory using the same apparatus for a series of 12.4.1) for temperatures between 15 °C and 100 °C.18
operations leading to a single result, would in the long run, in
the normal and correct operation of this test method, exceed the
values indicated only in one case in twenty:
Base oils at 40 °C10 0.0037 y (0.37 %)
Base oils at 100 °C10 0.0036 y (0.36 %)
Formulated oils at 40 °C10 0.0037 y (0.37 %)
Formulated oils at 100 °C10 0.0036 y (0.36 %)
Formulated oils at 150 °C11 0.015 y (1.5 %) 14
Petroleum wax at 100 °C12 0.0080 y (0.80 %) Supporting data have been filed at ASTM International Headquarters and may
Residual fuel oils at 50 °C13 0.0244 y (2.44 %) be obtained by requesting Research Report RR:D02-1421. These precision values
Residual fuel oils at 100 °C13 0.03 y (3 %) were obtained by statistical examination of interlaboratory results from eight
additives in the range from 145 mm2/s to 1500 mm2/s at 100 °C and were first
available in 1997.
15
Supporting data have been filed at ASTM International Headquarters and may
10
Supporting data has been filed at ASTM International Headquarters and may be obtained by requesting Research Report RR:D02-1422. These precision values
be obtained by requesting Research Report RR:D02-1788. These precision values were obtained by statistical examination of interlaboratory results from eight gas
were obtained by statistical examination of interlaboratory results for the following oils in the range from 1 mm2/s to 13 mm2/s at 40 °C and were first available in 1997.
samples: Base Oils with viscosities between (12.0 and 476.0) mm2/s at 40 °C tested Kerosine and diesel fuel samples, which can be considered as gas oils, were
in seven laboratories; Formulated Oils with viscosities between (28.0 and 472.0) included in a dataset to determine the precision for kerosine, diesel fuels, biodiesel
mm2/s at 40 °C tested in seven laboratories; Base Oils with viscosities between (2.90 fuels, and biodiesel fuel blends at 40 °C (RR:D02-1780). The precision stated in
and 32.0) mm2/s at 100 °C tested in eight laboratories; Formulated Oils with RR:D02-1780 was developed in a more recent interlaboratory study than the
viscosities between (6.50 and 107.0) mm2/s at 100 °C tested in eight laboratories. precision stated in RR:D02-1422. Therefore, the gas oil precision statements do not
Formulated Oils include automatic transmission fluids, hydraulic fluids, motor oils, apply to kerosine and diesel fuels and a user should refer to the precision statements
gear oils, polymers in base oil and additives in base oil. The determinability, for kerosine, diesel fuels, biodiesel fuels, and biodiesel fuel blends at 40 °C.
16
repeatability, and reproducibility results are for tests performed with manual Supporting data may be obtained by requesting ILS2017_71_3 from the
viscometers. Determinability, repeatability, and reproducibility for automated/ Energy Institute, http://www.energyinst.org. This data was obtained using manual
automatic instruments are no worse than that for the manual instruments. For the analysis.
17
precision of specific automated/automatic instruments see Research Report Supporting data have been filed at ASTM International Headquarters and may
RR:D02-1820. be obtained by requesting Research Report RR:D02-1780. These precision values
11
Supporting data have been filed at ASTM International Headquarters and may were obtained by statistical examination of interlaboratory results from seven
be obtained by requesting Research Report RR:D02-1333. These precision values samples including kerosine, diesel fuels, biodiesel fuels, and biodiesel fuel blends
were obtained by statistical examination of interlaboratory results for eight fully (RR:D02-1780) in the range from 2.06 mm2/s to 4.50 mm2/s at 40 °C. The
formulated engine oils in the range from 7 mm2/s to 19 mm2/s at 150 °C, and first determinability, repeatability, and reproducibility results are for tests performed with
published in 1991. See Guide D6074. manual viscometers. Determinability, repeatability, and reproducibility for
12
Supporting data have been filed at ASTM International Headquarters and may automated/automatic instruments are no worse than that for the manual instruments.
be obtained by requesting Research Report RR:D02-1334. These precision values For the precision of specific automated/automatic instruments see Research Report
were obtained by statistical examination of interlaboratory results from five RR:D02-1820.
petroleum waxes in the range from 3 mm2/s to 16 mm2/s at 100 °C, and were first 18
published in 1988. be obtained by requesting Research Report RR:D02-1852. The precision values
13
Supporting data have been filed at ASTM International Headquarters and may were obtained by statistical examination of interlaboratory results from ten used
be obtained by requesting Research Report RR:D02-1837. These precision values (in-service) formulated oil samples. These consisted of steam turbine, gas turbine,
were obtained by statistical examination of interlaboratory results from eleven diesel engine, hydraulic, and gasoline engine oil samples which were analyzed by
laboratories on residual fuel oil samples conforming to D396 Grades 5 or 6 and/or ten laboratories using both manual and automated apparatuses. The kinematic
ISO8217 RMG and RMK at 50 °C and 10 at 100 °C in the range from 27.34 mm2/s viscosities of these samples ranged from 25 mm2/s to 125 mm2/s at 40 °C, and from
to 2395 mm2/s at 50 °C and 6.36 mm2/s to 120.8 mm2/s at 100 °C. These precision 6 mm2/s to 16 mm2/s at 100 °C. The statistical output is based on ten laboratories
statements only refer to measurement of viscosity using manual viscometers. and eight samples at 40 °C and ten laboratories and ten samples at 100 °C.
9
D445 − 19a
17.2 Comparison of Results: 17.3 The precision for specific automated and automatic
17.2.1 Repeatability (r)—The difference between successive viscometers has been determined for sample types and tem-
results obtained by the same operator in the same laboratory peratures listed in 17.3.1. An analysis has been made of a large
with the same apparatus under constant operating conditions on dataset including both automated/automatic and manual vis-
identical test material would, in the long run, in the normal and cometers over the temperature range of 40 °C to 100 °C for the
correct operation of this test method, exceed the values sample types listed in 17.3.1. The determinability, repeatability,
indicated only in one case in twenty: and reproducibility of automated/automatic viscometer data are
Base oils at 40 °C10 0.0101 x (1.01 %)
no worse than the determinability, repeatability, and reproduc-
Base oils at 100 °C10 0.0085 x (0.85 %) ibility for the manual instruments. It is also shown in the
Formulated oils at 40 °C10 0.0074 x (0.74 %) research reports that no statistically significant bias was ob-
Formulated oils at 100 °C10 0.0084 x (0.84 %)
Formulated oils at 150 °C11 0.0056 x (0.56 %)
served between the automated/automatic data in comparison to
Petroleum wax at 100 °C12 0.0141 x1.2 the manual data.19 For the precision of specific automated/
Residual fuel oils at 80 °C13 0.013 (x + 8) automatic instruments, see RR:D02-1820.20
Residual fuel oils at 100 °C13 0.08088 x (8.08 %)
Residual oils at 50 °C13 0.07885 x (7.88 %)
17.3.1 The determinability, repeatability, and reproducibil-
Additives at 100 °C14 0.00192 x1.1 ity have been determined for automated/automatic viscometers
Gas oils at 40 °C15 0.0043 (x+1) for the following sample types and temperatures:
Jet fuels at –20 °C16 0.001368 x1.4
Kerosine, diesel fuels, biodiesel 0.0056 x (0.56 %)
Distillates, fatty acid methyl esters, and distillates contain-
fuels, and biodiesel fuel blends at ing fatty acid methyl esters at 40 °C
40 °C17 Base oils at 40 °C and 100 °C
Used (in-service) formulated oils at 0.000233 x1.722
40 °C18
Formulated oils at 40 °C and 100 °C
Used (in-service) formulated oils at 0.001005 x1.4633 For these sample types, determinability, repeatability, and
100 °C18 reproducibility for automated/automatic instruments are no
where: x is the average of results being compared. worse than that for the manual instruments. For the precision of
17.2.1.1 The degrees of freedom associated with the repeat- specific automated/automatic instruments see Research Report
ability estimate for the kerosine, diesel fuels, biodiesel fuels, RR:D02-1820.
and biodiesel fuel blends at 40 °C round robin study are 16. The precision has been determined for automated viscom-
Since the minimum requirement of 30 (in accordance with eters and the range of r and R values for automated instruments
Practice D6300) is not met, users are cautioned that the actual is shown in RR:D02-1820. For the samples listed in RR:D02-
repeatability may be significantly different than these esti- 1820, precision for automated instruments is no worse than that
mates. for the manual instruments.21
17.3.1.1 Degree of Agreement Between Results by Manual
17.2.2 Reproducibility (R)—The difference between two
and Automated Instruments in Test Method D445—Results for
single and independent results obtained by different operators
the sample types listed in RR:D02-1820 produced by manual
working in different laboratories on nominally identical test
and automated instruments in this test method have been
material would, in the long run, in the normal and correct
assessed in accordance with procedures outlined in Practice
operation of this test method, exceed the values indicated
D6708.
below only in one case in twenty.
17.3.1.2 The findings are: Results from manual and auto-
Base oils at 40 °C10 0.0136 x (1.36 %) mated instruments in Test Method D445 may be considered to
Base oils at 100 °C10 0.0190 x (1.90 %)
Formulated oils at 40 °C10 0.0122 x (1.22 %) be practically equivalent, for sample types listed in RR:D02-
Formulated oils at 100 °C10 0.0138 x (1.38 %) 1820. No sample-specific bias, as defined in Practice D6708,
Formulated oils at 150 °C11 0.018 x (1.8 %) was observed for the materials studied. Differences between
Petroleum wax at 100 °C12 0.0366 x1.2
Residual fuel oils at 80 °C13 0.04 (x + 8) results from manual and automated instruments in Test Method
Residual fuel oils at 100 °C13 0.1206 x (12.06 %) D445, for the samples listed in RR:D02-1820, are expected to
Residual oils at 50 °C13 0.08461 x (8.46 %)
exceed the following between methods reproducibility: 1.91 %
Additives at 100 °C14 0.00862 x1.1
Gas oils at 40 °C15 0.0082 (x+1) for distillates, fatty acid methyl esters, and distillates contain-
Jet fuels at –20 °C16 0.002899 x1.4 ing fatty acid methyl esters at 40 °C; 1.27 % for base oils at
Kerosine, diesel fuels, biodiesel fuels, 0.0224 x (2.24 %)
and biodiesel fuel blends at 40 °C17
40 °C; 1.23 % for formulated oils at 40 °C; 1.70 % for base oils
1.722
Used (in-service) formulated oils at 0.000594 x
40 °C18
19
Used (in-service) formulated oils at 0.003361 x1.4633 Supporting data have been filed at ASTM International Headquarters and may
100 °C18 be obtained by requesting Research Report RR:D02-1498. Contact ASTM Customer
Service at service@astm.org.
where: x is the average of results being compared. 20
17.2.2.1 The degrees of freedom associated with the repro- be obtained by requesting Research Report RR:D02-1820. Contact ASTM Customer
Service at service@astm.org.
ducibility estimate for the kerosine, diesel fuels, biodiesel 21
fuels, and biodiesel fuel blends at 40 °C round robin study are be obtained by requesting Research Report RR:D02-1787. These precision values
19. Since the minimum requirement of 30 (in accordance with were obtained by statistical examination of interlaboratory results from seven
samples including distillates, fatty acid methyl esters, and distillates containing fatty
Practice D6300) is not met, users are cautioned that the actual
acid methyl esters (RR:D02-1790) in the range from (2.06 to 4.50) mm2/s at 40 °C.
reproducibility may be significantly different than these esti- These seven samples were tested in 21 different Cannon and Herzog instruments to
mates. obtain the precision values shown.
10
D445 − 19a
at 100 °C; 1.21 % for formulated oils at 100 °C, as defined in 18. Keywords
Practice D6708, about 5 % of the time. These percent differ- 18.1 dynamic viscosity; kinematic viscosity; viscometer;
ences are based upon the highest calculated combined method viscosity
reproducibilities (Rxy in Practice D6708).22
22
Supporting data has been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D02-1787. These precision values
were obtained by statistical examination of interlaboratory results for the following
samples: Base Oils with viscosities between (12.0 and 476.0) mm2/s at 40 °C tested
in 22 laboratories; Formulated Oils with viscosities between (28.0 and 472.0) mm2/s
at 40 °C tested in 22 laboratories; Base Oils with viscosities between (2.90 and 32.0)
mm2/s at 100 °C tested in 21 laboratories; Formulated Oils with viscosities between
(6.50 and 107.0) mm2/s at 100 °C tested in 21 laboratories. Formulated Oils include
automatic transmission fluids, hydraulic fluids, motor oils, gear oils, polymers in
base oil, and additives in base oil.
ANNEXES
(Mandatory Information)
A1. VISCOMETER TYPES AND CERTIFIED VISCOSITY REFERENCE STANDARDS
A1.1 Viscometer Types TABLE A1.1 Viscometer Types

Viscometer Identification Kinematic Viscosity Range,A mm2/s
A1.1.1 Table A1.1 lists capillary viscometers commonly in
A. Ostwald Types for Transparent Liquids
use for viscosity determinations on petroleum products. For Cannon-Fenske routineB 0.5 to 20 000
specifications, operating instructions, and calibration, refer to Zeitfuchs
B
0.6 to 3 000
BS/U-tube 0.9 to 10 000
specifications in Specifications D446. BS/U/M miniature 0.2 to 100
SILB 0.6 to 10 000
A1.1.2 Table A1.2 lists certified viscosity reference stan- Cannon-Manning semi-micro 0.4 to 20 000
dards. PinkevitchB 0.6 to 17 000
B. Suspended-level Types for Transparent Liquids
BS/IP/SLB 3.5 to 100 000
B
BS/IP/SL(S) 1.05 to 10 000
BS/IP/MSL 0.6 to 3 000
UbbelohdeB 0.3 to 100 000
FitzSimons 0.6 to 1 200
AtlanticB 0.75 to 5 000
Cannon-Ubbelohde(A), Cannon 0.5 to 100 000
Ubbelohde dilutionB (B)
Cannon-Ubbelohde semi-micro 0.4 to 20 000
C. Reverse-flow Types for Transparent and Opaque Liquids
Cannon-Fenske opaque 0.4 to 20 000
Zeitfuchs cross-arm 0.6 to 100 000
BS/IP/RF U-tube reverse-flow 0.6 to 300 000
Lantz-Zeitfuchs type reverse-flow 60 to 100 000
A
Each range quoted requires a series of viscometers. To avoid the necessity of
making a kinetic energy correction, these viscometers are designed for a flow time
in excess of 200 s except where noted in Specifications D446.
B
In each of these series, the minimum flow time for the viscometers with lowest
constants exceeds 200 s.
11
D445 − 19a
TABLE A1.2 Certified Viscosity Reference Standards
Approximate Kinematic Viscosity, mm2/s
Designation
20 °C 25 °C 40 °C 50 °C 80 °C 100 °C
S3 4.6 4.0 2.9 ... ... 1.2
S6 11 8.9 5.7 ... ... 1.8
S20 44 34 18 ... ... 3.9
S60 170 120 54 ... ... 7.2
S200 640 450 180 ... ... 17
S600 2400 1600 520 280 67 32
S2000 8700 5600 1700 ... ... 75
S8000 37 000 23 000 6700 ... ... ...
S30 000 ... 81 000 23 000 11 000 ... ...
A2. KINEMATIC VISCOSITY TEST THERMOMETERS
A2.1 Short-Range Specialized Liquid-in-Glass Thermom- this requirement. The calibration report shall include data for a
eter series of temperatures which are appropriate for its intended
A2.1.1 Use a short-range specialized liquid-in-glass ther- use.
mometer conforming to the generic specification given in Table A2.2.2 The scale correction of liquid-in-glass thermometers
A2.1 and Table A2.2 and to one of the designs shown in Fig. can change during storage and use. Therefore, regular in-house
A2.1. As an alternative, use a digital contact thermometer ice-point verifications are required, and can be achieved within
(DCT) as defined in 6.4.2. the working laboratory, using an ice melting bath. However,
A2.1.2 The difference in the designs of the liquid-in-glass these checks may not be an adequate means of recalibration as
thermometers rests mainly in the position of the ice-point scale. the use of a single-point recalibration at the ice point adds an
In Design A, the ice point is within the scale range, in Design additional uncertainty to the updated thermometer calibration
B, the ice point is below the scale range, and in Design C, the result at every temperature but the ice point. The user must
ice point is above the scale range. determine if the thermometer requires complete re-calibration
A2.2 Calibration to continue to meet the expanded measurement uncertainty
requirements of this section. NIST Special Publication 1088,
A2.2.1 When using a liquid-in-glass thermometer, it shall Section 7.9 on determining uncertainty of correction, may be
have a report of temperature calibration traceable to a national helpful to the user in making this decision. If in-house ice-point
calibration or metrology standards body issued by a competent
verification brings the expanded measurement uncertainty out
calibration laboratory with demonstrated competency in tem-
of the requirements of A2.2.1, complete recalibration at a
perature calibration. An ISO 17025 accredited laboratory with
laboratory meeting the requirements of A2.2.1 is required.
temperature calibration in its accreditation scope would meet
TABLE A2.1 General Specification for Thermometers

NOTE 1—Table A2.2 gives a range of ASTM, IP, and ASTM/IP
thermometers that comply with the specification in Table A2.1, together
with their designated test temperatures. See Specification E1 and Test
Method E77.
Immersion Total
Scale marks:
Subdivisions °C 0.05
Long lines at each °C 0.1 and 0.5
Numbers at each °C 1
Maximum line width mm 0.10
Scale error at test temperature, max °C 0.1
Expansion chamber:
Permit heating to °C 105 up to 90, 120 between 90 and 95
130 between 95 and 105, 170 above
105
Total length mm 300 to 310
Stem outside diameter mm 6.0 to 8.0
Bulb length mm 45 to 55
Bulb outside diameter mm no greater than stem
Length of scale range mm 40 to 90
12
D445 − 19a
TABLE A2.2 Complying Thermometers
Test Test
Thermometer No. Temperature Thermometer No. Temperature
°C °F °C °F
ASTM 132C, IP 102C 150 ASTM 128C, F/IP 33C 0 32
ASTM 110C, F/IP 93C 135 275 ASTM 72C, F/IP 67C −17.8 0
ASTM 121C/IP 32C 98.9, 210, ASTM 127C/IP 99C −20 −4
100 212 ASTM 126C, F/IP 71C −26.1 −20
ASTM 129C, F/IP 36C 93.3 200 ASTM 73C, F/IP 68C −40 −40
ASTM 48C, F/IP 90C 82.2 180 ASTM 74C, F/IP 69C −53.9 −65
IP 100C 80
ASTM 47C, F/IP 35C 60 140
ASTM 29C, F/IP 34C 54.4 130
ASTM 46C F/IP 66C 50 122
ASTM 120C/IP 92C 40
ASTM 28C, F/IP 31C 37.8 100
ASTM 118C, F 30 86
ASTM 45C, F/IP 30C 25 77
ASTM 44C, F/IP 29C 20 68
FIG. A2.1 Thermometer Designs
A2.2.2.1 For liquid-in-glass thermometers, the interval for the first six months is recommended. A change of one or more
ice-point verification shall be no longer than six months (see scale divisions in the ice point means that the thermometer may
NIST GMP 11). For new thermometers, monthly checking for have been overheated or damaged, and it may be out of
13
D445 − 19a
calibration. Such thermometers shall be removed from service A2.2.3.4 Record the ice-point readings and determine the
until inspected, or recalibrated, or both. thermometer correction at this temperature from the mean
A2.2.2.2 Keep records of all recalibration. reading. If the correction is found to be higher or lower than
A2.2.3 Procedure for Ice-point Verification of Liquid-in- that corresponding to a previous calibration, change the cor-
Glass Thermometers. rection at all other temperatures by the same value. See A2.2.1
A2.2.3.1 Unless otherwise listed on the certificate of for discussion on expanded measurement uncertainty changes
calibration, the recalibration of calibrated kinematic viscosity when changing correction values from ice-point verifications.
thermometers requires that the ice-point reading shall be taken A2.2.3.5 During the procedure, apply the following condi-
within 60 min after being at test temperature for not less than tions:
3 min. NIST Special Publication 1088 from the NIST website (1) The thermometer shall be supported vertically.
describes an effective procedure for ice-point verification, (2) View the thermometer with an optical aid that gives a
including all formulae necessary for calculations of change of magnification of approximately five and also eliminates paral-
correction and measurement uncertainty. Alternatively, use lax.
Practice E563 or those in A2.2.3.2 through A2.2.3.5. (3) Express the ice-point reading to the nearest 0.01 °C.
A2.2.3.2 Select clear pieces of ice, preferably made from
distilled or pure water. Discard any cloudy or unsound por- A2.2.4 When in use, immerse the thermometric device to
tions. Rinse the ice with distilled water and shave or crush into the same depth as when it was fully calibrated. For example, if
small pieces, avoiding direct contact with the hands or any a liquid-in-glass thermometer was calibrated at the normal total
chemically unclean objects. Fill the Dewar vessel with the immersion condition, it shall be immersed to the top of the
crushed ice and add sufficient water to form a slush, but not mercury column with the remainder of the stem and the
enough to float the ice. As the ice melts, drain off some of the expansion volume at the uppermost end exposed to room
water and add more crushed ice. Insert the thermometer, and temperature and pressure. In practice, this means that the top of
pack the ice gently about the stem, to a depth approximately the mercury column shall be within a length equivalent to four
one scale division below the 0 °C graduation. scale divisions of the surface of the medium whose temperature
A2.2.3.3 After at least 3 min have elapsed, tap the thermom- is being measured.
eter gently and repeatedly at right angles to its axis while
A2.2.4.1 If this condition cannot be met, then an extra
making observations. Successive readings taken at least 1 min
apart shall agree within 0.005 °C. correction may be necessary.
A3. TIMER ACCURACY
A3.1 Regularly check timers for accuracy and maintain WWV Fort Collins, CO (2.5, 5, 10, 15, 20) MHz
records of such checks. WWVH Kauai, HI (2.5, 5, 10, 15) MHz
CHU Ottawa, Canada (3.33, 7.335, 14.67) MHz
A3.1.1 Time signals as broadcast by the National Institute A3.1.2 Radio broadcast of voice and audio on a telephone
of Standards and Technology are a convenient and primary line at phone 303-499-7111. Additional time services are
standard reference for calibrating timing devices. The follow- available from the National Institute of Standards and
ing can be used to an accuracy of 0.1 s: Technology.
A4. CALCULATION OF ACCEPTABLE TOLERANCE ZONE (BAND) TO DETERMINE CONFORMANCE WITH A CERTI-
FIED REFERENCE MATERIAL
NOTE A4.1—These calculations are based on Practice D6617. A4.2 Determine the combined extended uncertainty (CEU)
of the accepted reference value (ARV) of the certified reference
A4.1 Determine the standard deviation for site uncertainty,
material (CRM) from the supplier’s label or included docu-
σsite, from a laboratory quality control program. (See Practice
mentation. In this test method, the CRM is the Certified
D6299.)
Viscosity Reference Standard (CVRS) as defined in 9.2.
A4.1.1 If the standard deviation for site uncertainty, σsite, is NOTE A4.2—Combined Extended Uncertainty (CEU) is equivalent to
not known, use the value 0.19 %. Expanded Uncertainty (U). See NIST Technical Note 1297.
14
D445 − 19a
A4.3 Calculate the standard error of the accepted reference k 5 2 ~ from the CVRS label or documentation!
value (SEARV) by dividing the CEU by the coverage factor, k,
listed on the supplier’s label or included documentation. 0.22
SEARV 5 5 0.11
2
CEUARV
SEARV 5 (A4.1)
k TZ 5 61.44=0.192 10.112 5 61.44=0.036110.0121 5 60.32 %
NOTE A4.3—Standard Error (SEARV) is equivalent to Combined Stan-
dard Uncertainty (UC). See NIST Technical Note 1297. A4.5.1 In this example, the tolerance zone will be 60.32 %
A4.3.1 If the coverage factor, k, is not known, use the value of the certified viscosity reference standard value on the report
2. of test or bottle label. If this site uses a CVRS (for example)
with a kinematic viscosity of 33.98 mm2/s, the TZ =
A4.4 Construct the acceptable tolerance zone:
33.87 mm2/s to 34.09 mm2/s, with 95 % certainty. Viscosity
TZ 5 61.44 =σ site
2 2
1SEARV (A4.2) measurements made with this CVRS at that site should fall
within that tolerance zone (band) 19 out of 20 times.
A4.5 Worked out example for kinematic viscosity zone
(band):
σ site 5 0.19 % ~ default value from A4.1.1! (A4.3)
CEUARV 5 0.22 % ~ from the CVRS label or documentation!
APPENDIX
(Nonmandatory Information)
X1. TROUBLESHOOTING GUIDE
X1.1 There are many factors that can impact the precision relevant sections in this test method may require closer
of this test method. Subcommittee D02.07 has developed a attention. See Table X1.1.
troubleshooting guide to assist users in determining which
15
D445 − 19a
TABLE X1.1 Troubleshooting Guide
Observed Error Possible Causes Resolution Reference
Foreign particle lodged in the
Visually inspect for foreign particles in
viscometer capillary
capillary and back flush or clean with 13.2
Organic or inorganic deposits on
mild detergent or acid
viscometer capillary wall
Filter new samples to remove visible
particles. For used oil samples, the
Particulates in sample largest particle size should not exceed 11.1, 12.2, Note 6
one half the capillary diameter. Select
a larger viscometer tube range.
Allow sample to settle or use ultra-
Air bubbles in the sample 6.6, 11.1
sonic bath to remove air
Water in sample (such as with in- Remove water from sample prior to
service engine oils) testing
Samples tested at sub-ambient tem-
Test sample at warmer temperature or
peratures may have wax precipiates
remove wax from the sample prior to 12.1, 12.1.4, 12.1.5
which may clog the capillary during
testing
measurement
Sample is mixed phases or non- Precision in D445 is not known for
11.2.4, 12.4.1
homogeneous these types of samples
Flow times don’t meet determinability
Contact bath supplier to confirm/verify
of D445 or are drifting
equipment performance specifications
Temperature of bath not regulating meet the apparatus section of method.
6.3, 6.4
within method requirements If bath set point temperature is near
ambient, an external chiller might be
required.
Verify bath liquid is circulating and the
bath temperature uniformity using a
second reference temperature mea-
suring device. Verify the proper vis-
Bath has temperature gradients 6.3, 6.4, Fig. 1
cosity of bath fluid is being used as
per the manufacturer’s recommenda-
tions for the specific test temperature
being used.
Sample thermal equilibrium time too Allow sample to remain in viscometer
11.1.3 – 11.1.5, 12.2.3
short for 30 min prior to measurement
Sample requires thermal pretreatment
11.1.2, 12.1
prior to measurement
Verify timing device meets specifica-
Inaccurate flow time measurement 6.5
tions or operator technique is proper
Viscometer range too large Select smaller range viscometer 10.2
Verify bath temperature set point 6.3, 6.4
Verify reference temperature measur-
6.3, 6.4
Short flow times <200 s Actual bath temperature warmer than ing device calibration
desired target temperature Verify that any temperature calibration
offset (see calibration certificate) is 6.4.1, 6.4.4
being applied
Viscometer range too small Select a larger range viscometer 10.2
Set point temperature is close to am-
bient temperature and the viscosity
bath needs to be connected to an ex-
Excessively long flow times Actual bath temperature colder than ternal chiller
desired target temperature Verify reference temperature measur-
6.3, 6.4
ing device calibration
Verify that any temperature calibration
being applied
16
D445 − 19a
TABLE X1.1 Continued
Observed Error Possible Causes Resolution Reference
Verify reference temperature 6.3, 6.4
Temperature of bath is not at target measuring device calibration
temperature Verify that any temperature calibration
being applied
Viscometer tube is not properly Verify solvent system compatibility
7.2, 7.3, 7.4, 10.2.3
cleaned or dried with sample chemistry
Contaminated CVRS or check Verify with alternate CVRS or verify
9.2
standard check standard in different viscometer
Verify viscometer meets the specifica-
tions of D446 and that calibration was
performed by using reference viscom-
eters or by certified viscosity reference
standards with traceability in accord
with ISO 17025. Verify that the cali-
bration constant on the viscometer
Measured results with certified calibration certificate is appropriate for
viscosity reference standard (CVRS) the test temperature being used and
or check standard exceed the the gravitational correction is applied
published repeatability Viscometer tube calibration error or as required. See 6.2 and 6.3 of D446;
not in accord with D446 Note additional sources of error may see 9.3 of D445
arise from using certified viscosity ref-
erence standards: These may arise
from contamination, exposure to
sunlight, expired shelf life, or only one
standard being used instead of the
mandatory two standards, whereby
the second standard has a flow time
of at least 50 % longer than the first
oil and incorrect bath temperature dur-
ing the calibration.
Verify with supplier that viscometer is
constructed in accord with the dimen-
Viscometer tube does not meet D446 sions and tolerances noted in D446,
See D446
specification otherwise the viscometer precision
may deviate from the method preci-
sion
SUMMARY OF CHANGES
Subcommittee D02.07 has identified the location of selected changes to this standard since the last issue
(D445 – 19) that may impact the use of this standard. (Approved Dec. 1, 2019.)
(1) Revised subsection 10.2.2 to better describe viscometer (4) Revised subsection 11.1.4.1 to require a minimum equilib-
charging requirements when Jet Fuel at –20 °C is being rium time for jet fuel samples of 30 min.
undertaken and recommendations on the use of loose packed (5) Added new precision estimates for jet fuel at –20 °C in
drying tubes. 17.1.1, 17.2.1, and 17.2.2.
(2) Deleted subsection 10.2.2.1 as this captured in text of (6) Revised Footnote 16 describing the ILS conducted for the
subsection 10.2.2. above addition.
(3) Revised subsection 11.1.1 to restrict the viscometer type for (7) Old jet fuel precision estimates has been deleted.
analysis of jet fuel at –20 °C to the use of suspended-level type
viscometers as noted in Table A1.1.
(D445 – 18) that may impact the use of this standard. (Approved June 1, 2019.)
(1) Revised subsection 6.4.2.

(2) Added new Appendixes (nonmandatory information) sec-
tion and new Appendix X1.
(D445 – 17a) that may impact the use of this standard. (Approved Nov. 1, 2018.)
17
D445 − 19a
(1) Revised subsection 6.4 and Fig. 1; added new subsection
6.4.4.
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18
This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Designation: D3227 − 16
Designation: 342/00

(Thiol Mercaptan) Sulfur in Gasoline, Kerosine, Aviation
Turbine, and Distillate Fuels (Potentiometric Method)1
1. Scope* D4057 Practice for Manual Sampling of Petroleum and

1.1 This test method covers the determination of mercaptan Petroleum Products
sulfur in gasolines, kerosines, aviation turbine fuels, and D4177 Practice for Automatic Sampling of Petroleum and
distillate fuels containing from 0.0003 % to 0.01 % by mass of Petroleum Products
mercaptan sulfur. Organic sulfur compounds such as sulfides, D6299 Practice for Applying Statistical Quality Assurance
disulfides, and thiophene, do not interfere. Elemental sulfur in and Control Charting Techniques to Evaluate Analytical
amounts less than 0.0005 % by mass does not interfere. Measurement System Performance
Hydrogen sulfide will interfere if not removed, as described in 3. Summary of Test Method
9.2.
3.1 The hydrogen sulfide-free sample is dissolved in an
1.2 The values in acceptable SI units are to be regarded as alcoholic sodium acetate titration solvent and titrated potentio-
the standard. metrically with silver nitrate solution, using as an indicator the
1.2.1 Exception—The values in parentheses are for informa- potential between a glass reference electrode and a silver/
tion only. silver-sulfide indicating electrode. Under these conditions, the
1.3 This standard does not purport to address all of the mercaptan sulfur is precipitated as silver mercaptide and the
safety concerns, if any, associated with its use. It is the end point of the titration is shown by a large change in cell
responsibility of the user of this standard to establish appro- potential.
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. For specific 4. Significance and Use
warning statements, see Sections 6, 8, 9, and Appendix X1. 4.1 Mercaptan sulfur has an objectionable odor, an adverse
effect on fuel system elastomers, and is corrosive to fuel
2. Referenced Documents system components.
2.1 ASTM Standards:2
5. Apparatus
D1193 Specification for Reagent Water
D1250 Guide for Use of the Petroleum Measurement Tables 5.1 As described in 5.2 – 5.5; alternatively, any automatic
D1298 Test Method for Density, Relative Density, or API titration system may be used that, using the same electrode pair
Gravity of Crude Petroleum and Liquid Petroleum Prod- described in 5.3, is capable of performing the titration as
ucts by Hydrometer Method described in Section 9 and selecting the endpoint specified in
D4052 Test Method for Density, Relative Density, and API 11.1 with a precision that meets or is better than that given in
Gravity of Liquids by Digital Density Meter Section 14.
5.2 Meter—An electronic voltmeter, operating on an input
1
of less than 9 × 10− 12 A and having a sensitivity of 62 mV
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricantsand is the direct responsibility of over a range of at least 61 V. The meter shall be electrostati-
Subcommittee D02.03 on Elemental Analysis. cally shielded, and the shield shall be connected to the ground.3
Current edition approved Oct. 1, 2016. Published November 2016. Originally
approved in 1973. Last previous edition approved in 2013 as D3227 – 13. DOI: 5.3 Cell System, consisting of a reference and indicating
10.1520/D3227-16. electrode. The reference electrode should be a sturdy, pencil-
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or type glass electrode, having a shielded lead connected to
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
3
the ASTM website. Any apparatus that will give equal or better precision is acceptable.

1
D3227 − 16
ground. The indicating electrode shall be made from a silver NOTE 1—It is important to pass the propan-2-ol through a column of
wire, 2 mm (0.08 in.) in diameter or larger, mounted in an activated alumina to remove peroxides that may have formed on storage;
failure to remove peroxides will lead to low results. It is not necessary to
insulated support. Silver billet electrodes can also be used. perform this step if the alcohol is tested and found free of peroxides.
5.4 Buret, 10 mL capacity, graduated in 0.05 mL intervals, 6.6.1 Standardization—Add six drops of concentrated
with a tip that extends approximately 120 mm (5 in.) below the HNO3 (relative density 1.42) (Warning—Poison. Causes
stopcock. severe burns. Harmful or fatal if swallowed or inhaled) to
5.5 Titration Stand, preferably built as an integral part of the 100 mL of water in an appropriately sized beaker (for example,
meter housing and provided with supports for the electrodes a 200, 250, or 300 mL size beaker is typically large enough).
and electrical stirrer, all connected to ground. No permanent Remove oxides of nitrogen by boiling for 5 min. Cool to
change in meter reading should be noticeable upon connecting ambient temperature. Pipet 5 mL of 0.1 mol ⁄L KI solution into
or disconnecting the stirring motor. the beaker and titrate with the AgNO3 solution choosing the
end point at the inflection of the titration curve.
6. Reagents and Materials
6.7 Silver Nitrate, Standard Alcoholic Solution
6.1 Purity of Reagents—Reagent grade chemicals shall be (0.010 mol ⁄L)—Prepare daily when the test is being performed
used in all tests. Unless otherwise indicated, it is intended that by dilution of the 0.1 N standard. Pipet 100 mL of the
all reagents shall conform to the specifications of the Commit- 0.1 mol ⁄L standard into a 1 L volumetric flask and dilute to
tee on Analytical Reagents of the American Chemical Society, volume with propan-2-ol. Calculate the exact molarity.
where such specifications are available.4 Other grades may be
used, provided it is first ascertained that the reagent is of 6.8 Sodium Sulfide Solution (10 g ⁄L)—Dissolve 10 g of
sufficiently high purity to permit its use without lessening the Na2S in water and dilute to 1 L with water. Prepare fresh as
accuracy of the determination. needed.
6.1.1 Commercially available solutions may be used in NOTE 2—Anhydrous sodium sulfide is not widely available, and is
place of prepared laboratory solutions, when they are certified expensive. An aqueous solution of hydrated sodium sulfide (Na2S·9H2O)
to meet the required concentrations. at 30.6 g ⁄L is satisfactory.
6.1.2 Alternate volumes of solutions and solvents may be 6.9 Sulfuric Acid, dilute. Cautiously dilute five volumes of
prepared, when an equivalent concentration is maintained. water with one volume of sulfuric acid (relative density 1.84).
6.2 Water—Reagent grade, Type I, Specification D1193. (Warning—Adding the acid will generate heat: mix well. If
6.3 Cadmium Sulfate, Acid Solution (150 g ⁄L)—Dissolve water begins to boil, cool before adding more acid.) Note that
150 g of cadmium sulfate (3CdSO4·8H2O) in water. only limited volumes are required because only 10 mL are
(Warning—Poison. May be fatal if swallowed or inhaled. A needed for each litre of cadmium sulfate solution.
known carcinogen (animal positive).) Add 10 mL of dilute 6.10 Titration Solvent—Low molecular weight mercaptans,
H2SO4 (Warning—Poison. Causes severe burns. Harmful or as usually found in gasoline, are readily lost from the titration
fatal if swallowed or inhaled) and dilute to 1 L with water. solution if an acidic titration solvent is used. For the determi-
6.4 Potassium Iodide, Standard Solution (approximately nation of the higher molecular weight mercaptan as normally
0.1 mol ⁄L)—Dissolve 17 g of KI (weigh to 0.01 g) in 100 mL encountered in kerosines, aviation turbine fuels, and distillate
of water in a 1 L volumetric flask and dilute to 1 L. Calculate fuels, the acidic titration solvent is used to achieve more rapid
the exact molarity. equilibrium between successive additions of the titrant.
6.5 Propan-2-ol—(Warning—Flammable. Warning— 6.10.1 Alkaline Titration Solvent—Dissolve 2.7 g of sodium
Unless inhibited against it, peroxides can form in propan-2-ol acetate trihydrate (NaC2H3O2·3H2O) or 1.6 g of anhydrous
when stored in the same container that is exposed to air. When sodium acetate (NaC2H3O2) in 25 mL of water free of dis-
this happens and the propan-2-ol evaporates to dryness, an solved oxygen and pour into 975 mL of propan-2-ol (99 %)
explosion can occur. When peroxides are suspected, they may (Note 1). When necessary, remove dissolved oxygen by purg-
be removed by percolation through an activated alumina ing the solution with a rapid stream of nitrogen for 10 min each
column.) day prior to use; keep protected from the atmosphere. To
minimize oxygen from dissolving in the solution during
6.6 Silver Nitrate, Standard Alcoholic Solution storage, an option exists to nitrogen blanket the solution prior
(0.1 mol ⁄L)—Dissolve 17 g of AgNO3 in 100 mL of water in a to sealing the solvent container.
1 L volumetric flask and dilute to 1 L with propan-2-ol (99 %) 6.10.2 Acidic Titration Solvent—Dissolve 2.7 g of
(see Note 1). Store in a dark bottle and standardize at intervals NaC2H3O2·3H2O or 1.6 g of NaC2H3O2 in 20 mL of water free
frequent enough to detect a change of 0.0005 or greater in of dissolved oxygen and pour into 975 mL of propan-2-ol
molarity. (99 %) (Note 1) and add 4.6 mL of glacial acetic acid. When
necessary, remove dissolved oxygen by purging the solution
4
Reagent Chemicals, American Chemical Society Specifications, American with a rapid stream of nitrogen for 10 min each day prior to
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not use; keep protected from the atmosphere. To minimize oxygen
listed by the American Chemical Society, see Annual Standards for Laboratory
from dissolving in the solution during storage, an option exists
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, to nitrogen blanket the solution prior to sealing the solvent
MD. container.
2
D3227 − 16
6.11 Polishing Paper or Cloth, 6 µm to 20 µm average transfer temperature by use of the Petroleum Measurement
particle size abrasive. Tables (Guide D1250).
9.2 Removal of Hydrogen Sulfide—Test the sample qualita-
7. Sampling tively for hydrogen sulfide (H2S) by mixing 5 mL of the
7.1 Take the sample in accordance with Practice D4057 or sample with 5 mL of the acid CdSO4 solution. If no precipitate
Practice D4177. appears, proceed with the analysis of the sample as described
7.2 Methanethiol (methyl mercaptan) has a boiling point of in 9.3. If a yellow precipitate appears, remove the H2S in the
6.2 °C and may be expected to be present in light untreated following manner: Place a quantity of the sample, three to four
gasolines. Therefore, when the presence of this low boiling times that required for the analysis, in a separatory funnel
thiol (mercaptan) is known or expected, specimen to be tested containing a volume of the acid CdSO4 solution equal to one
shall be kept below 4 °C to prevent the loss of mercaptan from half that of the sample and shake vigorously. Draw off and
such samples. discard the aqueous phase containing the yellow precipitate.
Repeat the extraction with another portion of the CdSO4
7.3 Light naphtha fractions of high thiol content solution. Again draw off the aqueous phase, and wash the
(>100 mg ⁄kg) boiling below 85 °C have been shown to be very sample with three 25 mL to 30 mL portions of water, with-
sensitive to the titration temperatures. drawing the water after each washing. Filter the hydrocarbon
NOTE 3—Samples with a thiol content above 0.010 % by mass may be through a rapid paper. Test a small portion of the washed
analyzed by an appropriate reduction in test portion mass, ensuring that sample, such as in a test tube or vial, with a few millilitres of
the minimum volume of titration solvent plus test portion exceeds the CdSO4 solution as described previously. If no further
120 mL. If additional titration solvent is used to maintain this requirement, precipitate is formed, proceed as directed in 9.3. If a precipitate
a similar volume should be used for the blank titration. No precision has
been determined for thiol contents above 0.01 % by mass. appears, repeat the extraction with the CdSO4 solution until all
of the H2S has been removed. (Warning—Certain straight run
8. Preparation of Apparatus gasolines can contain significant amounts of both low molecu-
lar weight mercaptans and dissolved elemental sulfur, which,
8.1 Glass Electrode—After each manual titration, or batch when heated under total reflux conditions, may produce H2S by
of titrations, in the case of automatic titration systems, wipe the the inter-reaction of both. This phenomenon is particularly
electrode with a soft, clean tissue and rinse with water. Clean noticed in straight run gasolines produced from some natural
the electrode at frequent intervals (at least once a week) by gas condensates. Therefore, it is advisable that during the
stirring in cold chromic acid solution (Warning—Causes removal of H2S (and after all H2S has been extracted), that no
severe burns. A recognized carcinogen. Strong oxidizer— heat should be applied to the sample.)
contact with other material may cause fire. Hygroscopic. An 9.2.1 When the test results obtained are not for referee
equivalent, chromium-free cleaning solution may be used) for purposes and Quality Assurance/Quality Control (QA/QC)
a few seconds (10 s maximum). When not in use, keep lower protocol permits, an alternative test for, and a procedure for the
half of the electrode immersed in water. removal of, hydrogen sulfide can be used. This process uses
8.2 Silver/Silver-Sulfide Electrode—Each day prior to use, lead acetate paper and sodium hydrogen carbonate and is
or as triggered by the analysis of a quality control (QC) sample described in Appendix X1.
(see Section 12), prepare a fresh silver sulfide coating on the 9.2.2 There are available automated instruments that elimi-
electrode by the following method: nate the necessity to remove H2S when present, prior to
8.2.1 Burnish electrode with polishing paper or cloth until a performing the analysis, since the H2S titration curve does not
clean, polished silver surface shows. interfere with the titration curve of the thiol or mercaptan
8.2.2 Place electrode in operating position and immerse it in determination. Such equipment may be used when the test is
100 mL of titration solvent containing 8 mL of Na2S solution. not for referee purposes. The precision statement does not
8.2.3 Add slowly (for example, from a buret), with stirring, include data obtained from this alternate procedure.
10 mL of 0.1 mol ⁄L AgNO3 solution over a period from 10 min 9.2.3 For referee purposes, the protocol, as detailed in 9.2,
to 15 min. shall be used. A possible non-referee situation may be the
8.2.4 Remove electrode from solution, wash with water, and instance of routine refinery control.
wipe with a soft, clean tissue. 9.3 Measure with a pipet (or other suitable transfer device)
8.2.5 Between manual titrations, or batches of titrations in or weigh 20 mL to 50 mL of the original or treated sample into
the case of automatic titration systems, store the electrode a an appropriately sized beaker (for example, a 200 mL, 250 mL,
minimum of 5 min in 100 mL of titration solvent containing or 300 mL size beaker is typically large enough) containing
0.5 mL of the 0.1 mol ⁄L AgNO3 solution. 100 mL of the appropriate titration solvent. Place the beaker on
the titration stand or on the auto-sampler of an automatic
9. Procedure titration system. If an automatic titration system is used, set up
9.1 Determination of Density—If the sample is to be mea- the system to reproduce the experimental conditions specified
sured volumetrically, determine the density by Test Method in 9.3.1 – 9.3.3. Adjust the position of the titration stand so that
D1298 or Test Method D4052 at the temperature at which the the electrodes are about half immersed. Fill the buret with
test portion will be taken, either directly or from the density 0.01 mol ⁄L alcoholic AgNO3 solution and position it in the
determined at a reference temperature and converted to the titration assembly so that the tip extends approximately 25 mm
3
D3227 − 16
(1 in.) below the surface of the liquid in the beaker. Adjust the where:
speed of the stirrer to give vigorous stirring without spattering. A1 = millilitres of AgNO3 solution required to reach the
9.3.1 Record the initial buret and cell potential readings. end point in the vicinity of +300 mV (see Fig. 1),
The usual meter readings for mercaptan presence are in when a sample is being titrated,
the −250 mV to −350 mV range. Add suitable small portions of A0 = mL of AgNO3 solution required to reach the end
0.01 mol ⁄L AgNO3 solution and, after waiting until a constant point in the vicinity of +300mV (see Fig. 1), when
potential has been established, record the buret and meter only the blank is titrated. (Note, there are no other
readings. Consider the potential constant if it changes less than changes to the factors in the equation.)
6 mV ⁄min. d = density of sample at transfer temperature, g/mL,
D = dilution factor (if necessary, see Note 5),
NOTE 4—If potential readings obtained with freshly prepared electrodes I = grams of diluent used,
are erratic, it is possible that the electrodes are not properly conditioned. J = mL of diluent used,
This difficulty usually disappears in succeeding titrations. M = molarity of the AgNO3 solution,
NOTE 5—When analyzing samples with a relatively high mercaptan W = grams of sample used,
concentration, the use of a 20 mL to 50 mL sample size can require an 3.206 = 100 × g meq weight S in mercaptan, and
unreasonably long titration time and a large quantity of the titrant. For
V = mL of sample used.
such samples, a smaller sample size may be used or the original sample
may be diluted with a suitable solvent that is miscible with the sample and
free of mercaptans into the 20 mL to 50 mL sample size range prior to 11. Interpretation of Results
titrating the sample. The precision of samples using <20 mL sample sizes
or samples that have been diluted have not been determined in an 11.1 Treatment of Data—Plot the cumulative volumes of
interlaboratory study. 0.01 M AgNO3 solution added against the corresponding cell
NOTE 6—With certain instruments, the algebraic sign of the potentials potentials. Select the end point at the inflection point of the
may appear reversed. steepest portion of each “break” in the titration curve as shown
9.3.2 When the potential change is small for each increment in Fig. 1. The shape of the titration curve may change with
of AgNO3 solution, add volumes as large as 0.5 mL. When the different instruments. However, the above interpretation of the
change of potential becomes greater than 6 mV ⁄0.1 mL, use end point should be followed.
0.05 mL increments of 0.01 mol ⁄L AgNO3 solution. Near the 11.1.1 Mercaptans Only—If mercaptans alone are present in
end point of the titration, 5 min or 10 min may elapse before a the sample, the titration produces a curve of the first type
constant potential is obtained. Although it is important to wait shown in Fig. 1, having an initial plateau at a potential equal to
for equilibrium conditions, it is also important that the duration or more negative than −250 mV, and an end point when a
of the titration be as short as possible to avoid oxidation of the potential change of less than 6 mV/min is reached and the
sulfur compounds by atmospheric oxygen. Once started, a change in mV/min of titrant is reduced with each incremental
titration must never be interrupted and resumed later. addition.
9.3.3 Continue the titration until the meter reading change 11.1.2 Mercaptans and Elemental Sulfur—When elemental
of the cell potential per 0.1 mL of 0.01 M AgNO3 solution has sulfur and mercaptans are both present in the sample, a
become relatively constant. Consider the potential constant if it chemical interaction occurs which, in the titration solvent used,
changes less than 6 mV ⁄min. Remove the titrated solution, precipitates silver sulfide (Ag2S) during the titration.
rinse the electrodes with alcohol, and wipe with a dry tissue. If 11.1.3 When mercaptans are present in excess, the end of
an automatic titration system is used, rinse the electrodes well the Ag2S precipitation occurs at about −550 mV to −350 mV,
with alcohol, allow the excess alcohol to drain off the electrode and is followed by the precipitation of the silver mercaptide to
and then proceed with the next sample. Between successive the +300 mV end point. This situation is shown in the middle
determinations (or batches of determinations in the case of curve of Fig. 1. Since all of the Ag2S originates from an
automatic titration systems) on the same day, store the elec- equivalent amount of mercaptan, the total titration to the
trodes in accordance with 8.1 and 8.2.5. mercaptide end point must be used to calculate the amount of
mercaptan sulfur.
9.4 As often as is required and preferably, at least daily, 11.1.4 When elemental sulfur is present in excess, the end of
when the test equipment is being used, perform a blank the Ag2S precipitation is taken in the same region ( +300 mV)
titration following 9.3 – 9.3.3 without adding a test sample. as in the case of silver mercaptide, and is calculated as
mercaptan sulfur.
10. Calculation 11.1.5 When samples of light gasolines containing meth-
10.1 Calculate the mercaptan sulfur content of the sample as anethiol (methyl mercaptan) or heavier thiols (mercaptans)
follows: appear to give erratic results, it may be necessary to cool and
maintain the test apparatus below 4 °C prior to proceeding, as
Mercaptan sulfur, mass % 5 ~ DM ~ A 1 2 A 0 ! 3 3.206! /W (1)
detailed in 9.2 – 9.4 inclusive. For these samples, this step may
or
be necessary for more reproducible test results.
Mercaptan sulfur, mass % 5 ~ DM ~ A 1 2 A 0 ! 3 3.206! / ~ d 3 V !
(2) 12. Quality Assurance/Quality Control
D 5 ~ W1I ! /W (3) 12.1 Confirm the performance of the instrument and the test
D 5 ~ V1J ! /V (4) procedure by analyzing a control (QC) sample.
4
D3227 − 16
FIG. 1 Illustrative Potentiometric Titration
12.1.1 When QA/QC protocols are already established in operation of the test method, exceed the following values only
the testing facility, these may be used when they confirm the in one case in twenty:
reliability of test result. Repeatability 0.00007 + 0.027x (see Note 7)
12.1.2 When there is no QA/QC protocol established in the
where:
testing facility, Appendix X2 may be used as the QA/QC
system. x = average mercaptan sulfur, mass %.
NOTE 7—This amount is shown graphically in Fig. 2.
12.2 Users of this test method are advised that in contractual
agreements, one or more of the contracting parties can and may 14.1.2 Reproducibility—The difference between two single
make Appendix X2 a mandatory practice. and independent results obtained by different operators work-
ing in different laboratories on identical test material would, in
13. Report the long run, in the normal and correct operation of the test
method, exceed the following values only in one case in
13.1 Report the result to the nearest 0.0001 % (m ⁄m) or to
twenty:
the nearest 1 mg ⁄kg.
Reproducibility 0.00031 + 0.042x (see Note 7)
14. Precision and Bias where:
14.1 Precision—The precision of this test method as deter- x = average mercaptan sulfur, mass %.
mined by statistical examination of interlaboratory results is as
follows: 14.2 Bias—The bias for the procedure in this test method
14.1.1 Repeatability—The difference between two succes- has not been determined.
sive test results, obtained by the same operator with the same
apparatus under constant operating conditions on identical test 15. Keywords
material, would in the long run, in the normal and correct 15.1 mercaptan; potentiometric; sulfur
5
D3227 − 16
FIG. 2 Precision Curve for Mercaptan Sulfur in Gasolines, Kerosines, Aviation Turbine, and Distillate Fuels
APPENDIXES
X1. AN ALTERNATIVE METHOD FOR THE REMOVAL OF HYDROGEN SULFIDE
X1.1. Scope until the sample indicates the absence of hydrogen sulfide in
X1.1.1 This test method provides an alternative to using a accordance with the lead acetate test.
cadmium sulfate acid solution. (Warning—Poison. May be X1.3. Reagents and Materials
fatal if swallowed or inhaled. A known carcinogen (animal
positive).) (Warning—Poison. Causes severe burns. Harmful X1.3.1 Purity of Reagents—All reagents shall conform to
or fatal if swallowed or inhaled.) the details specified in 6.1 of the main procedure.
X1.1.2 This test method uses lead acetate test paper X1.3.2 Commercially prepared solutions and test paper may
(Warning—Poison, health hazard, may be toxic by ingestion, be used when it is certain they will conform to the specifica-
inhalation, or absorption through the skin) to test for the tions detailed in 6.1 of the main procedure.
presence of hydrogen sulfide and sodium hydrogen carbonate X1.3.3 Lead Acetate, Aqueous Solution—Prepare a 5 %
for the removal of hydrogen sulfide. (m/m) solution of lead acetate [(CH3COO)2Pb.3H2O] in water.
X1.1.3 This test method shall not be used when the sample X1.3.4 Lead Acetate, Test Paper—Soak to saturation test
is a referee sample or when QA/QC protocols specify the test strips of filter paper in the lead acetate solution and allow to
method as written. Instances in which they can be used may be dry. (Warning —Since these papers react with hydrogen
instances of routine refinery control samples. sulfide, it is necessary to dry and store them in a hydrogen
sulfide free atmosphere.)
X1.2. Summary of Test Method X1.3.5 Sodium Hydrogen Carbonate, Aqueous Solution—
X1.2.1 Hydrogen sulfide is detected by saturating strips of Prepare this solution by dissolving 50 g 6 1 g of sodium
filter paper with lead acetate and drying them prior to use. hydrogen carbonate (Na2HCO3) in water; dilute to 1 L in a
When properly prepared and used, they will turn from a white volumetric flask.
color to a darker color due to the precipitation of lead sulfide X1.3.6 Test Paper—Any standard laboratory filter paper,
by hydrogen sulfide. capable of absorbing the lead acetate solution may be used.
X1.2.2 The hydrogen sulfide is removed by repeated wash- (Warning—Any paper containing active sulfides will interfere
ings with an aqueous solution of sodium hydrogen carbonate with the test.)
6
D3227 − 16
X1.4. Procedure, Testing and Removal of Hydrogen X1.4.2.3 Allow the two phases to settle, and when settled,
Sulfide draw off and discard the aqueous phase.
X1.4.1 Test a small portion of the sample by inserting a X1.4.2.4 Test the hydrocarbon phase again with fresh lead
small strip of lead acetate test paper into it. When the test paper acetate paper.
is discolored by turning to a brown or black, the presence of X1.4.2.5 Continue with the washing process until the
hydrogen sulfide is indicated. washed sample tests negative to the presence of hydrogen
X1.4.2 When the presence of hydrogen sulfide is indicated, sulfide. (Warning—When elemental sulfur and mercaptans are
proceed as follows: both present, it is possible that upon reheating the washed
X1.4.2.1 Take a portion of the sample that is 3 to 4 times the sample, more hydrogen sulfide will form. Because the forma-
volume required for the actual test and pour it into a separatory tion of more hydrogen sulfide (after washing) will affect the
funnel. test result, do not reheat the washed portion of the sample.)
X1.4.2.2 Add a volume of sodium hydrogen carbonate
X1.4.2.6 When the test portion is free of all hydrogen
equal to about half the volume of the test portion and shake
sulfide, the determination of the thiol (mercaptan) content may
thoroughly. (Warning—When the sample is volatile, release
proceed.
any pressure developed by the shaking, cautiously.)
X2. GENERIC QUALITY CONTROL STATEMENT FOR D02 TEST METHODS
X2.1 Confirm the performance of the instrument and the test criticality of the quality being measured, the demonstrated
procedure by analyzing a QC sample. stability of the testing process, and customer requirements.
Generally, a QC sample should be analyzed on each day of
X2.2 Prior to monitoring the measurement process, the user testing routine samples. The QC frequency should be increased
of the method needs to determine the average value and control when a large number of samples are routinely analyzed.
limits of the QC sample (see Practice D6299 and MNL75). However, when it is demonstrated that the testing is under
X2.3 Record the QC results and analyze by control charts or statistical control, the QC testing frequency may be reduced.
other statistically equivalent techniques to ascertain the statis- The QC sample precision should be periodically checked
tical control status of the total testing process (see Practice against the ASTM method precision to ensure data quality.
D6299 and MNL75). Any out-of-control data should trigger
investigation for root cause(s). The results of this investigation X2.5 It is recommended that, when possible, the type of QC
may, but not necessarily, result in instrument recalibration. sample that is regularly tested be representative of the samples
routinely analyzed. An ample supply of QC sample material
X2.4 In the absence of explicit requirements given in the should be available for the intended period of use and must be
test method, the frequency of QC testing is dependent on the homogeneous and stable under the anticipated storage condi-
tions.
5
ASTM MNL7, Manual of Presentation of Data Control Chart Analysis, 6th ed.,
Section 3: Control Chart for Individuals, ASTM International, W. Conshohocken, X2.6 See Practice D6299 and MNL75 for further guidance
PA. on QC and Control Charting techniques.
SUMMARY OF CHANGES
(D3227 – 13) that may impact the use of this standard. (Approved Oct. 1, 2016.)
(1) Subsection 8.2.3 was revised.
7
D3227 − 16
8
Designation: D4052 − 18a

Density, Relative Density, and API Gravity of Liquids by
Digital Density Meter1
1. Scope* bubbles in the U-tube can be established with certainty. For the
1.1 This test method covers the determination of the density, determination of density in crude oil samples use Test Method
relative density, and API Gravity of petroleum distillates and D5002.
viscous oils that can be handled in a normal fashion as liquids 1.4 The values stated in SI units are regarded as the
at the temperature of test, utilizing either manual or automated standard, unless stated otherwise. The accepted units of mea-
sample injection equipment. Its application is restricted to sure for density are grams per millilitre (g/mL) or kilograms
liquids with total vapor pressures (see Test Method D5191) per cubic metre (kg/m3).
typically below 100 kPa and viscosities (see Test Method D445 1.5 This standard does not purport to address all of the
or D7042) typically below about 15 000 mm2/s at the tempera- safety concerns, if any, associated with its use. It is the
ture of test. The total vapor pressure limitation however can be responsibility of the user of this standard to establish appro-
extended to >100 kPa provided that it is first ascertained that priate safety, health, and environmental practices and deter-
no bubbles form in the U-tube, which can affect the density mine the applicability of regulatory limitations prior to use.
determination. Some examples of products that may be tested For specific warning statements, see 3.2.1, Section 7, 9.1, 10.2,
by this procedure include: gasoline and gasoline-oxygenate and Appendix X1.
blends, diesel, jet, basestocks, waxes, and lubricating oils. 1.6 This international standard was developed in accor-
1.1.1 Waxes and highly viscous samples were not included dance with internationally recognized principles on standard-
in the 1999 interlaboratory study (ILS) sample set that was ization established in the Decision on Principles for the
used to determine the current precision statements of the Development of International Standards, Guides and Recom-
method, since all samples evaluated at the time were analyzed mendations issued by the World Trade Organization Technical
at a test temperature of 15 °C. Wax and highly viscous samples Barriers to Trade (TBT) Committee.
require a temperature cell operated at elevated temperatures
necessary to ensure a liquid test specimen is introduced for 2. Referenced Documents
analysis. Consult instrument manufacturer instructions for
2.1 ASTM Standards:2
appropriate guidance and precautions when attempting to
D287 Test Method for API Gravity of Crude Petroleum and
analyze wax or highly viscous samples. Refer to the Precision
Petroleum Products (Hydrometer Method)
and Bias section of the method and Note 9 for more detailed
D445 Test Method for Kinematic Viscosity of Transparent
information about the 1999 ILS that was conducted.
and Opaque Liquids (and Calculation of Dynamic Viscos-
1.2 In cases of dispute, the referee method is the one where ity)
samples are introduced manually as in 6.2 or 6.3, as appropri- D1193 Specification for Reagent Water
ate for sample type. D1250 Guide for Use of the Petroleum Measurement Tables
1.3 When testing opaque samples, and when not using D1298 Test Method for Density, Relative Density, or API
equipment that is capable of automatic bubble detection, Gravity of Crude Petroleum and Liquid Petroleum Prod-
proper procedure shall be established so that the absence of air ucts by Hydrometer Method
D4057 Practice for Manual Sampling of Petroleum and
Petroleum Products
1
2
Subcommittee D02.04.0D on Physical and Chemical Methods. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Dec. 15, 2018. Published February 2019. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1981. Last previous edition approved in 2018 as D4052 – 18. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D4052-18A. the ASTM website.

Copyright by ASTM Int'l (all rights reserved); Sun Feb 23 23:58:06 EST 2020
1
D4052 − 18a
D4177 Practice for Automatic Sampling of Petroleum and 3.2.5.1 Discussion—Sample material residing in filling
Petroleum Products nozzles, tubing and valve manifolds is not considered “Test
D4377 Test Method for Water in Crude Oils by Potentiomet- Specimen.” A test specimen can be measured only once.
ric Karl Fischer Titration
D5002 Test Method for Density, Relative Density, and API 4. Summary of Test Method
Gravity of Crude Oils by Digital Density Analyzer 4.1 A volume of approximately 1 mL to 2 mL of liquid
D5191 Test Method for Vapor Pressure of Petroleum Prod- sample is introduced into an oscillating U-tube and the change
ucts and Liquid Fuels (Mini Method) in oscillating frequency caused by the change in the mass of the
D7042 Test Method for Dynamic Viscosity and Density of U-tube is used in conjunction with calibration data to deter-
Liquids by Stabinger Viscometer (and the Calculation of mine the density, relative density, or API Gravity of the sample.
Kinematic Viscosity) Both manual and automated injection techniques are described.
3. Terminology 5. Significance and Use

3.1 Definitions: 5.1 Density is a fundamental physical property that can be
3.1.1 density, n—mass per unit volume at a specified tem- used in conjunction with other properties to characterize both
perature. the light and heavy fractions of petroleum and petroleum
products.
3.1.1.1 Discussion—The SI unit of density is kg/m3; the unit
5.2 Determination of the density or relative density of
of measure g/cm3 is commonly used in industry.
petroleum and its products is necessary for the conversion of
3.1.2 relative density, n—the ratio of the density of a measured volumes to volumes at the standard temperature of
material at a stated temperature to the density of water at a 15 °C.
stated temperature.
6. Apparatus
3.1.2.1 Discussion—Relative density is also commonly
known as specific gravity. Commonly used stated temperatures 6.1 Digital Density Analyzer—A digital analyzer consisting
are 20 °C ⁄20 °C, 15 °C ⁄15 °C, 20 °C ⁄4 °C and 60 °F ⁄60 °F. of a U-shaped, oscillating tube, U-tube, and a system for
“Relative density” was historically known as the deprecated electronic excitation, frequency counting, and display. The
term “specific gravity.” analyzer shall accommodate the accurate measurement of the
3.2 Definitions of Terms Specific to This Standard: sample temperature during measurement or shall control and
3.2.1 adjustment, v—the operation of bringing the instru- keep the sample temperature constant to 60.05 °C. The instru-
ment to a state of performance suitable for its use, by setting or ment shall be capable of meeting the precision requirements
adjusting the density meter constants. described in this test method.
3.2.1.1 Discussion—On some digital density analyzer 6.2 Syringes, for use primarily in manual injections, at least
instruments, an adjustment may be made rather than calibrating 2 mL in volume with a tip or an adapter tip that will fit the
the instrument. The adjustment procedure uses air and freshly opening of the U-tube.
boiled reagent water (Warning—Handling water at boiling or
6.3 Flow-Through or Pressure Adapter, for use as an alter-
near boiling temperature can present a safety hazard. Wear
native means of introducing the sample into the density
appropriate personal protective equipment.) as standards to
analyzer either by a pump, by pressure, or by vacuum.
establish the linearity of measurements over a range of NOTE 1—It is highly recommended that a vacuum not be applied to
operating temperatures. samples prone to light-end loss, as it can easily lead to the formation of
3.2.2 API gravity, n—a special function of relative density bubbles in the U-tube. It is recommended to fabricate a special cap or
stopper for sample containers so that air, such as from a squeeze pump, is
60 °F ⁄60 °F, represented by: used to displace a test specimen to the U-tube measuring cell by the
141.5 flow-through method.
°API= 2 131.5 (1)
relative density 6.4 Autosampler, required for use in automated injection
3.2.2.1 Discussion—No statement of reference temperature analyses. The autosampler shall be designed to ensure the
is required since 60 °F is included in the definition. integrity of the test specimen prior to and during the analysis
and be equipped to transfer a representative portion of sample
3.2.3 calibration, v—set of operations that establishes the
aliquot to the digital density analyzer.
relationship between the reference density of standards and the
corresponding density reading of the instrument. 6.5 Ultrasonic Bath, Unheated, (optional), of suitable di-
3.2.4 sample aliquot, n—the fraction of the original labora- mensions to hold container(s) placed inside of bath, for use in
tory sample dedicated for this test. effectively dissipating and removing air or gas bubbles that
may be entrained in viscous sample types prior to analysis.
3.2.4.1 Discussion—The sample aliquot is typically residing
in syringes, sample vials, beakers, or containers for the purpose 7. Reagents and Materials
of transferring a representative test specimen into the appara- 7.1 Purity of Reagents—Reagent grade chemicals shall be
tus’ U-tube. used in all tests. Unless otherwise indicated, it is intended that
3.2.5 test specimen, n—the volume of the sample aliquot all reagents shall conform to the specifications of the Commit-
residing in the U-tube during the measurement cycle. tee on Analytical Reagents of the American Chemical Society,
2
D4052 − 18a
where such specifications are available.3 Other grades may be sample properties in relation to both ambient temperature and pressure.
used, provided it is first ascertained that the reagent is of 8.3.2 For manual injections, draw the test specimen from a
sufficiently high purity to permit its use without lessening the properly mixed laboratory sample using an appropriate sy-
accuracy of the determination. ringe. If the proper density analyzer attachments and connect-
7.2 Purity of Water—Unless otherwise indicated, references ing tubes are used, as described in 6.3, then the test specimen
to water shall be understood to mean reagent water as defined can be delivered directly to the analyzer’s U-tube from the
by Type II of Specification D1193 or higher. mixing container. For automated injections, it is necessary to
first transfer a portion of sample by appropriate means from a
7.3 Water, reagent water, freshly boiled to remove dissolved
properly mixed laboratory sample to the autosampler vials, and
gasses, for use as primary calibration standard. (Warning—
take the necessary steps to ensure the integrity of the test
Handling water at boiling or near boiling temperature can
specimen prior to and during the analysis. Sample vials for the
present a safety hazard. Wear appropriate personal protective
autosampler shall be sealed immediately after filling up to
equipment.)
80 % 6 5 % and shall be kept closed until the auto sampler
7.4 Cleaning Solvent, such as petroleum naphtha4 transfers the test specimen into the measuring cell. For highly
(Warning—Petroleum naphtha is extremely flammable), or volatile samples, cool the sample prior to measurement. Follow
other materials that are capable of flushing and removing the manufacturer’s instructions.
samples entirely from the U-tube.
NOTE 3—Overfilled sample vials can result in cross-contamination
7.5 Acetone, for flushing and drying the U-tube. between sample vials.
(Warning—Extremely flammable.)
7.6 Dry Air, for drying the U-tube. 9. Preparation of Apparatus
9.1 Set up the density analyzer following the manufacturer’s
8. Sampling, Test Specimens, and Test Units instructions. Set the internal temperature control so that the
8.1 Sampling is defined as all the steps required to obtain an desired test temperature is established and maintained in the
aliquot of the contents of any pipe, tank, or other system, and U-tube of the analyzer. Verify the instrument’s calibration at
to place the sample into the laboratory test container. The the same temperature at which the density or relative density of
laboratory test container and sample volume shall be of the sample is to be measured or perform an adjustment (see
sufficient capacity to mix the sample and obtain a homoge- 3.2.1–Discussion) in preparation of analyzing samples.
neous sample for analysis. (Warning—Precise setting and control of the test temperature
8.2 Laboratory Sample—Use only representative samples in the U-tube is extremely important. An error of 0.1 °C can
obtained as specified in Practices D4057 or D4177 for this test result in a change in density of one in the fourth decimal when
method. measuring in units of grams per millilitre.)
8.3 Test Specimen—A portion or volume of sample aliquot 10. Verification and Adjustment
obtained from the laboratory sample and delivered to the
density analyzer U-tube. The test specimen is obtained as 10.1 As a minimum requirement, calibration verification of
follows: the instrument is required when first set up and whenever the
8.3.1 Mix the sample if required to homogenize, taking care test temperature is changed. Whenever the apparatus fails a
to avoid the introduction of air bubbles. The mixing may be calibration verification without discernible cause, the apparatus
accomplished as described in Practice D4177 or Test Method must be adjusted. See 3.2.1.
D4377. Mixing at room temperature in an open container can 10.2 The adjustment routine for digital density meters
result in the loss of volatile material from certain sample types involves using a minimum of two reference media. Typically,
(for example, gasoline samples), so mixing in closed, pressur- this will be air and freshly boiled reagent water under atmo-
ized containers or at least 10 °C below ambient temperature is spheric conditions. (Warning—Handling water at boiling or
required for such sample types where loss of volatile material near boiling temperature can present a safety hazard. Wear
is a potential concern. For some sample types, such as viscous appropriate personal protective equipment.) Other materials
lube oils that are prone to having entrained air or gas bubbles such as n-nonane, n-tridecane, cyclohexane, and n-hexadecane
present in the sample, the use of an ultrasonic bath (see 6.5) (for high temperature applications) can also be used as appro-
without the heater turned on (if so equipped), has been found priate adjustment materials, provided the reference materials
effective in dissipating bubbles typically within 10 min. have density values that are certified and traceable to national
standards.
NOTE 2—When mixing samples with volatile components, consider the
10.3 Follow the manufacturer’s instructions for the proper
3
adjustment of the apparatus. If the apparatus is adjusted using
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not air and reagent water, observe the proper entries of air and
listed by the American Chemical Society, see Analar Standards for Laboratory water density values.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia 10.3.1 The density of air varies with pressure and relative
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
humidity (see Table 1). Therefore, it is important that the
MD.
4
Suitable solvent naphthas are marketed under various designations such as dewpoint of ambient air is below the adjustment temperature of
“Petroleum Ether,” “Ligroine,” or “Precipitation Naphtha.” the instrument as to avoid condensation of water in the U-tube.
3
D4052 − 18a
TABLE 1 Density of WaterA the laboratory to be in an out-of-control situation, such as
NOTE 1—Several metrological entities have issued water density tables exceeding the laboratory’s control limits, instrument adjust-
and alternative water density data is referenced in publications external to ment is required. An ample supply of QC sample material
ASTM and this test method. Using water density data from an alternative should be available for the intended period of use, and must be
recognized source does not pose a compliance issue with this test method
homogeneous and stable under the anticipated storage condi-
as the variation in the data typically is limited to the sixth decimal place.
tions. Prior to monitoring the measurement process, the user of
Temperature, Density, g/mL Temperature, Density, Temperature, Density,
°C °C g/mL °C g/mL the method needs to determine the average and control limits of
0.01 0.999844 21.0 0.997996 40.0 0.992216 the QC sample. The QC sample precision should be checked
3.0 0.999967 22.0 0.997773 45.0 0.990213 against the method precision to ensure data quality.
4.0 0.999975 23.0 0.997541 50.0 0.988035
5.0 0.999967 24.0 0.997299 55.0 0.985693 11.2 Although not mandatory, it is recommended that peri-
10.0 0.999703 25.0 0.997048 60.0 0.983196 odic analyses of certified density standards (that is, traceable to
15.0 0.999103 26.0 0.996786 65.0 0.980551
15.56 0.999016 27.0 0.996516 70.0 0.977765
national standards) that are separate from those that may be
16.0 0.998946 28.0 0.996236 75.0 0.974843 used in adjusting the instrument, be used to confirm testing
17.0 0.998778 29.0 0.995947 80.0 0.971790 accuracy.
18.0 0.998599 30.0 0.995650 85.0 0.968611
19.0 0.998408 35.0 0.994033 90.0 0.965310
20.0 0.998207 37.78 0.993046 99.9 0.958421
12. Procedure
A
Densities conforming to the International Temperature Scale 1990 (ITS 90) were 12.1 Manual Injection:
extracted from Lemmon, E. W., McLinden, M. O., and Friend, D. G., “Thermo- 12.1.1 Introduce a volume of about 1 mL to 2 mL, of sample
physical Properties of Fluid Systems,”NIST Chemistry WebBook, NIST Standard
Reference Database No. 68, Eds. P.J. Linstrom and W.G. Mallard, National
into the clean, dry U-tube of the instrument using a suitable
Institute of Standards and Technology, Gaithersburg, MD, http://webbook.nist.gov. syringe or alternative, as described in 6.3.
(retrieved July 24, 2013). 12.1.2 The sample can also be introduced by siphoning.
Plug the external TFE-fluorocarbon capillary tube into the
entry port of the U-tube. Immerse the other end of the capillary
This can be achieved by flushing ambient air through a in the sample and apply suction to the other port using a
desiccant container and into the U-tube. syringe or vacuum line until the U-tube is properly filled (see
10.3.2 The density of air varies with ambient pressure as a Note 1).
consequence of site elevation and atmospheric changes in 12.1.3 Ensure that the U-tube is properly filled and that no
pressure. The air density can be calculated using this formula: gas bubbles are present. The sample must be homogeneous and
ρ air 5 0.001293@ 273.15 ⁄ T #@ P/101.325# g/mL (2) free of even the smallest gas bubbles. Check the integrity of the
filled sample by using optical or physical methods to verify
where: absence of gas bubbles. If gas bubbles are detected, empty and
ρair = density of air, refill the U-tube, and recheck for gas bubbles.
T = temperature, K, and
NOTE 6—If the sample is too dark in color to determine the absence of
P = site atmospheric pressure at the time of adjustment, bubbles with certainty, the density cannot be measured within the stated
kPa. precision limits of Section 15.
NOTE 4—P should preferably be determined by direct measurement of
the barometric pressure at the site of calibration. If direct measurement is 12.1.4 For most instrument models, it is recommended to
not available, and common sources providing weather data are consulted, turn the illumination light off with minimal delay after sample
the pressure reported is typically corrected to Sea Level, PSL. Therefore, introduction and checking for bubbles because the heat gener-
such pressure data must be corrected back to site pressure, P. For ated can affect the measurement temperature. For some models
correction of PSL to P:
however, the cell light may be left on without affecting results.
P=P SL 2 @ Site Elevation ~meters!/82.3# (3) Refer to the manufacturer’s recommendations concerning
NOTE 5—In the International Standard Atmosphere, ISA, the pressure whether to leave the illumination light off or on.
drops 1 kPa per 82.3 m of elevation. 12.1.5 After the instrument displays a steady reading to four
10.3.3 The water density values are given in Table 1. Water significant figures for density, relative density, or API Gravity,
density values are considered constant with respect to pressure and five for T-values, indicating that temperature equilibrium
in the range of normally occurring atmospheric pressure. has been reached, record the density, relative density, API
Gravity or T-values, or both, as appropriate. For instruments
11. Quality Control Checks that can print out results from the display, the print out can be
11.1 Confirm the instrument is in statistical control at least used to meet the recording requirements.
once a week when it is in use, by analyzing a quality control 12.1.6 Based on the 1999 ILS6 testing protocols (see Note
(QC) sample that is representative of samples typically ana- 9), precision determinations involving a single manual
lyzed. Analysis of a single QC sample can be sufficient. injection, as well as taking the average of two manual
Analysis of QC sample results can be carried out using control injections, was evaluated. See the Precision and Bias section
chart techniques.5 If the QC sample result determined causes for more details. If the laboratory performs a single manual
5 6
ASTM MNL 7, Manual on Presentation of Data Control Chart Analysis, Supporting data have been filed at ASTM International Headquarters and may
Section 3: Control Charts for Individuals, 6th ed., ASTM International, W. be obtained by requesting Research Report RR:D02-1734. Contact ASTM Customer
Conshohocken, PA. Service at service@astm.org.
4
D4052 − 18a
determination, the density, relative density, or API Gravity 12.2.3 Record the density, relative density, or API Gravity
values recorded in 12.1.5, or a combination thereof, is to be results, or a combination thereof, determined by the analyses as
used for reporting purposes. In most cases, a single manual appropriate, such as by using the instrument print out of results
injection determination is sufficient for sample analysis. to meet the recording requirements.
12.1.6.1 If the laboratory decides to perform a second
manual injection determination for a given sample, repeat 13. Calculation
12.1.1 – 12.1.5. If the two determinations do not differ by more 13.1 Calculating Density Analyzers—The recorded or
than 0.0002 g ⁄mL for density or 0.0002 for relative density, printed value is the final result when a single determination is
average the two determinations, otherwise, discard both deter- conducted (or taking the average of two determinations as the
minations and repeat the analysis using two new test specimens final result as identified in Section 12), expressed either as
until the acceptance criteria identified above is satisfied. With density in g/mL, kg/m3 or as relative density. Note that kg/m3 =
respect to API Gravity determinations of gasoline or RFG 1000 × g/mL.
samples, if the two determinations do not differ by more than
0.05° API Gravity units, average the two determinations, 13.2 If it is necessary to convert a result obtained using the
otherwise, discard both determinations and repeat the analysis density meter to API Gravity, or a density or relative density at
using two new test specimens until the acceptance criteria is another temperature, Guide D1250 can be used only if the glass
satisfied. With respect to API Gravity determinations of expansion factor has been excluded.
distillates, basestocks, and lubricating oils, follow the protocol NOTE 8—Some digital density analyzers are equipped to automatically
calculate and report sample results in API gravity units (see Test Method
in the prior sentence except use 0.03° API Gravity units as the D287 or D1298), based on the density or relative density results, or a
acceptance criteria. Averaged results meeting the criteria iden- combination thereof, determined by this test method and using the
tified in this section is to be used for reporting purposes. appropriate conversion equation derived from Guide D1250 (which
excludes the glass expansion factor), for the specific sample type being
12.2 Automated Injection: analyzed.
12.2.1 The use of an autosampler (see 6.4) is required when
analyzing samples by automated injection. Follow manufactur- 14. Report
er’s instructions for ensuring the integrity of the test specimen
14.1 In reporting density, state the test temperature and the
prior to analysis, as well as transferring a representative test
units (for example: density at 20 °C = 0.8765 g ⁄mL or
specimen into the instrument for analysis.
876.5 kg ⁄m3).
12.2.1.1 If the laboratory decides to perform a second
automated injection determination for a given distillate, 14.2 In reporting relative density, state both the test tem-
basestock, or lubricating oil (see Note 9 and the Precision and perature and the reference temperature, but no units (for
Bias section), use the same acceptance criteria in 12.1.6.1 for example: relative density, 20/20 °C = 0.xxxx).
allowed differences between each determination for density 14.3 Report the final result for density or relative density to
(0.0002 g ⁄mL), relative density (0.0002) and API Gravity units four significant figures and reference this test method.
(0.03°) as for manually injected samples. Averaged results
14.4 If reporting sample results in API gravity units (see
meeting the necessary acceptance criteria are to be used for
Note 8), report the final results to the nearest 0.1° API.
reporting purposes.
14.5 In some cases, it may be necessary to report if results
NOTE 7—Density meters equipped with autosamplers allow for unat-
were based on a single determination or an average of two
tended operation, and erroneous results rooted in filling problems may
pass unnoticed. Performing duplicate determinations may uncover sample determinations, as well as if results were determined by manual
filling issues regardless of the sample material being tested. injection or automated injection to meet specific requirements,
12.2.2 Opaque samples may be tested using either manual such as data recipients wanting to know such information in
injection method described in 12.1 or using an autosampler as order to understand how to interpret results relative to the
described in 12.2. When testing opaque samples, proper published method precision values. In such cases, it is permis-
procedure shall be established by which the absence of air sible to report this information along with the test results.
bubbles in the measuring cell can be confirmed with certainty.
Such procedures include multiple determinations and evalua- 15. Precision and Bias6
tion of closeness of determinations, utilizing optical or physical 15.1 The precision of the method as obtained by statistical
methods for air bubble detection, or both. examination of interlaboratory test results at a test temperature
12.2.2.1 This test method does not offer precision and bias of 15 °C is as follows for the following sample types and
values for opaque samples and because sample properties vary ranges:
greatly, determinability criteria is not offered, but shall be 15.1.1 Repeatability—The difference between successive
established by a series of tests determinations on representative test results obtained by the same operator with the same
sample material. Perform a minimum of three consecutive apparatus under constant operating conditions on identical test
determinations of different test specimens from the same material, would in the long run, in the normal and correct
syringe or sample vial without removing the syringe from the operation of the test method, exceed the following value only
apparatus and without any rinsing or cleaning between deter- in one case in twenty:
minations. Average the two determinations with the highest 15.1.1.1 Density (g/mL) and Relative Density—See Table 2.
density or lowest API number and report per 12.2.3. 15.1.1.2 API Gravity—See Table 3.
5
D4052 − 18a
TABLE 2 Density (g/mL) and Relative Density (Repeatability)
Range Sample Types Testing Condition Repeatability
0.71–0.78 Gasoline and RFG Single Determination 0.00045
(Manual injection)
Average of 2 Determinations 0.00031
(Manual or automated injections)
0.80–0.88 Distillates, Basestocks, and Single Determination 0.00016
Lubricating Oils (Manual or automated injection)
TABLE 3 API Gravity (Repeatability)

Range Sample Types Testing Condition Repeatability
51–66 Gasoline and RFG Single Determination 0.090
(Manual injection)
29–45 Distillates, Basestocks, and Single Determination 0.032
TABLE 4 Density (g/mL) and Relative Density (Reproducibility)

Range Sample Types Testing Condition Reproducibility
0.71–0.78 Gasoline and RFG Single Determination 0.00190–0.0344 (D–0.75)
(Manual injection)
Average of 2 Determinations 0.00195–0.0315 (D–0.75)
0.80–0.88 Distillates, Basestocks, and Single Determination 0.00052
where: D = density or relative density value obtained
TABLE 5 API Gravity (Reproducibility)

Range Sample Types Testing Condition Reproducibility
51–66 Gasoline and RFG Single Determination 0.60 + 0.040 (G–60)
(Manual injection)
Average of 2 Determinations 0.60 + 0.037 (G–60)
29–45 Distillates, Basestocks and Single Determination 0.133
where: G = API Gravity value obtained
15.1.2 Reproducibility—The difference between two single single determination) versus taking the average of the two determinations
and independent results, obtained by different operators work- from each analysis set, as well as determining if there was a precision
ing in different laboratories on identical test material, would in effect between manual and automated injections. The repeatability and
reproducibility statements determined by the statistician reflect the corre-
the long run, in the normal and correct operation of the test sponding precision values associated with testing conditions identified. It
method, exceed the following values only in one case in should be noted that the precision statements determined for the gasoline
twenty: and RFG sample types in the 1999 ILS were poorer than expected relative
15.1.2.1 Density (g/mL) and Relative Density—See Table 4. to the precision statements determined for the distillates, basestocks, and
15.1.2.2 API Gravity—See Table 5. lubricating oils as well as relative to the previously published method
NOTE 9—The ASTM Interlaboratory Study (ILS) conducted in Fall version precision statements (which were based on the analysis of just
19996 involved 11 laboratories and 23 samples. The samples included 5 three pure compounds (benzene, toluene, and xylene) analyzed by 3
motor gasolines, 1 motor gasoline + ethanol, 4 reformulated gasolines laboratories in duplicate). The poorer than expected precision statements
(RFG), 2 lube oils, 1 basestock oil, 4 Jet-A fuels, 1 JP8 fuel, and 5 diesel for the gasoline and RFG sample types are likely due to the volatile nature
fuels. The ILS protocol required laboratories to perform a total of four of these materials, even though the ILS participants were provided
measurements per sample, which included both manual and automated instructions for how to properly handle these materials to minimize or
injections, with the first two determinations representing the first analysis prevent sample losses. The subcommittee responsible for the method is
set and the second two determinations representing the second analysis planning to conduct a subsequent ILS for gasoline and RFG sample types
set. This protocol was used to evaluate if a precision effect existed with additional scrutiny paid to sample handling issues as a means to try
between taking the first determination from each analysis set (that is, and improve the precision statements for these materials.
6
D4052 − 18a
NOTE 10—Four (4) of the samples analyzed in the ILS indicated in Note ing densities in the range of 747 kg ⁄m3 to 927 kg/m3 at 20 °C,
9 were ASTM Interlaboratory Crosscheck samples (that is, Gaso- with viscosities between 1 mPa.s and 5000 mPa.s (also at
line–MG9808 and MG9812, RFG–RFG9807, and RFG9809). The robust
mean of the total vapor pressures reported by Test Method D5191 for
20 °C). This study is documented in ASTM Research Report
these samples ranged from a low of 7.77 psi (MG9808) to a high of 13.40 RR:D02-1387.8 Method users should, therefore, be aware that
psi (RFG9809). This corresponds to an approximate total vapor pressure results obtained by this test method can be biased by as much
range of 54 to 92 kPa. as 0.6 kg ⁄m3 (0.0006 g ⁄mL).
15.2 Bias—After suggestions of its existence from NOTE 11—Newer instrumentation exists which purports to correct
density results due to the influence of viscosity. However, the responsible
literature,7 a study has been performed which has confirmed ASTM Technical Committee has not yet performed a new interlaboratory
the presence of a bias between known density values for study to confirm the elimination of the bias described in ASTM Research
reference materials and from values determined according to Report RR:D02-1387.8
this test method on the same reference materials. The matrix
16. Keywords
for this bias study comprised 15 participants, each analyzing
four reference oils with certified density values, established by 16.1 API Gravity; density; digital density analyzer; petro-
the Netherlands Meet Instituut (NMI), by pyknometry, cover- leum distillates; petroleum products; relative density
8
7
Fitzgerald, H. and D., “An Assessment of Laboratory Density Meters,” be obtained by requesting Research Report RR:D02-1387. Contact ASTM Customer
Petroleum Review, November 1992, pp. 544–549. Service at service@astm.org.
APPENDIXES
X1. ADJUSTMENT AND CALIBRATION PROCEDURE FOR NON-CALCULATING DENSITY METERS
X1.1 When calibration of the instrument is required, it is and free of even the smallest air or gas bubbles. Allow the
necessary to calculate the values of the constants A and B from display to reach a steady reading and record the T-value for
the periods of oscillation (T) observed when the sample cell water.
contains air and freshly boiled reagent water. (Warning—
Handling water at boiling or near boiling temperature can X1.2 Calculate the density of air at the temperature of test
present a safety hazard. Wear appropriate personal protective using the following equation:
equipment.) Other calibrating materials such as n-nonane, d a 5 0.001293@ 273.15 ⁄ T #@ P/101.325# g/mL (X1.1)
n-tridecane, cyclohexane, and n-hexadecane (for high tempera-
ture applications) can also be used as appropriate, provided the where:
reference materials have density values that are certified and T = temperature, K, and
traceable to national standards. P = barometric pressure, kPa.
NOTE X1.1—On certain newer, commercially available instruments, a X1.2.1 Determine the density of water at the temperature of
viscosity correction feature may be available and utilized in density
determinations to minimize potential biases. Refer to information in the test by reference to Table 1.
Section 15 for more specifics. X1.2.2 Using the observed T-values and the reference
X1.1.1 While monitoring the oscillator period, T, flush the values for water and air, calculate the values of the Constants
sample tube with cleaning solvent, followed with an acetone A and B using the following equations:
flush, and dry with dry air. Contaminated or humid air can A 5 @ T w2 2 T 2a # ⁄ @ d w 2 d a # (X1.2)
affect the calibration. When these conditions exist in the 2
B 5 T 2 ~ A 3 d a! (X1.3)
laboratory, pass the air used for calibration through a suitable a
purification and drying train. In addition, the inlet and outlet where:
ports for the U-tube must be plugged during measurement of Tw = observed period of oscillation for cell containing water,
the calibration air to prevent ingress of moist air. µs,
X1.1.2 Allow the dry air in the U-tube to come to thermal Ta = observed period of oscillation for cell containing air,
equilibrium with the test temperature and record the T-value µs,
for air. dw = density of water at test temperature, g/mL, and
da = density of air at test temperature, g/mL.
X1.1.3 Introduce a small volume, about 1 mL to 2 mL, of
X1.2.2.1 Alternatively, use the T and d values for the other
freshly boiled reagent water into the sample tube using a
reference liquid if one is used.
suitable syringe or alternate, as described in 6.4 and 6.5.
(Warning—Handling water at boiling or near boiling tempera- X1.2.3 If the instrument is equipped to calculate density
ture can present a safety hazard. Wear appropriate personal from the constants A and B and the observed T-value from the
protective equipment.) The test portion must be homogeneous sample, then enter the constants in the instrument memory in
7
D4052 − 18a
accordance with the manufacturer’s instructions. Alternatively, been calibrated to display the relative density, adjust the
if the instrument is equipped to do so, let it make the reading to the value 1.0000.
appropriate corrections in the calibration or adjustment con- NOTE X1.2—If performing a weekly calibration adjustment, it can be
stants as part of the built in calibration or adjustment proce- found that more than one value each for A and B, differing in the fourth
dure. decimal place, will yield the correct density reading for the density of air
and water. The setting chosen would then be dependent upon whether it
X1.2.4 Check the calibration and adjust if needed by per- was approached from a higher or lower value. The setting selected by this
forming the routine calibration check described in X1.3. method could have the effect of altering the fourth place of the reading
obtained for a sample.
X1.2.5 To calibrate the instrument to display relative
density, that is, the density of the sample at a given temperature X1.4 Some analyzer models are designed to display the
referred to the density of water at the same temperature, follow measured period of oscillation only (T-values) and their
X1.1 to X1.2.3, but substitute 1.000 for dw in performing the calibration requires the determination of an instrument constant
calculations described in X1.2.2. K, which must be used to calculate the density or relative
X1.3 On some density meter analyzers, weekly calibration density from the observed data.
adjustments to constants A and B can be made if required, X1.4.1 Flush and dry the sample tube as described in X1.1
without repeating the calculation procedure. The need for a and allow the display to reach a steady reading. Record the
change in calibration is generally attributable to deposits in the T-value for air.
sample tube that are not removed by the routine flushing
procedure. Although this condition can be compensated for by X1.4.2 Introduce freshly boiled reagent water into the
adjusting A and B, it is good practice to clean the tube with a sample tube as described in X1.1.3, allow the display to reach
strong oxidizing acid (Warning—Causes severe burns) or a steady reading and record the T-value for water. (Warning—
surfactant cleaning fluids whenever a major adjustment is Handling water at boiling or near boiling temperature can
required. present a safety hazard. Wear appropriate personal protective
equipment.)
X1.3.1 Flush and dry the sample tube as described in X1.1
and allow the display to reach a steady reading. If the display X1.4.3 Using the observed T-values and the reference
does not exhibit the correct density for air at the temperature of values for water and air (X1.2 and X1.2.1), calculate the
test, repeat the cleaning procedure or adjust the value of instrument constant K using the following equations:
constant B commencing with the last decimal place until the For density:
correct density is displayed. K 1 5 @ d w 2 d a # ⁄ @ T w2 2 T 2a # (X1.4)
X1.3.2 If adjustment to constant B was necessary in X1.3.1, For relative density:
then continue the recalibration by introducing freshly boiled K 2 5 @ 1.000 2 d a # ⁄ @ T w2 2 T 2a # (X1.5)
(Warning—Handling water at boiling or near boiling tempera-
ture can present a safety hazard. Wear appropriate personal where:
protective equipment.) reagent water into the sample tube as Tw = observed period of oscillation for cell containing water,
described in X1.1.3and allow the display to reach a steady µs,
reading. If the instrument has been calibrated to display the Ta = observed period of oscillation for cell containing air,
density, adjust the reading to the correct value for water at the µs,
test temperature (Table 1) by changing the value of constant A, dw = density of water at test temperature, g/mL, and
commencing with the last decimal place. If the instrument has da = density of air at test temperature, g/mL.
X2. CALCULATIONS
X2.1 Noncalculating Density Analyzers—Using the ob- For relative density:

served T-value for the sample and the T-value for water and relative density, t⁄t 5 11K 2 ~ T 2s 2 T w2 ! (X2.2)
appropriate instrument constants determined in X1.4.3, calcu-
where:
late the density or relative density using Eq X1.4 and Eq X1.5.
Carry out all calculations to six significant figures and round Tw = observed period of oscillation for cell containing water,
the final results to four.
Ts = observed period of oscillation for cell containing air,
For density:
dw = density of water at test temperature,
density, g/mL~ kg/m3 ! at t 5 d w 1K 1 ~ T 2s 2 T w2 ! (X2.1) K1 = instrument constant for density,
K2 = instrument constant for relative density, and
T = temperature of test, °C.
8
D4052 − 18a
SUMMARY OF CHANGES
(1) Revised Section 3, 6, 10, and 13. (4) Added new Appendix X1.
(2) Replaced “Sample tube” with “U-tube” throughout.
(3) Other language about samples/specimens/tubes was cor-
rected throughout.
(D4052 – 16) that may impact the use of this standard. (Approved May 1, 2018.)
(1) Revised subsection 12.2, deleting former subsections (2) Added new Note 7.
12.2.2, 12.2.3, and 12.2.4; subsequent subsections were renum-
bered accordingly.
9
Designation: D4294 − 16´1

Sulfur in Petroleum and Petroleum Products by Energy
Dispersive X-ray Fluorescence Spectrometry1
ε1 NOTE—The overall layout of the Appendix sections was editorially corrected in February 2016.
1. Scope* 1.4 Volatile samples (such as high vapor pressure gasolines

1.1 This test method covers the determination of total sulfur or light hydrocarbons) may not meet the stated precision
in petroleum and petroleum products that are single-phase and because of selective loss of light materials during the analysis.
either liquid at ambient conditions, liquefiable with moderate 1.5 A fundamental assumption in this test method is that the
heat, or soluble in hydrocarbon solvents. These materials can standard and sample matrices are well matched, or that the
include diesel fuel, jet fuel, kerosine, other distillate oil, matrix differences are accounted for (see 5.2). Matrix mis-
naphtha, residual oil, lubricating base oil, hydraulic oil, crude match can be caused by C/H ratio differences between samples
oil, unleaded gasoline, gasoline-ethanol blends, biodiesel (see and standards (see Section 5) or by the presence of other
Note 2), and similar petroleum products. heteroatoms.
NOTE 1—Oxygenated fuels with ethanol or methanol contents exceed- 1.6 The values stated in SI units are to be regarded as
ing the limits given in Table 1 can be dealt with using this test method, but standard. No other units of measurement are included in this
the precision and bias statements do not apply (see Appendix X3). standard.
NOTE 2—For samples with high oxygen contents (>3 weight %) sample
dilution as described in 1.3 or matrix matching must be performed to 1.7 This standard does not purport to address all of the
assure accurate results. safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
1.2 Interlaboratory studies on precision revealed the scope
to be 17 mg ⁄kg to 4.6 mass %. An estimate of this test
bility of regulatory limitations prior to use.
method’s pooled limit of quantitation (PLOQ) is 16.0 mg ⁄kg as
calculated by the procedures in Practice D6259. However,
2. Referenced Documents
because instrumentation covered by this test method can vary
in sensitivity, the applicability of the test method at sulfur 2.1 ASTM Standards:3
concentrations below approximately 20 mg/kg must be deter- D4057 Practice for Manual Sampling of Petroleum and
mined on an individual basis. An estimate of the limit of Petroleum Products
detection is three times the reproducibility standard deviation, D4177 Practice for Automatic Sampling of Petroleum and
and an estimate of the limit of quantitation2 is ten times the Petroleum Products
reproducibility standard deviation. D6259 Practice for Determination of a Pooled Limit of
Quantitation for a Test Method
1.3 Samples containing more than 4.6 mass % sulfur can be
D6299 Practice for Applying Statistical Quality Assurance
diluted to bring the sulfur concentration of the diluted material
and Control Charting Techniques to Evaluate Analytical
within the scope of this test method. Samples that are diluted
Measurement System Performance
can have higher errors than indicated in Section 16 than
D7343 Practice for Optimization, Sample Handling,
non-diluted samples.
Calibration, and Validation of X-ray Fluorescence Spec-
trometry Methods for Elemental Analysis of Petroleum
Products and Lubricants
1
Subcommittee D02.03 on Elemental Analysis.
3
Current edition approved Jan. 1, 2016. Published February 2016. Originally For referenced ASTM standards, visit the ASTM website, www.astm.org, or
approved in 1983. Last previous edition approved in 2010 as D4294 – 10. DOI: contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
10.1520/D4294-16E01. Standards volume information, refer to the standard’s Document Summary page on
2
Analytical Chemistry, Vol 55, 1983, pp. 2210-2218. the ASTM website.

1
D4294 − 16´1
TABLE 1 Concentrations of Interfering SpeciesA TABLE 2 Matrix Diluents
Element Mass % Tolerated Matrix Matrix Diluent Alternate Diluent
Phosphorus 0.3 #2 Diesel #2 Diesel Kerosine
Zinc 0.6 Naphtha Kerosine —
Barium 0.8 Kerosine Kerosine #2 Diesel
Lead 0.9 Residuals Lube Oil MOWHA
Calcium 1 Lubricating Base Oils Lube Oil MOWLB
Chlorine 3 Hydraulic Oils Lube Oil MOWLB
Ethanol (Note 11) 8.6 Crude Oil Lube Oil MOWHA
Methanol (Note 11) 6 Jet Fuels Kerosine —
Fatty Acid Methyl Ester (FAME) 5 Gasoline Gasoline —
A
The concentrations of substances in this table were determined by the calcula- A
MOWH = mineral oil white heavy
tion of the sum of the mass absorption coefficients times mass fraction of each B
MOWL = mineral oil white light
element present. This calculation was made for dilutions of representative samples
containing approximately 3 % of interfering substances and 0.5 % sulfur.
million—mass ppm). Follow the manufacturer’s operating-

guide to compensate for the interferences.
E29 Practice for Using Significant Digits in Test Data to 5.2 Matrix effects are caused by concentration variations of
Determine Conformance with Specifications the elements in a sample. These variations directly influence
X-ray absorption and change the measured intensity of each
3. Summary of Test Method element. For example, performance enhancing additives, such
3.1 The sample is placed in the beam emitted from an X-ray as oxygenates in gasoline, may affect the apparent sulfur
tube. The resultant excited characteristic X radiation is reading. Other matrix related interferences may arise from
measured, and the accumulated count is compared with counts heavy metal additives, lead alkyls, and elements such as
from previously prepared calibration samples to obtain the silicon, phosphorus, calcium, potassium, and the halides,
sulfur concentration in mass percent or mg/kg, or both. A especially if present at concentrations greater than one tenth of
minimum of three groups of calibration samples are required to the measured concentration of sulfur, or more than a few
span the concentration range: 0.0 mass % to 0.1 mass %, hundred milligrams/kilogram (parts per million—ppm). These
0.1 mass % to 1.0 mass %, and 1.0 mass % to 5.0 mass % types of interferences are always present in X-ray fluorescence
sulfur. (See Practice D7343.) analysis and are completely unrelated to spectral interferences.
5.3 The interferences mentioned in 5.1 and 5.2 may be
4. Significance and Use
compensated for in contemporary instruments with the use of
4.1 This test method provides rapid and precise measure- built-in software for spectra deconvolution or overlap correc-
ment of total sulfur in petroleum and petroleum products with tion and inter-element correction by multiple regression or by
a minimum of sample preparation. A typical analysis time is other mathematical methods.
1 min to 5 min per sample.
5.4 In general, petroleum materials with compositions that
4.2 The quality of many petroleum products is related to the vary from oils as specified in 9.1 may be analyzed with
amount of sulfur present. Knowledge of sulfur concentration is standards made from base materials that are of the same, or
necessary for processing purposes. There are also regulations similar, composition. Thus, a gasoline may be simulated by
promulgated in federal, state, and local agencies that restrict mixing isooctane and toluene in a ratio that approximates the
the amount of sulfur present in some fuels. true aromatic content of the samples to be analyzed. Standards
4.3 This test method provides a means of determining made from this simulated gasoline will produce results that are
whether the sulfur content of petroleum or a petroleum product more accurate than results obtained using white oils. Sugges-
meets specification or regulatory limits. tions are given in Table 2.
NOTE 3—In the case of petroleum materials that contain suspended
4.4 When this test method is applied to petroleum materials water, it is recommended that the water be removed before testing or that
with matrices significantly different from the calibration mate- the sample be thoroughly homogenized and immediately tested. The
rials specified in 9.1, the cautions and recommendations in interference is greatest if the water creates a layer over the transparent film
Section 5 should be observed when interpreting results. as it will attenuate the X-ray intensity for sulfur. One such method to
accomplish the removal of water is to centrifuge the sample first under
ambient sealed conditions, taking care that the sample integrity is not
5. Interferences compromised.
5.1 Spectral interferences are caused by the closeness of the
X-ray characteristic lines of the elements present in a sample 6. Apparatus
and the limited detector ability to completely resolve them. As 6.1 Energy-dispersive X-ray Fluorescence Analyzer—
a result, the lines produce spectral peaks that overlap with each Energy dispersive X-ray fluorescence analyzer may be used if
other. Spectral interferences may arise from samples contain- its design incorporates, as a minimum, the following features
ing lead alkyls, silicon, phosphorus, calcium, potassium, and if test results from it are shown to be equivalent on the
halides, and catalyst particles if present at concentrations samples of interest. Required design features include:
greater than one tenth of the measured concentration of sulfur, 6.1.1 Source of X-ray Excitation , X-ray tube with excitation
or more than a few hundred milligrams/kilogram (parts per energy above 2.5 keV.
2
D4294 − 16´1
6.1.2 Removable Sample Cup, equipped with replaceable include a renewable liquid petroleum material, a metal alloy, or
X-ray transparent plastic film windows and providing a sample a fused glass disk. The monitor’s counting rate, in combination
depth of at least 4 mm and a diameter of at least 10 mm. with count time, shall be sufficient to give a relative counting
6.1.3 X-ray Detector, with high sensitivity and a resolution error of less than 1 %. The counting rate for the monitor sample
value (Full Width at Half Maximum, FWHM) not to exceed is determined during calibration (see 9.2.1) and again at the
800 eV at 2.3 keV. time of analysis (see 12.2). These counting rates are used to
6.1.4 Filters or other means of discriminating between calculate a drift correction factor (see 15.6).
sulfur Kα radiation and other X-rays of higher energy. 7.3.1 Drift correction is usually implemented automatically
6.1.5 Signal conditioning and data handling electronics that in software, although the calculation can readily be done
include the functions of X-ray intensity counting, a minimum manually. For X-ray instruments that are highly stable, the
of two energy regions, spectral overlap corrections, and con- magnitude of the drift correction factor may not differ signifi-
version of sulfur X-ray intensity into mass percent sulfur cantly from unity.
concentration. 7.4 Polysulfide Oil, generally nonyl polysulfides containing
6.1.6 The analyzer shall have the sensitivity under opti- a known percentage of sulfur diluted in a hydrocarbon matrix.
mized measurement conditions to measure the concentration of (Warning—May cause allergic skin reactions.)
sulfur at the 0.05 % level with a demonstrated error due to NOTE 6—Polysulfide oils are high molecular weight oils that contain
counting statistics with one standard deviation not greater than high concentrations of sulfur, as high as 50 weight %. They exhibit
0.5 % relative at the 500 mg ⁄ kg level. This requirement excellent physical properties such as low viscosity, low volatility, and
pertains to sample measurements of less than 1000 mg/kg. durable shelf life while being completely miscible in white oil. Polysulfide
oils are readily available commercially. The sulfur content of the polysul-
6.1.7 Display or Printer that reads out in mass percent fide oil concentrate is determined via mass dilution in sulfur-free white oil
sulfur or mg/kg sulfur, or both. followed by a direct comparison analysis against NIST reference materi-
6.2 Analytical Balance, with an accuracy and resolution of als.
0.1 mg and capable of weighing up to 100 g. 7.5 Mineral Oil, White (MOW), ACS Reagent Grade con-
NOTE 4—Operation of analyzers using X-ray tube sources is to be taining less than 2 mg/kg sulfur or other suitable base material
conducted in accordance with the manufacturer’s safety instructions. containing less than 2 mg/kg sulfur. When low level (<200
mg/kg) measurements are anticipated, then the sulfur content,
7. Reagents if any, of the base material needs to be included in the
7.1 Purity of Reagents—Reagent grade chemicals shall be calculation of calibration standard concentration (see 9.1).
used in all tests. Unless otherwise indicated, it is intended that When the sulfur content of the solvent or reagent is not
all reagents conform to the specifications of the Committee on certified, verify the absence of sulfur. Use the purest available
Analytical Reagents of the American Chemical Society (ACS) grades for chemicals to be used for preparing calibration
where such specifications are available.4 Other grades may be standards.
used, provided it is first ascertained that the reagent is of 7.6 X-ray Transparent Film—Any film that resists attack by
sufficiently high purity to permit its use without lessening the the sample, is free of sulfur, and is sufficiently X-ray transpar-
accuracy of the determination. ent can be used. Film types can include polyester,
7.2 Di-n-Butyl Sulfide (DBS), a high-purity standard with a polypropylene, polycarbonate, and polyimide. However,
certified analysis for sulfur content. Use the certified sulfur samples of high aromatic content can dissolve polypropylene,
content and the material purity when calculating the exact polycarbonate, and polyester films.
concentrations of the calibration standards (see 9.1). 7.7 Helium Purge Gas (optional) , Follow manufacturer’s
(Warning—Di-n-butyl sulfide is flammable and toxic.) recommendations for corresponding specifications when use of
NOTE 5—It is essential to know the concentration of sulfur in the helium purge gas is required.
di-n-butyl sulfide, not only the purity, since impurities may also be sulfur
containing compounds. 7.8 Counting Gas, for instruments equipped with flow
7.3 Drift Correction Monitor(s) (Optional)—Several differ- proportional counters. The purity of the counting gas should be
ent materials have been found to be suitable for use as drift in agreement with the specification provided by the instrument
correction monitors. Appropriate drift monitor samples should manufacturer.
be permanent materials that are stable with respect to repeated 7.9 Sample Cells, compatible with the sample and the
exposure to X-rays. Stable liquids like polysulfide oils, glass, geometry requirements of the spectrometer. Disposable cells
or metallic specimens are recommended. Liquids, pressed are preferred over reusable ones for ultra low (<50 mg/kg)
powders, and solid materials that degrade with repeated expo- sulfur levels.
sure to X-rays should not be used. Examples of sulfur 7.10 Calibration Check Samples, portions of one or more
containing materials that have been found to be suitable liquid petroleum or product standards of known or certified
sulfur content (including polysulfide oils, di-n-butyl sulfide,
4
Reagent Chemicals, American Chemical Society Specifications , American
thiophenes, etc.) and not used in the generation of the calibra-
Chemical Society, Washington, DC. For suggestions on the testing of reagents not tion curve. The check samples shall be used to determine the
listed by the American Chemical Society, see Analar Standards for Laboratory precision and accuracy of the initial calibration (see Section 9).
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 7.11 Quality Control (QC) Samples, stable petroleum or
MD. product samples or solids representative of the samples of
3
D4294 − 16´1
TABLE 3 Composition of Primary Standards purposes. The concentration of sulfur can be calculated using
Sulfur Content, Mass of Matrix Mass of the following equation:
mass % Diluent, g Di-n-Butyl Sulfide, g
S 5 @ ~ DBS 3 S DBS! 1 ~ MOW 3 S MOW! # / ~ DBS1MOW! (1)
5 48.6 14.4
0.1 43.6 0.2
where:
S = mass % sulfur of the prepared standards,
DBS = actual mass of DBS, g,
interest that are run on a regular basis to verify that the system SDBS = the mass % sulfur in DBS, typically 21.91 %,
is in statistical control (see Section 15). MOW = actual mass of white oil, g, and
NOTE 7—Verification of system control through the use of QC samples SMOW = mass % sulfur in the white oil.
and control charting is highly recommended. It is recognized that QC For any generic source of sulfur use the following equation:
procedures are the province of the individual laboratory.
NOTE 8—Suitable QC samples can often be prepared by combining S 5 @ ~ M SC 3 S SC! 1 ~ M D 3 S D ! # / ~ M SC1M D ! (2)
retains of typical samples if they are stable. For monitors, solid materials
are recommended. QC samples must be stable over long periods. where:
S = mass % of sulfur in standard,
8. Sample Cell Preparation MSC = mass of sulfur compound, g,
8.1 If you employ reusable cups, clean and dry cells before SSC = mass % of sulfur in sulfur compound,
use. Disposable sample cups are not to be reused. Window MD = mass of diluent, g, and
material usually is <10 µm polyester or polycarbonate film (see SD = mass % of sulfur in diluent.
7.6). Polycarbonate is preferred due to its high transmissivity 9.1.1 Calibration standards can also be prepared by careful
of sulfur X-rays. Renewal of the window of the sample cup is mixing of certified reference materials (CRM) of the same
essential for the measurement of each sample. Avoid touching matrix, so long as the sulfur values of the resulting blends and
the inside of the sample cup or portion of the window film in their uncertainties are characterized by the certifying body.5
the cup or in the instrument window that is exposed to X-rays. 9.1.2 Alternatively, standards may be prepared by mass
Oil from fingerprints can affect the reading when analyzing for serial dilution of polysulfide oils (Note 5) with sulfur-free
low levels of sulfur. Wrinkles in the film will affect the number white oil. A freshly prepared polysulfide oil calibration curve
of sulfur X-rays transmitted. Therefore, the importance of the should be verified using CRMs traceable to NIST, or other
film’s smoothness and cleanliness cannot be over stressed to national metrology institute that has demonstrated proficiency
ensure reliable results. The analyzer will need recalibration if for measuring sulfur in the matrix of interest. Once a polysul-
the type or thickness of the window film is changed. fide oil calibration curve is established, the calibration stan-
8.2 Impurities which may affect the measurement of low dards are stored at room temperature, out of direct sunlight, and
levels of sulfur have been found in polyester films and may in amber glass bottles. Polysulfide oil standards can be pre-
vary from lot to lot. Therefore, if using a polyester film, the pared over a wide concentration range from low mg/kg to high
calibration should be checked after starting each new roll. mass % levels of sulfur. They are easily prepared in quantity
and make excellent quality control standards. Shaking polysul-
8.3 Samples of high aromatic content may dissolve fide oil standards before fresh aliquots are taken is recom-
polyester, polypropylene, and polycarbonate films. In these mended to ensure the standard is uniformly blended. The high
cases, other materials besides these films may be used for molecular weight of these sulfur compounds results in a very
X-ray windows, provided that they do not contain any elemen- low vapor pressure that inhibits X-ray film diffusion.
tal impurities. An optional window material is 6 µm thick Therefore, an autosampler can be employed during the mea-
polyimide foil. While polyimide foil absorbs sulfur X-rays surement process. Calibration curves prepared from polysul-
more than other films, it may be a preferred window material fide also demonstrate excellent linearity and help the analyst
as it is much more resistant to chemical attack by aromatics and visualize the full dynamic range of their analytical method.
exhibits higher mechanical strength.
NOTE 9—Commercially available standards can be used provided their
9. Calibration sulfur concentrations are accurately known and they approximate the
nominal concentrations listed in Table 3.
9.1 Prepare Calibration Standards by careful mass dilution
of the certified di-n-butyl sulfide with a sulfur-free white oil or 9.1.3 Accurately weigh the appropriate quantity of matrix
other suitable base material (see 7.5). The concentrations of the diluent, shown in Table 3, into a suitable, narrow-necked
unknown samples must lie within the calibration range that is container and then accurately weigh in the appropriate quantity
used. Approximate recommended nominal sulfur concentration of completely pure di-n-butyl sulfide. Mix thoroughly (a
standards are listed in Table 3 for the sulfur concentration polytetrafluoroethylene (PTFE)-coated magnetic stirrer is ad-
ranges of interest. Take into account any sulfur in the base visable) at room temperature.
material when calculating the concentration of standards below 9.1.4 Make calibration standards using one or more of the
0.02 mass % (200 mg/kg), as shown in Eq 1. Weigh the DBS three ranges suggested in Table 4, according to the expected
and matrix diluent to the recommended mass as closely as
possible. It is important that the exact mass is known and thus 5
Refer to Kelly, W. R., MacDonald, B. S., and Leigh, S. D., “A Method for the
the exact concentration of the prepared standards can be Preparation of NIST Traceable Fossil Fuel Standards with Concentrations Interme-
calculated and entered into the instrument for calibration diate to SRM Values,” Journal of ASTM International, Vol 4, No. 2, 2007.
4
D4294 − 16´1
TABLE 4 Suggested Sulfur Standard Calibration Ranges TABLE 5 Typical Counting Times For Sulfur Content
0–1000 0.10–1.00 1.0–5.0 Determination
mg/kg mass % mass % Sulfur Content Range, Counting Time,
0.0A,B 0.100 1.0 Mass % seconds
5B 0.250 2.0 0.0000 to 0.1000 200 to 300
10B 0.500 3.0 0.1 to 5.0 100
100B 1.000 4.0 1.0 to 5.0 100
250 5.0
500
750
1000
A
9.4 Quality Control Samples—Several additional standards
Base material.
B
Analyze these standards in duplicate and use either both individual values or the
(quality control standards) may prove useful. Quality control
average in the calibration. standards, independently prepared as per 9.1, may be used as
well as any appropriate certified standards as per 9.2. The
concentration of the QC standards should be near the expected
concentration of the samples being analyzed.
level of sulfur of the samples to be analyzed, by diluting 9.5 Storage of Standards—Store all standards in dark, glass
primary standards with the applicable matrix diluent. bottles, with screw caps with a chemically resistant lining, in a
Alternatively, standards may be prepared by mixing of certified cool, dark place until required. As soon as any sediment or
reference materials (as in 9.1.1) or diluting polysulfide oils (as change of concentration is observed, discard the standard.
in 9.1.2).
10. Preparation of Apparatus
NOTE 10—If desired, additional standards can be prepared and analyzed
with concentrations between those listed in Table 4, see 9.1.1. 10.1 Set up the apparatus in accordance with the manufac-
9.1.5 Alternatively, prepared standards for the above refer- turer’s instructions. Whenever possible the instrument is left on
enced matrices are commercially available. continuously to maintain optimum stability.
9.1.6 If the matrix diluent being used for the preparation of
11. Sampling
standards contains sulfur, add this value to the calculated sulfur
content of the prepared standards as per Eq 1 (consult your 11.1 Obtain a test specimen in accordance with Practice
supplier for an accurate sulfur concentration or test the mineral D4057 or D4177. Samples should be analyzed immediately
oil using some other low level sulfur analyzing method). after pouring into a sample cup and allowing for the escape of
the air bubbles caused by mixing.
9.2 Certified Calibration Standards:
9.2.1 Calibration standards which are certified by a respon- 12. Procedure
sible standards organization may be used when applicable to
the sample of interest. Such standards included Standard 12.1 A quality control sample is measured prior to analyzing
Reference Materials (SRM) prepared and certified by the unknowns to verify that the test method is in control. It is run
National Institute of Standards and Technology (NIST), and identically to any unknown sample. If the chosen quality
Standard Sample of Sulfur in Residual Fuel Oil certified by the control sample’s repeatability varies by more than the repeat-
Japan Petroleum Institute or other national metrology institute ability value of this test method expected for that concentration
that has demonstrated proficiency in measuring sulfur in the (acceptance value obtained from Table 6) then the procedure is
matrix of interest. deemed to be out of control and the instrument should be
9.2.2 Standards containing 100 mg/kg total sulfur or less recalibrated before running any further analysis. A synthetic
must be analyzed in duplicate. Use either both individual solid quality control sample may be used in lieu of liquid
values or the average value of these measurements in the samples (see Section 15).
calibration. 12.2 Analysis of Unknown Samples—Fill the cup with the
9.3 Instrument Calibration—Calibrate the instrument for sample to be measured to about 75 % of cup capacity. Before
the appropriate range as listed in Table 4, following manufac- filling the cell, it may be necessary to heat viscous samples so
turer’s instructions. Typically, the calibration procedure in- that they are easy to pour into the cell. Ensure that no air
volves setting up the instrument for recording of net sulfur bubbles are present between the cup window and the liquid
X-ray intensity, followed by the measurement of known sample. Measure each sample once. If the concentration from
standards. Obtain one reading on each standard using the the first analysis is less than 100 mg ⁄kg, repeat the measure-
recommended counting time for the instrument as per Table 5. ment using a freshly prepared sample cup and a fresh portion
In the case of calibration standards less than 100 mg/kg, repeat of the sample, and obtain the average of the readings for the
the measurement using a freshly prepared sample cup and a sulfur content in the unknown sample.
fresh portion of the sample. Immediately repeat the procedure 12.3 When analyzing more than a single unknown sample,
using freshly prepared cells and fresh portions of samples. measure a quality control sample at the end of each batch of
Once all the standards have been analyzed, follow manufac- unknown samples, but no less than every ten unknown
turers instructions for generating the optimum calibration curve samples, to verify that the method is in control. In all situations
based on the net sulfur counts for each standard. (Warning— where the quality control samples vary by more than the
Avoid spilling flammable liquids inside the analyzer.) repeatability expected for that concentration (Table 6), the
5
D4294 − 16´1
TABLE 6 Precision Values, All Sample Types program might be the regular use and charting6 of quality
X, mg/kg
Repeatability r, mg/kg Reproducibility R, mg/kg control samples (see 7.11). It is recommended that at least one
Eq 3 Values Eq 5 Values type of quality control sample be analyzed that is representa-
16.0 2.6 11 tive of typical laboratory samples as defined in Practice D6299.
25.0 3.4 15
50.0 5.4 24 15.2 In addition to running a quality control sample (7.11),
100.0 8.5 37
500 24 105
it is strongly recommended that the calibration blank (for
1000 37 165 example, diluent oil) be analyzed on a daily basis.
5000 105 465 15.2.1 The measured concentration for the blank should be
10 000 165 727
46 000 440 1943
less than 2 mg ⁄kg (0.0002 mass %) sulfur. If the measured
concentration for the blank is greater than 2 mg/kg
(0.0002 mass %), re-standardize the instrument and repeat the
measurement of the blank (use a fresh sample and fresh cell).
If the result falls outside the acceptable range, carry out a full
analysis must be discontinued and corrective action taken to calibration. If the sample loading port becomes contaminated,
find the source of error. Use a quality control sample close to especially when analyzing <20 mg ⁄kg sulfur level samples, it
the unknown samples’ sulfur concentration. Refer to Section is necessary to open and clean it according to manufacturer’s
15. recommendations before further use.
15.2.2 It should be noted that in order to obtain a good fit for
12.4 For samples containing 100 mg/kg total sulfur or less, the calibration at low concentrations, it may be necessary to
duplicate determinations are required. Each determination change the weighting factor in the regression.
must be made on a new portion of sample material and
analyzed in accordance with 12.1 and 12.2. The difference 15.3 Results Validation—Once a standard or sample has
between the duplicate analyses should be equal to or less than been measured, a procedure should be carried out to validate
the repeatability values indicated in Table 6. If the difference is that measurement. This requires the operator to check for
larger, investigate sample preparation to identify any possible obvious signs of damage to the sample such as leaking sample
sources of sample contamination, and repeat the analysis. The cells, crinkled sample cell window and inspection of any
reason for duplicate measurements is to identify problems secondary film.
associated with sample contamination, leading to improved 15.4 Observation of the resultant analysis. If a result is
results precision at the lower sulfur levels. considered outside normal thresholds, a repeat of the analysis
NOTE 11—The concentrations of ethanol and methanol were calculated should be carried out to confirm anomalous results.
assuring a theoretical mixture of hydrocarbons and di-butyl sulfide to
which ethanol (or methanol) was added until the sum of the mass 15.5 Regular checks should be carried out to ensure that
coefficients times mass fractions increased by 5 %. In other words, the purging gas performance is within the instrument manufactur-
amount of ethanol (or methanol) that caused a negative 5 % error in the er’s specification.
sulfur measurement was calculated. This information is included in Table
1 to inform those who wish to use Test Method D4294 for determining 15.6 Drift and quality control standards/monitors must be
sulfur in gasohol (or M-85 and M-100) of the nature of the error involved. run on a regular basis while drift monitors may also be run on
a regular basis. . The tolerance levels of the checks made using
13. Calculation these monitors should be such that a protocol of either drift
13.1 The concentration of sulfur in the sample is automati- correction or total recalibration is carried out if the results fall
cally calculated from the calibration curve. outside these levels. All measurements should be repeated
between the last accepted monitor result and point of noncom-
14. Report pliance should a current monitor measurement prove to be
outside acceptable levels.
14.1 Report the results as total sulfur content mass percent
to three significant figures for concentrations greater than 16. Precision and Bias7
0.01 %. For concentrations less than or equal to 0.01 %, report
16.1 Precision—The precision of the test method was de-
results in milligrams per kilogram. Report results in milligrams
termined by statistical analysis of results obtained in an
per kilogram to two significant figures between 100 mg ⁄kg and
interlaboratory study that included 27 samples including
10 mg/kg, and to one significant figure below 10 mg/kg. Report
distillates, gasoline with or without oxygenates, kerosine,
that results were obtained according to Test Method D4294.
diesel, biodiesel E-85, residual oils, and crude oils. The
Use Practice E29 as a guide for rounding purposes.
laboratory study on precision covered a variety of materials
14.1.1 For samples containing less than 100 mg/kg total
with sulfur concentrations ranging from approximately
sulfur, average the duplicate determinations and report that
1 mg ⁄kg to 4.6 mass %. A pooled limit of quantitation (PLOQ)
value as in 14.1.
15. Quality Control 6

ASTM MNL 7, Manual on Presentation of Data and Control Chart Analysis ,
Section 3, Control Chart for Individuals, ASTM International, W. Conshohocken,
15.1 It is recommended that each laboratory establish a
PA.
program to ensure that the measurement system described in 7
this test method is in statistical control. One part of such a be obtained by requesting Research Report RR:D02-1635.
6
D4294 − 16´1
TABLE 7 Comparison of NIST and ASTM Interlaboratory Study (RR) Results
Sulfur, Apparent
NIST Sulfur, RR
mg/kg Bias Relative
SRM mg/kg, Sample Matrix Significant?
ASTM RR mg/kg Bias, %
Number NIST Number
avg Sulfur
2296 40.0 2 Reformulated Gasoline 46.3 +6.3 +15.8 No
(nominal 13 % ETBE)
2299 13.6 3 Reformulated Gasoline 18.1 +4.5 +33.1 No
2770 41.6 7 Diesel 49.4 +7.8 +18.8 No
2724b 426.5 8 Diesel 430.8 +4.3 +1.01 No
2721 15 832 9 Crude Oil (light-sour) 16 118 +288 +1.82 Yes
2722 2104 10 Crude Oil (heavy-sweet) 2082 -21 -1.00 No
1619b 6960 12 Residual Fuel Oil 6654 -306 -4.40 Yes
1620c 45 610 13 Residual Fuel Oil 45 801 +191 +0.42 No
of 16.0 mg ⁄kg sulfur, was determined for all sample types. method exceed the following values only in one case in twenty.
Separate precision statements for diesel and gasoline are Reproducibility (R) may be calculated as shown in Eq 5 or Eq
included in Appendix X1 and Appendix X2. The ranges of 6 for all materials covering the full scope of this method. See
sulfur concentrations represented by the sample sets, together Table 6 for calculated values.
with the precisions, are listed in 16.1.1 and 16.1.2. These Reproducibility ~ R ! 5 1.9182·X 0.6446 mg/kg (5)
statistics apply only to samples having less than the level of
Reproducibility ~ R ! 5 ~ 1.9182· ~~ Y·10 000! 0.6446!! /10 000 mass %
interfering materials present shown in Table 1.
(6)
NOTE 12—Volatile materials may not meet the stated precision of the
method because selective loss of light materials is possible before and where:
during analysis by this method. Another possible mechanism is the sulfur X = sulfur concentration in mg/kg total sulfur, and
enrichment of the sample cup window resulting in higher sulfur values.
Y = sulfur concentration in mass percent total sulfur.
16.1.1 Repeatability—The difference between successive
16.1.3 Repeatability and reproducibility values for diesel in
test results obtained by the same operator with the same
the aforementioned interlaboratory study7 may be found in
apparatus under constant operating conditions on identical test
Appendix X1 and for gasoline in Appendix X2.
materials would, in the long run, in the normal and correct
operation of the test method, exceed the following values only 16.2 Bias—The interlaboratory study7 included ten NIST
in one case in twenty. Repeatability (r) may be calculated as standard reference materials (SRM’s). The certified sulfur
shown in Eq 3 or Eq 4 for all materials covering the full scope value, interlaboratory round robin (RR) value, apparent bias,
of this method. See Table 6 for calculated values. and relative bias are given in Table 7. The white oil was
assumed to have a C/H mass ratio of 5.698 (C22H46). There
Repeatability ~ r ! 5 0.4347·X 0.6446 mg/kg (3)
was no apparent bias that could be attributed to C/H ratio.
0.6446
Repeatability ~ r ! 5 ~ 0.4347· ~~ Y·10 000! !! /10 000 mass % (4) 16.2.1 Based on the analysis of eight NIST Standard Ref-
where: erence Materials (SRMs), there was no significant bias based
on D2PP calculations between the certified values and the
X = sulfur concentration in mg/kg total sulfur, and
results obtained in this interlaboratory study for any sample
Y = sulfur concentration in mass percent total sulfur.
type.
16.1.2 Reproducibility—The difference between two single
and independent results obtained by different operators work- 17. Keywords
ing in different laboratories on identical test material would, in 17.1 analysis; diesel; gasoline; jet fuel; kerosine; petroleum;
the long run, in the normal and correct operation of the test spectrometry; sulfur; X-ray
7
D4294 − 16´1
APPENDIXES
X1. ADDITIONAL DIESEL PRECISION STATEMENTS
X1.1 Diesel Precision—Six samples in the interlaboratory TABLE X1.1 Precision Values, Diesel
study7 were diesels; they contained between approximately S, mg/kg
Repeatability (r), mg/kg Reproducibility (R), mg/kg
20 mg ⁄kg and 5500 mg/kg total sulfur: Eq X1.1 Values Eq X1.3 Values
25 4.8 26
Number 5 Diesel
100 7.6 41
Number 7 NIST SRM 2770
500 13 70
Number 8 NIST SRM 2724b
1000 16 88
Number 15 Diesel
5500 29 154
Number 17 Diesel
Number 22 B-5 diesel containing 5 %
biodiesel
X1.1.1 Repeatability (r)—The difference between succes- X1.1.2 Reproducibility (R)—The difference between two
sive test results obtained by the same operator with the same single and independent results obtained by different operators
apparatus under constant operation conditions on identical test working in different laboratories on identical test material
material would, in the long run, in the normal and correct would, in the long run, in the normal and correct operation of
operation of the test method exceed the following values only the test method exceed the following values only in one case in
in one case in twenty. Repeatability (r) may be calculated as twenty. Reproducibility (R) may be calculated as shown in Eq
shown in Eq X1.1 or Eq X1.2 for the six diesel samples. See X1.3 or Eq X1.4 for six diesel samples. See Table X1.1 for
Table X1.1 for calculated values. calculated values.
Repeatability ~ r ! 5 1.6658·X 0.3300 mg/kg (X1.1) Reproducibility ~ R ! 5 8.9798·X 0.3300 mg/kg (X1.3)
0.3300 0.3300
Repeatability ~ r ! 5 ~ 1.6658 · ~~ Y·10 000! ! / 10 000 mass % Reproducibility ~ R ! 5 ~ 8.9798· ~~ Y·10 000! !! /10 000 mass %
(X1.2) (X1.4)
where: where:
X = sulfur concentration in mg/kg total sulfur, and X = sulfur concentration in mg/kg total sulfur, and
Y = sulfur concentration in mass % total sulfur. Y = sulfur concentration in mass % total sulfur.
X2. ADDITIONAL GASOLINE PRECISION STATEMENTS
TABLE X2.1 Precision Values, Gasoline Repeatability ~ r ! 5 1.4477·X 0.3661 mg/kg (X2.1)
Repeatability (r), mg/kg Reproducibility (R), mg/kg
S, mg/kg Repeatability ~ r ! 5 ~ 1.4477· ~~ Y·10 000! 0.3661!! /10 000 mass %
Eq X2.1 Values Eq X2.3 Values
50 6.0 30
(X2.2)
100 7.8 38
500 14 69 where:
1000 18 89 X = sulfur concentration in mg/kg total sulfur, and
5500 34 167
Y = sulfur concentration in mass % total sulfur.
X2.1.2 Reproducibility (R)—The difference between two
X2.1 Gasoline Precision—Five samples in the interlabora- single and independent results obtained by different operators
tory study7 were gasolines; they contained between approxi- working in different laboratories on identical test material
mately 11 mg ⁄kg and 5500 mg/kg total sulfur: would, in the long run, in the normal and correct operation of
Number 2 Gasoline with 13 % ETBE the test method exceed the following values only in one case in
Number 3 Reformulated gasoline
twenty. Reproducibility (R) may be calculated as shown in Eq
Number 4 Gasoline with 5 % ethanol
Number 11 Gasoline X2.3 or Eq X2.4 for five gasoline samples. See Table X2.1 for
Number 20 E-85 calculated values.
X2.1.1 Repeatability (r)—The difference between succes- Reproducibility ~ R ! 5 7.1295·X 0.3661 mg/kg (X2.3)
sive test results obtained by the same operator with the same
apparatus under constant operation conditions on identical test Reproducibility ~ R ! 5 ~ 7.1295· ~~ Y·10 000! 0.3661!! /10 000 mass %
material would, in the long run, in the normal and correct (X2.4)
operation of the test method exceed the following values only where:
in one case in twenty. Repeatability (r) may be calculated as
X = sulfur concentration in mg/kg total sulfur, and
shown in Eq X2.1 or Eq X2.2 for the five gasoline samples. See Y = sulfur concentration in mass % total sulfur.
Table X2.1 for calculated values.
8
D4294 − 16´1
X3. HANDLING OXYGENATED FUELS
X3.1 M-85 and M-100 are fuels containing 85 % and 100 % X3.2 When analyzing M-85 or M-100 fuels with a calibra-
methanol, respectively. E-85 contains 85 % ethanol. As such, tion determined with white oil based standards, divide the
they have a high oxygen content, hence, absorption of sulfur result obtained in 12.3 as in the following equations. This
Kα radiation. Such fuels can, however, be analyzed using this correction is not required if the standards are prepared in the
test method provided that the calibration standards are prepared same matrix as the samples, as described in 5.2.
to match the matrix of the sample. There may be a loss of
sensitivity and precision. The repeatability, reproducibility, and S ~ in M 2 85! , mass % 5 S, mass %/0.59 (X3.1)
bias obtained in this test method did not include M-85 and S ~ in M 2 100! , mass % 5 S, mass %/0.55 (X3.2)
M-l00 samples.
SUMMARY OF CHANGES
(D4294 – 10) that may impact the use of this standard. (Approved Jan. 1, 2016.)
(1) Updated subsections 16.1, 16.1.1, 16.1.2, 16.1.3, X1.1.1,

X1.1.2, X2.1.1, and X2.1.2.
9
Designation: 379/88

Trace Nitrogen in Liquid Hydrocarbons by Syringe/Inlet
Oxidative Combustion and Chemiluminescence Detection1
1. Scope* 2. Referenced Documents

1.1 This test method covers the determination of the trace 2.1 ASTM Standards:2
total nitrogen naturally found in liquid hydrocarbons boiling in D1298 Test Method for Density, Relative Density, or API
the range from approximately 50 °C to 400 °C, with viscosities Gravity of Crude Petroleum and Liquid Petroleum Prod-
between approximately 0.2 cSt and 10 cSt (mm2/s) at room ucts by Hydrometer Method
temperature. This test method is applicable to naphthas, D4052 Test Method for Density, Relative Density, and API
distillates, and oils containing 0.3 mg ⁄kg to 100 mg ⁄kg total Gravity of Liquids by Digital Density Meter
nitrogen. For liquid hydrocarbons containing more than D5762 Test Method for Nitrogen in Liquid Hydrocarbons,
100 mg ⁄kg total nitrogen, Test Method D5762 can be more Petroleum and Petroleum Products by Boat-Inlet Chemi-
appropriate. This test method has been successfully applied, luminescence
during interlaboratory studies, to sample types outside the D6299 Practice for Applying Statistical Quality Assurance
range of the scope by dilution of the sample in an appropriate and Control Charting Techniques to Evaluate Analytical
solvent to bring the total nitrogen concentration and viscosity Measurement System Performance
to within the range covered by the test method. However, it is
the responsibility of the analyst to verify the solubility of the
3. Summary of Test Method
sample in the solvent and that direct introduction of the diluted
sample by syringe into the furnace does not cause low results 3.1 The sample of liquid petroleum hydrocarbon is intro-
due to pyrolysis of the sample or solvent in the syringe needle. duced either by syringe or boat inlet system, into a stream of
1.2 The values stated in SI units are to be regarded as inert gas (helium or argon). The sample is vaporized and
standard. No other units of measurement are included in this carried to a high temperature zone where oxygen is introduced
standard. and organically bound nitrogen is converted to nitric oxide
(NO). The NO contacts ozone, and is converted to excited
1.3 This standard does not purport to address all of the
nitrogen dioxide (NO2). The light emitted as the excited NO2
safety concerns, if any, associated with its use. It is the
decays is detected by a photomultiplier tube and the resulting
signal is a measure of the nitrogen contained in the sample.
bility of regulatory limitations prior to use. See 6.2, 6.4, 6.5,
6.9, and Section 7. 4. Significance and Use
1.4 This international standard was developed in accor- 4.1 Some process catalysts used in petroleum and chemical
dance with internationally recognized principles on standard- refining may be poisoned when even trace amounts of nitrog-
ization established in the Decision on Principles for the enous materials are contained in the feedstocks. This test
Development of International Standards, Guides and Recom- method can be used to determine bound nitrogen in process
mendations issued by the World Trade Organization Technical feeds and may also be used to control nitrogen compounds in
Barriers to Trade (TBT) Committee. finished products.
1
2
Subcommittee D02.03 on Elemental Analysis. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Dec. 15, 2017. Published February 2018. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1986. Last previous edition approved in 2017 as D4629 – 12 (2017). Standards volume information, refer to the standard’s Document Summary page on
DOI: 10.1520/D4629-17. the ASTM website.

1
D4629 − 17
5. Apparatus 5.11 Analytical Balance (Optional), with a precision of
60.01 mg.
5.1 Furnace, electric, held at a temperature sufficient to
volatilize and pyrolyze all of the sample and oxidize the 6. Reagents
organically bound nitrogen to NO. Furnace temperature(s)
shall be as recommended by the manufacturer (typically 6.1 Purity of Reagents—Reagent grade chemicals shall be
around 1000 °C). used in all tests. Unless otherwise indicated, it is intended that
all reagents shall conform to the specifications of the Commit-
5.2 Combustion Tube, fabricated to meet the instrument tee on Analytical Reagents of the American Chemical Society,3
manufacturer’s specifications. where such specifications are available. Other grades may be
5.3 Drier Tube—The reaction products include water vapor used, provided it is first ascertained that the reagent is of
that must be eliminated prior to measurement by the detector. sufficiently high purity to permit its use without lessening the
This can be accomplished with a magnesium perchlorate accuracy of the determination.
Mg(ClO4)2 scrubber or a membrane drying tube (permeation 6.2 Magnesium Perchlorate Mg(ClO4)2, for drying products
drier), or by whatever other means the instrument manufacturer of combustion (if permeation drier is not used.) (Warning—
specifies as appropriate for the instrument being used. Strong oxidizer, irritant.)
5.4 Chemiluminescent Detector, capable of measuring light 6.3 Inert Gas, argon or helium, ultra-high purity grade
emitted from the reaction between NO and ozone. (UHP).
5.5 Totalizer, having variable attenuation, and capable of 6.4 Oxygen, (99.8 % or better, 99.996 % is recommended).
measuring, amplifying, and integrating the current from the (Warning—Vigorously accelerates combustion.)
chemiluminescent detector. A built in microprocessor or at- 6.5 Solvents, for diluting and matrix matching such as,
tached computer system may perform these functions. toluene, isooctane, xylene, acetone, cetane. (Other solvents
5.6 Micro-litre Syringe, of 5 µL, 10 µL, 25 µL, 50 µL, or similar to those occurring in samples to be analyzed are also
250 µL capacity capable of accurately delivering micro-litre acceptable). Solvents should contain less than 0.1 µg N/mL.
quantities is required. The needle should be long enough to (Warning—Flammable solvents.)
reach the hottest portion of the inlet section of the furnace 6.6 Nitrogen Stock Solution, 1000 µg N/mL, Prepare a stock
when injecting the sample. The syringe may be part of an solution by accurately weighing approximately 1.195 g of
automatic sampling and injection device used with the instru- carbazole or 0.565 g of pyridine to the nearest milligram, into
ment. a tared 100 mL volumetric flask (see 6.6.1). Fifteen millilitres
5.7 Strip Chart Recorder (Optional). of acetone may then be added when using carbazole to help
dissolve it. Dilute to volume with the selected solvent. Calcu-
5.8 Sample Inlet System—One of the following must be late the exact concentration of the stock solution based on the
used: actual mass of pyridine or carbazole used and corrected for any
5.8.1 Manually Operated Syringe. known purity factors for the specific lot of pyridine or
5.8.2 Syringe, with a constant rate injector system, capable carbazole. This stock may be further diluted to desired nitrogen
of delivering a sample at a precisely controlled rate. concentrations.
5.8.3 Boat Inlet System, to facilitate analysis of samples that 6.6.1 Calibration standards from commercial sources may
would react with the syringe or syringe needle. The pyrolysis be used if they conform to the requirements of the test method.
tube for boat inlet use may require specific construction to NOTE 1—Pyridine should be used with low boiling solvents (<220 °C).
permit insertion of a boat fully into the inlet section of the NOTE 2—Carbazole should be used with high boiling solvents
furnace. The boat inlet system external to the furnace may be (>220 °C).
cooled to a temperature below room temperature to aid in NOTE 3—Working standards should be remixed on a regular basis
depending upon frequency of use and age. Typically, standards have a
dissipating the heat from the boat when it is removed from the useful life of about 3 months, and should be refrigerated when not being
furnace. Cooling the boat inlet system may also reduce the used.
chances of the sample combusting in the boat before introduc-
6.7 Cupric Oxide Wire, as recommended by instrument
tion into the furnace and may be necessary when running
manufacturer.
volatile samples such as naphtha using a boat inlet system.
6.8 Quartz Wool (optional), or other suitable absorbent
5.9 Quartz Insert Tube (Optional), may be packed with material that is stable and capable of withstanding temperatures
cupric oxide (CuO) or other oxidation catalyst as recom- inside the furnace (Note 4).
mended by the instrument manufacturer, to aid in completing NOTE 4—Materials meeting the requirements in 6.8 are recommended
oxidation. This is inserted into the exit end of the pyrolysis to be used in sample boats to provide a more uniform injection of the
tube.
5.10 Vacuum System (Optional), The chemiluminescence 3
Reagent Chemicals, American Chemical Society Specifications , American
detector may be equipped with a vacuum system to maintain Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
the reaction cell at reduced pressure (typically 20 mm to
25 mm Hg). This can improve the signal to noise ratio of the and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
detector. MD.
2
D4629 − 17
sample into the boat by wicking any remaining drops of the sample from 1.0 µL ⁄s). Rate of injection is dependent on such factors as
the tip of the syringe needle prior to introduction of the sample into the viscosity, hydrocarbon type, and nitrogen concentration. Each
furnace. Consult instrument manufacturer recommendations for further
guidance.
user must adopt a method whereby a consistent and uniform
injection rate is ensured. An automatic sampling and injection
6.9 Pyridine. (Warning—Flammable, irritant.) device may be used to introduce the material at a reproducible
6.10 Carbazole. rate. If an automatic sampling and injection device is not being
used, determine the quantity of material injected using either
7. Hazards 10.2.1 (volumetric injection procedure) or 10.2.3 (gravimetric
7.1 High temperature is employed in this test method. injection procedure).
Exercise care when using flammable materials near the pyroly- NOTE 5—For the most consistent injection rate and best analytical
sis furnace. results, a constant rate injection unit or automatic sampling and injection
device may be helpful. Coke formation at the outlet of the combustion
8. Sampling tube may indicate too rapid of an injection rate. Consult manufacturer for
recommendations.
8.1 To preserve volatile components, which may be in some NOTE 6—With direct injection below 5 mg ⁄kg of nitrogen, the needle
samples, do not uncover samples any longer than necessary. septum blank may become increasingly important. Error due to this can be
Analyze samples as soon as possible after taking from the bulk avoided by inserting the syringe needle into the hot inlet and allowing the
supplies to prevent loss of nitrogen or contamination due to needle-septum blank to dissipate before injecting the sample.
exposure or contact with sample container. 10.4 If a boat inlet system is used, then the material to be
analyzed is injected into a quartz boat using one of the
9. Assembly Apparatus procedures described in 10.2.1, 10.2.2, or 10.2.3 and the quartz
9.1 Assemble apparatus in accordance with manufacturer’s boat is moved into the hot portion of the combustion tube.
instructions. Refer to the manufacturer’s instructions for selecting the rate of
boat movement into the furnace and boat residence time in the
9.2 Adjust the gas flows and the pyrolysis temperature as hot portion of the combustion tube.
recommended by the instrument manufacturer.
10.5 Calibration curves shall be generated in one of the
10. Calibration and Standardization following manners depending on the capability of the instru-
mentation used.
10.1 Prepare a series of calibration standards from the stock
10.5.1 For systems that use a microprocessor or computer
solution (see 6.6) covering the range of operation and consist-
system for data collection and calibration curve generation, the
ing of nitrogen type and matrix similar to samples to be
calibration curve shall be based on the linear regression of a
analyzed. There shall be a minimum of two calibration
minimum of three repeat measurements of each calibration
standards in addition to the solvent blank, used to generate the
standard.
calibration curve.
10.5.2 For those detectors not equipped with a micropro-
10.2 Determine the volume or mass of the material to be cessor or computer system for generating a calibration curve,
analyzed by using one of the volumetric or gravimetric construct a standard curve as follows. Repeat the determination
methods described below. of each calibration standard and the blank three times to
10.2.1 Volumetric measurement of the injected material is determine the average net response for each. Construct a curve
obtained by filling the syringe to the 80 % level, retracting the plot of detector response (integration counts) versus nanograms
plunger so that the lower liquid meniscus falls on the 10 % of nitrogen injected and apply the best straight line fit through
scale mark, and recording the volume of liquid in the syringe. the plotted data.
After the material has been injected, again retract the plunger
so that the lower liquid meniscus falls on the 10 % scale mark 10.6 The response curve should be linear with a minimum
and record the volume of liquid in the syringe. The difference R2 of 0.999. The intercept should not be forced through zero.
between the two volume readings is the volume of material The calibration curve shall be checked each day that the
injected. instrument is used (see Section 14).
10.2.2 Alternatively, an automatic sampling and injection
device may be used to volumetrically inject a reproducible 11. Procedure
volume of the material into the furnace. 11.1 Obtain a test specimen using the procedure in Section
10.2.3 Gravimetric measurement of the injected material is 8. The nitrogen concentration in the test specimen must be less
obtained by weighing the syringe before and after injection to than the concentration of the highest standard used in the
determine the amount of material injected. This procedure calibration. Injection volumes ranging from 3 µL to 100 µL are
provides greater precision than the volumetric procedure, acceptable depending on the instrument being used. The size of
provided a balance with a precision of at least 60.01 mg is the injected sample shall be similar to the size of the injected
used. standards used for calibration.
10.3 To introduce the sample into the furnace, insert the 11.2 Flush a clean microlitre syringe several times with the
syringe needle through the inlet septum up to the syringe barrel sample to be determined, and introduce it into the furnace
and inject the sample or standard at a uniform rate as specified using the procedure outlines in 10.2 – 10.4 (depending on
by the instrument manufacturer (typically 0.2 µL ⁄s to whether a boat inlet system is being used). For samples with
3
D4629 − 17
total nitrogen concentration in the range 1 mg ⁄kg to TABLE 1 Repeatability and Reproducibility
100 mg ⁄kg, sample sizes injected are typically up to 10 µL. For Concentration (mg/kg N) r R
samples with total nitrogen concentration less than 1 mg ⁄kg, 100 2.0 8.7
75 1.7 7.5
injected sample size can be up to 100 µL. Follow the instru- 50 1.4 6.1
ment manufacturer’s recommendation on sample size based on 25 1.0 4.2
type of sample and level of nitrogen present. 10 0.6 2.6
1 0.18 0.81
11.3 To obtain one result, measure each test specimen a 0.3 0.10 0.44
minimum of three times and calculate the average detector
response.
14. Quality Assurance/Quality Control (QA/QC)
12. Calculation
14.1 Confirm the performance of the instrument and the test
12.1 For samples introduced volumetrically (10.2.1 or
procedure by analyzing a quality control (QC) sample.
10.2.2), density values used for calculations are to be measured
14.1.1 When QA/QC protocols are already established in
using Test Method D1298, Test Method D4052 or their
the testing facility, these may be used when they confirm the
equivalent, at ambient temperature.
reliability of test results.
12.2 Calculate the nitrogen content of the sample in mg/kg 14.1.2 When there is no QA/QC protocol established in the
for the average of the three determinations that make up a testing facility, Appendix X1 may be used as the QA/QC
single result as follows: system.
nitrogen, mg/kg 5 ~ I 2 I 0 ! 3 K/ ~ S 3 V 3 D ! (1) 14.2 Users of this test method are advised that in contractual
or agreements, one or more of the contracting parties can and may
make Appendix X1 a mandatory practice.
nitrogen, mg/kg 5 ~ I 2 I 0 ! 3 K/ ~ S 3 M ! (2)
where: 15. Precision and Bias4

D = density of sample, g/mL, 15.1 The precision of this test method as determined by
S = slope of the calibration curve, counts/ng N, statistical examination of interlaboratory results is as follows
V = volume of sample, µL, (see Table 1):
K = dilution factor, 15.1.1 Repeatability—The difference between two test re-
M = mass of sample, mg, sults obtained by the same operator with the same apparatus
I = average detector response, integration counts, and under constant operating conditions on identical test material
I0 = intercept of the calibration curve, integration counts. would, in the long run, in the normal and correct operation of
12.3 For analyzers equipped with a calibration adjust, cal- the test method, exceed the following values in only one case
culate the nitrogen content of the sample in mg/kg as follows in twenty, where X = the average of the two test results.
(the average of three determinations make up a single result): r 5 0.1825~ X ! 0.5149
(5)
nitrogen, mg/kg 5 ~ I 2 B ! 3 K/ ~ V 3 D ! (3) 15.1.2 Reproducibility—The difference between two single
or and independent test results obtained by different operators
working in different laboratories on identical test material
nitrogen, mg/kg 5 ~ I 2 B ! 3 K/M (4)
would, in the long run, in the normal and correct operation of
where: the test method, exceed the following values in only one case
D = density of sample, g/mL, in twenty, where X = the average of the two test results.
S = slope of the calibration curve, counts/ng N, R 5 0.8094~ X ! 0.5149
(6)
V = volume of sample, µL,
K = dilution factor, 15.2 The bias of this test method cannot be determined since
M = mass of sample, mg, an appropriate standard reference material containing a known
I = visual display reading of the sample, ng N trace level of nitrogen in a liquid petroleum hydrocarbon is not
B = average of visual display readings of the blank, ng N. available to form the basis of a bias study.
13. Report 16. Keywords

13.1 For results equal to or greater than 1 mg ⁄kg, report the 16.1 liquid hydrocarbons; total nitrogen
nitrogen result to two significant figures when two or more
significant figures are available. For results less than 1 mg ⁄kg, 4
report the nitrogen result to the nearest tenth of a mg/kg. State be obtained by requesting Research Reports RR:D02-1199 and RR:D02-1527.
that results were obtained according to Test Method D4629. Contact ASTM Customer Service at service@astm.org.
4
D4629 − 17
APPENDIX
X1. QUALITY CONTROL (QC) MONITORING
X1.1 Confirm the performance of the instrument or the test stability of the testing process, and customer requirements.
procedure by analyzing QC sample(s). Generally, a QC sample is analyzed each testing day with
routine samples. The QC frequency should be increased if a
X1.2 Prior to monitoring the measurement process, deter-
large number of samples are routinely analyzed. However,
mine the average value and control limits of the QC sample.
when it is demonstrated that the testing is under statistical
Refer to Practice D6299 and ASTM MNL 7.5
control, the QC testing frequency may be reduced. The QC
X1.3 Record the QC results and analyze by control charts or sample precision should be periodically checked against the
other statistically equivalent techniques to ascertain the statis- ASTM method precision to ensure data quality. Refer to
tical control status of the total test process.6 Refer to Practice Practice D6299 and ASTM MNL 7.5
D6299 and ASTM MNL 7.5 Investigate any out-of-control data
for root cause(s). The results of this investigation may, but not X1.5 It is recommended that, if possible, the type of QC
necessarily, result in instrument recalibration. sample that is regularly tested be representative of the material
routinely analyzed. An ample supply of QC sample material
X1.4 The frequency of QC testing is dependent on the should be available for the intended period of use, and must be
criticality of the quality being measured, the demonstrated homogenous and stable under the anticipated storage condi-
5
tions.
MNL 7, Manual on Presentation of Data and Control Chart Analysis , ASTM
International, West Conshohocken, PA.
6
In the absence of explicit requirements given in the test method, this clause X1.6 See Practice D6299 and ASTM MNL 75 for further
provides guidance in QC testing frequency. guidance on QC and control charting techniques.
SUMMARY OF CHANGES
(D4629 – 12 (2017)) that may impact the use of this standard. (Approved Dec. 15, 2017.)
(1) Updated the title.
5
Designation: 435/15

Freezing Point of Aviation Fuels (Automatic Phase
Transition Method)1
1. Scope* 3.2 Definitions of Terms Specific to This Standard:

1.1 This test method covers the determination of the tem- 3.2.1 automatic phase transition method, n—in this test
perature below which solid hydrocarbon crystals form in method, the procedures of automatically cooling a liquid
aviation turbine fuels. aviation fuel specimen until solid hydrocarbon crystals appear,
followed by controlled warming and recording of the tempera-
1.2 This test method is designed to cover the temperature ture at which the solid hydrocarbon crystals completely redis-
range of −80 °C to 20 °C; however, 2003 Joint ASTM/IP solve into the liquid phase.
Interlaboratory Cooperative Test Program mentioned in 12.4
3.2.2 Peltier device, n—a solid-state thermoelectric device
has only demonstrated the test method with fuels having
constructed with dissimilar semiconductor materials, config-
freezing points in the range of −42 °C to −60 °C.
ured in such a way that it will transfer heat to and away from
1.3 The values stated in SI units are to be regarded as a test specimen dependent on the direction of electric current
standard. No other units of measurement are included in this applied to the device.
standard.
1.4 This standard does not purport to address all of the 4. Summary of Test Method
safety concerns, if any, associated with its use. It is the 4.1 A specimen is cooled at a rate of 15 °C ⁄min 6 5 °C ⁄min
responsibility of the user of this standard to establish appro- by a Peltier device while continuously being illuminated by a
priate safety and health practices and determine the applica- light source. The specimen is continuously monitored by an
bility of regulatory limitations prior to use. For specific array of optical detectors for the first formation of solid
warning statements, see 7.1, 7.3, and 7.5. hydrocarbon crystals. Once the hydrocarbon crystals are
formed, the specimen is then warmed at a rate of 10 °C ⁄min 6
2. Referenced Documents 0.5 °C ⁄min until the last hydrocarbon crystals return to the
2.1 ASTM Standards:2 liquid phase. The detectors are sufficient in number to ensure
D2386 Test Method for Freezing Point of Aviation Fuels that any solid hydrocarbon crystals are detected. The specimen
temperature at which the last hydrocarbon crystals return to the
3. Terminology liquid phase is recorded as the freezing point.
3.1 Definitions: 5. Significance and Use
3.1.1 freezing point, n—in aviation fuels, the fuel tempera-
ture at which solid hydrocarbon crystals, formed on cooling, 5.1 The freezing point of an aviation fuel is the lowest
disappear when the temperature of the fuel is allowed to rise temperature at which the fuel remains free of solid hydrocar-
under specified conditions of test. bon crystals. These crystals can restrict the flow of fuel through
the fuel system of the aircraft. The temperature of the fuel in
1
the aircraft tank normally decreases during flight depending on
aircraft speed, altitude, and flight duration. The freezing point
Subcommittee D02.07 on Flow Properties. of the fuel must always be lower than the minimum operational
Current edition approved June 1, 2016. Published June 2016. Originally fuel temperature.
approved in 1996. Last previous edition approved in 2015 as D5972 – 15. DOI:
10.1520/D5972-16. 5.2 Petroleum blending operations require precise measure-
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or ment of the freezing point.
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on 5.3 This test method produces results which have been
the ASTM website. found to be equivalent to Test Method D2386 and expresses

1
D5972 − 16
results to the nearest 0.1 °C, with improved precision over Test 7.4 Pipette, capable of dispensing 0.15 mL 6 0.01 mL of
Method D2386. This test method also eliminates most of the sample.
operator time and judgment required by Test Method D2386. 7.5 Cotton Swabs—Plastic- or paper-shaft cotton swabs to
5.4 When specification requires Test Method D2386, do not clean the specimen cup. (Warning—The use of swabs with
substitute this test method or any other test method. wooden shafts may damage the mirrored surface of the
specimen cup.)
6. Apparatus
6.1 Automatic Apparatus3—This apparatus consists of a 8. Preparation of Apparatus
microprocessor-controlled test chamber that is capable of 8.1 Install the analyzer for operation in accordance with the
cooling and heating the test specimen, optically observing the manufacturer’s instructions.
appearance and disappearance of solid hydrocarbon crystals,
8.2 Turn on the liquid cooling medium and ensure its
and recording the temperature of the specimen. A detailed
temperature is appropriate for the specimen being tested in
description of the apparatus is provided in Annex A1.
accordance with the manufacturer’s instructions (see Note 1).
6.2 The apparatus shall be equipped with a specimen cup,
8.3 Turn on the purge gas and ensure that it is regulated to
optical detector array, light source, digital display, Peltier
the appropriate pressure in accordance with the manufacturer’s
device, and a specimen temperature measuring device.
instructions.
6.3 The temperature measuring device in the specimen cup
8.4 Turn on the main power switch of the analyzer.
shall be capable of measuring the temperature of the test
specimen from −80 °C to +20 °C at a resolution of 0.1 °C and NOTE 2—Some apparatus are capable of generating a source of dry
accuracy of 0.1 °C. purge gas, thus eliminating the need for an external supply of a
compressed gas.
6.4 The apparatus shall be equipped with fittings to permit
the circulation of a liquid medium to remove heat generated by 9. Calibration and Standardization
the Peltier device and other electronic components of the 9.1 Ensure that all of the manufacturer’s instructions for
apparatus. calibrating, checking, and operating the apparatus are fol-
6.5 The apparatus shall be equipped with fittings to permit lowed.
the circulation of purge gas to purge the test chamber contain- 9.2 To verify the performance of the apparatus, an aviation
ing the specimen cup of any atmospheric moisture. turbine fuel sample for which extensive data has been obtained
7. Reagents and Materials by freeze point, Test Method D2386, may be used. Samples
such as those used in the ASTM interlaboratory cross-check
7.1 n-Octane—Reagent grade is suitable. (Warning— program would meet this criterion. Such verification materials
Flammable. Harmful if inhaled. Keep away from heat, sparks, can also be prepared from intracompany cross-checks.
and open flame.) Alternatively, high-purity n-octane or n-nonane with known
7.2 Cooling Medium—Liquid heat exchange medium to freezing points can be used to verify the calibration of the
remove the heat generated by the Peltier device and other temperature-measuring device in the apparatus.
electronic components from the apparatus.
10. Procedure
NOTE 1—Some apparatus are designed to use tap water as a cooling
medium to bring the specimen temperature to −60 °C. To achieve cooling 10.1 Open the test chamber lid and clean the specimen cup
of the specimen to −80 °C, provide circulation of the cooling medium at inside the test chamber with a cotton swab.
−30 °C or lower to the apparatus. Since water freezes at 0 °C, a
commercial or technical grade isopropanol is suitable as the cooling
10.2 Rinse the specimen cup by pipetting 0.15 mL 6
medium. Refer to the manufacturer’s operating instructions on the 0.01 mL of specimen into the cup. Clean the specimen out of
relationship between the cooling medium temperature and the minimum the cup by using a cotton swab. The cup should be cleaned to
specimen temperature. the point where no visible droplets of specimen remain in the
7.3 Purge Gas—A gas such as air, nitrogen, helium, or cup.
argon with a dew point below the lowest temperature attained 10.3 Rinse the cup a second time by repeating 10.2.
by the specimen under the conditions of the test. (Warning—
Compressed gas under high pressure.) (Warning—Inert gas 10.4 Carefully measure 0.15 mL 6 0.01 mL of specimen
can be an asphyxiant when inhaled.) into the specimen cup.
10.5 Close and lock the test chamber lid.
3
The sole source of supply of the Phase Technology Freezing Point Analyzer 10.6 Start the operation of the apparatus according to the
Model Series 70, 70V, and 70X known to the committee at this time is Phase manufacturer’s instructions. From this point up to and includ-
Technology, No. 135-11960 Hammersmith Way, Richmond, B.C. Canada, V7A
5C9. All the model series previously mentioned have identical test chambers and ing the termination of the measurement, the apparatus auto-
electronics. The distinction between different model series is the low temperature matically controls all operations. Purge gas and liquid cooling
limit. Refer to manufacturer’s product information on the low-temperature limit of medium will begin to flow through the apparatus. The Peltier
various models. If you are aware of alternative suppliers, please provide this
device cools the specimen at a rate of 15 °C ⁄min 6 5 °C ⁄min.
information to ASTM International Headquarters. Your comments will receive
careful consideration at a meeting of the responsible technical committee,1 which The optical detectors continuously monitor the specimen for
you may attend. the formation of hydrocarbon crystals. The temperature of the
2
D5972 − 16
specimen is continuously monitored by the apparatus and Test Method D2386. There was no lab bias demonstrated in the
displayed on its front panel. Once hydrocarbon crystals are 2003 Joint ASTM / IP Interlaboratory Cooperative Test Pro-
detected, the specimen is then warmed at 10 °C ⁄min 6 gram.5
0.5 °C ⁄min until all the crystals redissolve into the liquid
phase. When the disappearance of the last crystals is detected, 12.4 The precision statements were derived from a 2003
the specimen temperature is recorded and the measurement is Joint ASTM/IP interlaboratory cooperative test program. Par-
terminated. ticipants analyzed 13 samples comprised of various aviation
fuels over the temperature range of −42 °C to −60 °C. The
10.7 The freezing point value will be displayed by the
2003 study did not include Jet B or JP4 samples. Twelve
apparatus.
laboratories participated with the automatic phase transition
10.8 Unlock and open the test chamber lid and clean the apparatus and 15 participated with the manual Test Method
specimen out of the specimen cup with a cotton swab. D2386 test method. The precision statistics were compiled and
11. Report calculated based on the 0.1 °C resolution offered by the
automatic phase transition method. Models 70, 70V, and 70X
11.1 Report the temperature recorded in 10.7 as the freezing participated in this study. Information on the types of samples
point, Test Method D5972. and their respective average freezing point is contained in the
12. Precision and Bias research report.5
NOTE 3—In the 1994 interlaboratory study, the 30, 50, and 70 series
12.1 Repeatability—The difference between two test results models were used, and among all the fuels, all the differences were within
obtained by the same operator with the same apparatus under the reproducibility of Test Method D2386 (2.5 °C) except for two. These
constant operating conditions on identical test material would, two were the only samples of fuels of Grades JP4 and Jet B, and for these
in the long run, in the normal and correct operation of this test the average results were 2.5 °C and 2.8 °C warmer than those of Test
method, exceed 0.50 °C only in one case in twenty. Method D2386. Based on these two samples in the 1994 interlaboratory
12.1.1 Reproducibility—The difference between two single study, there may be a bias for these sample types relative to the manual
method for Jet B and JP4 samples.4
and independent results obtained by different operators work-
ing in different laboratories on identical test material would, in
the long run, in the normal and correct operation of this test 13. Keywords
method, exceed 0.80 °C only in one case in twenty. 13.1 aviation turbine fuels; freezing point; Peltier; thermo-
12.2 Bias—Because there are no liquid hydrocarbon mix- electric; wax crystals
tures of known freezing point, which simulate aviation fuels,
bias cannot be established.
12.3 Relative Bias—The results for all the samples from the
interlaboratory program4 were examined for biases relative to
4 5
Supporting data (the results of the 1994 Interlaboratory Cooperative Test Supporting data (the results of the 2003 Joint ASTM/IP Interlaboratory
Program) have been filed at ASTM International Headquarters and may be obtained Cooperative Test Program) have been filed at ASTM International Headquarters and
by requesting Research Report RR:D02-1385. may be obtained by requesting Research Report RR:D02-1572.
ANNEX
A1. DETAILED DESCRIPTION OF APPARATUS
A1.1 Test Chamber, comprised of optical detectors, lens, is purged by dry gas. The dry gas inlet and outlet are shown in
light source, specimen cup, temperature sensor, Peltier device, Fig. A1.1. The test chamber wall is made of black-colored
and heat sink arranged in a configuration as shown in Fig. metal and plastic components to minimize light reflection.
A1.1. The lid of the test chamber can be opened to allow A1.1.1 Specimen Cup, comprised of a black plastic wall and
cleaning of specimen cup and introduction of new specimen. a highly polished metal bottom. The polished surface of the
Once closed and locked, the chamber becomes airtight. An bottom serves as a reflective surface for light. The transfer of
O-ring is used to seal the mating surfaces between the lid and heat to and away from the specimen, through the metal bottom,
the rest of the chamber. The air trapped in the closed chamber is controlled by the Peltier device.
3
D5972 − 16
FIG. A1.1 Schematic of Test Chamber FIG. A1.2 Detection of Crystal Formation
A1.2 Apparatus Exterior Interface—The exact layout may

vary; however, the following displays and push buttons are
A1.1.2 Temperature Sensor, reading to 0.1 °C and minimum recommended. A typical apparatus (see Fig. A1.3) is shown as
accuracy to 0.1 °C, permanently embedded into the bottom of an example.
the specimen cup and positioned less than 0.1 mm below the A1.2.1 Message Display, provides information on the status
top surface of the cup bottom. This temperature sensor, which of the apparatus. It shall display an appropriate message when
is made of a single strand of platinum, provides accurate the apparatus is idle and no fault is found. At the end of a test,
measurement of the specimen temperature. the result is displayed. It displays a diagnostic message if a
A1.1.3 Peltier Device, capable of controlling the specimen fault is detected in any of the major components of the
temperature over a wide range. The range varies depending on apparatus. Detailed explanation of the diagnostic messages is
the model series. During specimen cooling, heat is transferred available in the manufacturer’s service manual.
from the top of the device to the bottom. Since the top is in A1.2.2 Specimen Temperature Display, gives an update of
thermal contact with the bottom of the specimen cup, the the specimen temperature during the measurement.
specimen will be chilled. The bottom of the Peltier device is in
thermal contact with the heat sink, where heat is dissipated to A1.2.3 Light Signal Display, gives an update of the scat-
the cooling medium. During specimen warming, the reverse tered light level received by the optical detectors. This infor-
process will take place. mation may be used by service personnel for trouble-shooting
purposes.
A1.1.4 Light Source, to provide a beam of light with a
wavelength of 660 nm 6 10 nm. The light source is positioned A1.2.4 MENU Buttons, allow the operator to change the
such that it provides an incident beam (Fig. A1.1) impinging temperature from Celsius to Fahrenheit and vice versa; noting
onto the specimen at an acute angle. The light is reflected from that the Celsius scale is regarded as the standard.
the polished bottom of the specimen cup. When the specimen A1.2.5 RUN Button, allows the operator to start the mea-
is a homogeneous liquid, the reflected beam impinges onto the surement sequence once the specimen is put inside the test
chamber lid, which is black in color. The reflected light is then chamber.
absorbed by the black surface. When wax crystals appear in the
A1.2.6 RESET Button, allows the operator to stop the
specimen, the reflected beam is scattered by the solid-liquid
measurement sequence. Upon pressing this button, the appa-
phase boundaries. A significant amount of scattered light
ratus will immediately stop the measurement sequence and
impinges onto the lens (Fig. A1.2).
warm the specimen to ambient temperature.
A1.1.5 Optical Detectors, positioned above the lens to
NOTE A1.1—A full description, installation, setup instructions, and
monitor the clarity of the specimen. The distance between the maintenance instructions are contained within the manufacturer’s manual
optical detectors and the lens is adjusted such that the image of supplied with each instrument. They are included in the research report.6
the specimen is projected onto the light-sensitive surface of the
optical detectors. Sufficient optical detectors are used to cover 6
the image area. be obtained by requesting Research Report RR:D02-1398.
4
D5972 − 16
FIG. A1.3 Apparatus Exterior
SUMMARY OF CHANGES
(1) Updated IP designation to 435/15. (2) Revised subsection 4.1.
(D5972 – 05 (2010)) that may impact the use of this standard. (Approved Dec. 1, 2015.)
(1) Added IP designation 435/12 to the heading. (2) Revised subsection 12.1.
5
D5972 − 16
6

Evaluating Lubricity of Diesel Fuels by the High-Frequency
Reciprocating Rig (HFRR)1

1.1 This test method covers the evaluation of the lubricity of 2.1 ASTM Standards:2
diesel fuels using a high-frequency reciprocating rig (HFRR). D975 Specification for Diesel Fuel Oils
1.2 This test method is applicable to middle distillate fuels, Petroleum Products
such as Grades No. 1-D S15, S500, and S5000, and Grades No. D4177 Practice for Automatic Sampling of Petroleum and
2-D S15, S500, and S5000 diesel fuels, in accordance with Petroleum Products
Specification D975; and other similar petroleum-based fuels D4306 Practice for Aviation Fuel Sample Containers for
which can be used in diesel engines. This test method is Tests Affected by Trace Contamination
applicable to biodiesel blends. B5 was included in the round D6078 Test Method for Evaluating Lubricity of Diesel Fuels
robin program that determined the precision statement. by the Scuffing Load Ball-on-Cylinder Lubricity Evalua-
NOTE 1—It is not known that this test method will predict the
tor (SLBOCLE)
performance of all additive/fuel combinations. Additional work is under- E18 Test Methods for Rockwell Hardness of Metallic Ma-
way to establish this correlation and future revisions of this test method terials
may be necessary once this work is complete. E92 Test Methods for Vickers Hardness and Knoop Hard-
1.3 The values stated in SI units are to be regarded as ness of Metallic Materials
standard. No other units of measurement are included in this 2.2 SAE Standard:3
standard. SAE-AMS 6440 Steel, Bars, Forgings, and Tubing, 1.45 Cr
(0.93-1.05C) (SAE 52100), for Bearing Applications
safety concerns, if any, associated with its use. It is the 2.3 ISO Standard:4
responsibility of the user of this standard to establish appro- ISO 3290 Roller Bearings, Balls – Dimensions and toler-
priate safety, health, and environmental practices and deter- ances
mine the applicability of regulatory limitations prior to use.
Specific warning statements are given in Section 7. 3. Terminology
1.5 This international standard was developed in accor- 3.1 Definitions:
dance with internationally recognized principles on standard- 3.1.1 boundary lubrication, n—a condition in which the
ization established in the Decision on Principles for the friction and wear between two surfaces in relative motion are
Development of International Standards, Guides and Recom- determined by the properties of the surfaces and the properties
mendations issued by the World Trade Organization Technical of the contacting fluid, other than bulk viscosity.
Barriers to Trade (TBT) Committee. 3.1.1.1 Discussion—Metal to metal contact occurs and the
chemistry of the system is involved. Physically adsorbed or
1
2
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Subcommittee D02.E0 on Burner, Diesel, Non-Aviation Gas Turbine, and Marine contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Fuels. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved Aug. 1, 2018. Published September 2018. Originally the ASTM website.
3
approved in 1999. Last previous edition approved in 2016 as D6079 – 11 (2016). Available from SAE International (SAE), 400 Commonwealth Dr., Warrendale,
DOI: 10.1520/D6079-18. PA 15096-0001, http://www.sae.org.
4
This test method was developed by ISO/TC22/SC7/WG6 and is a part of ISO Available from American National Standards Institute (ANSI), 25 W. 43rd St.,
12156. 4th Floor, New York, NY 10036, http://www.ansi.org.

1
D6079 − 18
chemically reacted soft films (usually very thin) support
contact loads. As a result, some wear is inevitable.
3.1.2 lubricity, n—a qualitative term describing the ability
of a fluid to affect friction between, and wear to, surfaces in
relative motion under load.
3.1.2.1 Discussion—In this test method, the lubricity of a
fluid is evaluated by the wear scar, in microns, produced on an
oscillating ball from contact with a stationary disk immersed in
the fluid operating under defined and controlled conditions.
3.2 Abbreviations:
3.2.1 HFRR—high frequency reciprocating rig
3.2.2 WSD—wear scar diameter FIG. 1 Schematic Diagram of HFRR (not including instrumenta-
tion)
4.1 A 2 mL test specimen of fuel is placed in the test
reservoir of an HFRR. scribed test conditions. Correlation of HFRR test results with
field performance of diesel fuel injection systems has not yet
4.2 A vibrator arm holding a nonrotating steel ball and
been determined.
loaded with a 200 g mass is lowered until it contacts a test disk
completely submerged in the fuel. When the fuel temperature 5.6 This test method is designed to evaluate boundary
has stabilized, the ball is caused to rub against the disk with a lubrication properties. While viscosity effects on lubricity in
1 mm stroke at a frequency of 50 Hz for 75 min. this test method are not totally eliminated, they are minimized.
4.3 The test fuel temperature is maintained at 60 °C and the 6. Apparatus
ambient relative humidity is maintained between 30 % and
85 %. 6.1 High-Frequency Reciprocating Rig (HFRR),6,7(see Fig.
1) capable of rubbing a steel ball loaded with a 200 g mass
4.4 At the conclusion of the test, the upper specimen holder against a stationary steel disk completely submerged in a test
is removed from the vibrator arm and cleaned. The image of fuel. The apparatus uses a 1 mm stroke length at a frequency of
the wear scar is captured using the microscope digital camera, 50 Hz for 75 min. Complete operating conditions are listed in
and the dimensions of the major and minor axes of the wear Table 1.
scar are measured and recorded.
6.2 Test Reservoir, capable of holding a test disk in a rigid
5. Significance and Use manner beneath the test fuel. The temperature of this reservoir,
5.1 Diesel fuel injection equipment has some reliance on and consequently the test fuel contained in it, is maintained by
lubricating properties of the diesel fuel. Shortened life of means of a closely attached electrically controlled heater pad.
engine components, such as diesel fuel injection pumps and 6.3 Control Unit6,7for controlling stroke length, frequency,
injectors, has sometimes been ascribed to lack of lubricity in a test reservoir temperature, friction force, electrical contact
diesel fuel. potential, and test duration, with an electronic data acquisition
5.2 The trend of HFRR test results to diesel injection system and control system.
pump component distress due to wear has been demonstrated 6.4 Microscope, with Digital Camera6,7capable of 100×
in pump rig tests for some fuel/hardware combinations where magnification, installed and calibrated according to manufac-
boundary lubrication is believed to be a factor in the operation turer instructions, capable of capturing a crisp image of the
of the component.5 wear scar. Camera system resolution should be a minimum of
5.3 The wear scar generated in the HFRR test is sensitive to 2048 × 1536 pixels. The measurement system should allow
contamination of the fluids and test materials, the temperature horizontal and vertical measurement devices or cursors to be
of the test fuel, and the ambient relative humidity. Lubricity positioned at the wear scar boundaries with an accuracy of 1
evaluations are also sensitive to trace contaminants acquired micron.
during test fuel sampling and storage. 6.5 Cleaning Bath, ultrasonic seamless stainless steel tank
5.4 The HFRR and Scuffing Load Ball on Cylinder Lubric- with adequate capacity and a cleaning power of 40 W or
ity Evaluator (SLBOCLE, Test Method D6078) are two meth- greater.
ods for evaluating diesel fuel lubricity. No absolute correlation 6.6 Desiccator, capable of storing test disks, balls, and
has been developed between the two test methods. hardware.
5.5 The HFRR may be used to evaluate the relative effec-
tiveness of diesel fuels for preventing wear under the pre- 6
The sole source of supply of the apparatus known to the committee at this time
is PCS Instruments, 78 Stanley Gardens, London W3 7SZ, England.
5 7
Nikanjam, M., Crosby, T., Henderson, P., Gray, C., Meyer, K, and Davenport, If you are aware of alternative suppliers, please provide this information to
N., “ISO Diesel Fuel Lubricity Round Robin Program,” SAE, Paper No. 952372, ASTM International Headquarters. Your comments will receive careful consider-
SAE Fuels and Lubricants Meeting, Oct. 16-19, 1995, Toronto, Canada. ation at a meeting of the responsible technical committee,1 which you may attend.
2
D6079 − 18
TABLE 1 Test Conditions demonstrating that test balls and test disks meet the requirements listed in
Fluid volume 2 mL ± 0.20 mL 7.8 and 7.9.
Stroke length 1 mm ± 0.02 mm 7.10 Wiper, wiping tissue, light-duty, lint-free, hydrocarbon-
Frequency 50 Hz ± 1 Hz
Fluid temperature 60 °C ± 2 °C free, disposable.
Relative humidity between 30 % and 85 %
Applied load 200 g ± 1 g 8. Sampling and Sample Containers
Test duration 75 min ± 0.1 min
Bath surface area 6 cm2 ± 1 cm2 8.1 Unless otherwise specified, samples shall be taken by
the procedure described in Practice D4057 or Practice D4177.
8.2 Because of the sensitivity of lubricity measurements to
7. Reagents and Materials trace materials, sample containers shall be only fully epoxy-
7.1 Acetone, reagent grade (Warning—Extremely flam- lined metal, amber borosilicate glass, or polytetrafluorethylene
mable. Vapors may cause flash fire). (PTFE), cleaned and rinsed thoroughly at least three times with
7.2 Compressed Air, containing less than 0.1 ppmv hydro- the product to be sampled before use, as specified under
carbons and 50 ppmv water. (Warning—Compressed gas Containers for Lubricity Testing in Practice D4306.
under high pressure. Use with extreme caution in the presence 8.3 New sample containers are preferred, but if not
of combustible material.) available, the Containers for Lubricity Testing section of
7.3 Gloves, appropriate for the reagents used. Practice D4306 gives guidance on suitable cleaning procedures
for each type of container.
7.4 Reference Fluids:
7.4.1 Fluid A8—High lubricity reference (Warning— 9. Preparation of Apparatus
Flammable). Store in clean, borosilicate glass with an alumi-
9.1 Test Disks, (as received):
num foil-lined insert cap or a fully epoxy-lined metal container.
9.1.1 Place disks in a clean beaker. Transfer a sufficient
Store in dark area.
volume of heptane or 50/50 isooctane/2-propanol into the
7.4.2 Fluid B8—Low lubricity reference (Warning—
beaker to completely cover the test disks.
Flammable. Vapor harmful). Store in clean, borosilicate glass
9.1.2 Place beaker in ultrasonic cleaner and turn on for
with an aluminum foil-lined insert cap or a fully epoxy-lined
7 min.
metal container. Store in a dark area.
9.1.3 Handle all clean test pieces with clean forceps. Re-
7.5 Heptane, reagent grade (Warning—Extremely flam- move the test discs and repeat the above cleaning procedure
mable. Vapors may cause flash fire.) from 9.1.1 with acetone for 2 min.
7.6 Isooctane, reagent grade (Warning—Extremely flam- 9.1.4 Dry and store in desiccator.
mable. Vapors may cause flash fire.) NOTE 3—Drying operations can be accomplished using compressed air
7.7 2–propanol, reagent grade (Warning—Extremely flam- jet at 140 kPa to 210 kPa-pressure.
mable. Vapors may cause flash fire.) 9.2 Test Balls, (as received)—The test balls are to be cleaned
7.8 Test Ball, (Grade 28 per ISO 3290) of SAE-AMS 6440 following the same procedure, 9.1.1 to 9.1.4, as for the test
steel, with a diameter of 6.00 mm, having a Rockwell hardness disks.
“C” scale (HRC) number of 58 - 66, in accordance with Test 9.3 Hardware—All hardware and utensils that come into
Methods E18. contact with the test disks, test balls, or test fuel, shall be
7.8.1 Test balls are an extremely important part of the cleaned by washing thoroughly with heptane or 50/50
process and can significantly affect results. An equivalency isooctane/2-propanol, rinsed with acetone, and dried.
evaluation was conducted on test balls and test disks and can be
found in ASTM Research Report RR: RR:D02-1890.9 10. Test Apparatus Inspection and Verification
7.9 Test Disk,—10 mm disk of SAE-AMS 6440 steel ma- 10.1 Recommended Calibration Intervals:
chined from annealed rod, having a Vickers hardness “HV 30,” 10.1.1 Stroke length—every three months.
in accordance with Specification E92, a scale number of 10.1.2 Temperature probes—every twelve months.
190-210, turned, lapped, and polished to a surface finish of less 10.2 Test Apparatus—Verify test apparatus performance and
than 0.02 µm Ra. accuracy at least every 20 tests by testing each reference fluid
7.9.1 Test disks are an extremely important part of the in accordance with this section. Perform one test with each
process and can significantly affect results. An equivalency reference fluid. If the WSD for either fluid is outside the
evaluation was conducted on test balls and test disks and can be specified limits provided with each fluid by the ASTM Test
found in ASTM Research Report RR: RR:D02-1890.9 Monitoring Center, verify that the test is performed correctly,
NOTE 2—Users are encouraged to request a certificate of conformance and repeat both reference tests. If necessary, calibrate the
HFRR by following the steps in the instrument manual, and
8
Reference Fluids A and B are available from ASTM Test Monitoring Center, then test each of the high and low reference fluids.
6555 Penn Ave., Pittsburgh, PA 15026–4489.
9
Supporting data have been filed at ASTM International Headquarters and may 11. Procedure
be obtained by requesting Research Report RR:D02-1890. Contact ASTM Customer
Service at service@astm.org. 11.1 Table 1 summarizes the test conditions.
3
D6079 − 18
11.2 Strict adherence to cleanliness requirements and to the where:
specified cleaning procedures is required. During handling and WSD = wear scar diameter, µm,
installation procedures, protect cleaned test parts (disks, balls, M = major axis, µm, and
reservoir, screws, heater block, and push rod) from contami- N = minor axis, µm.
nation by using clean forceps and wearing appropriate gloves.
11.3 Using forceps, place the test disk into the test reservoir, 14. Report
shiny side up. Secure the test disk to the test reservoir and the 14.1 Report the following information:
test reservoir to the test apparatus. Ensure the unit’s tempera- 14.1.1 Major axis and minor axis to the nearest 10 µm, and
ture probe is properly placed in the reservoir. Ensure the wear scar diameter to the nearest 10 µm.
relative humidity in the test laboratory is between 30 % and 14.1.2 Description of the test fuel and date sample taken.
85 %. (Warning—Relative humidity is an important param-
14.1.3 Record the batch number of the test specimens.
eter. Performing the test outside of the relative humidity limits
14.1.4 Date of testing.
will affect the lubricity result.)
14.1.5 Report the test method number, D6079.
11.4 Using forceps, place the test ball into the upper
specimen holder and attach the holder to the end of the vibrator 15. Precision and Bias10,11
arm. Ensure the holder is horizontal before fully securing the
unit. 15.1 Precision—The precision was developed using fuels
representing a range of lubricity levels as well as a practical
11.5 Using a pipette, place 2 mL 6 0.2 mL of the test fuel mix of common types of fuels, such as Grade No. 1-D, Grade
into the test reservoir. No. 2-D, additized, and a biodiesel blend. The precision data
11.6 Set the test parameters according to Table 1. were developed in a 2008 cooperative testing program involv-
11.7 Lower the vibrator arm and suspend a 200 g weight ing ten testing laboratories from the United States, Canada, and
from the arm. Start the test. South Africa. There were six distinct fluids and each laboratory
received four samples of each fuel to conduct replicate testing
11.8 At the completion of the test, lift up the vibrator arm. both with the microscope and the digital camera. The fluids
Remove the upper specimen holder. were blind coded so that replicate samples were not known to
11.9 Rinse the test ball (still in the holder) in cleaning the operator. A randomized test sequence was provided and
solvents and wipe and dry thoroughly with a tissue. each laboratory was requested to use the same operator and
11.10 Remove the test reservoir and properly dispose of the equipment for all 24 samples.
fuel. 15.1.1 The difference between two test results obtained by
the same operator with the same apparatus under constant
11.11 Place the test ball holder under the microscope and operating conditions on identical test material would, in the
measure the wear scar diameter in accordance with Section 12. long run, in the normal and correct operation of the test
12. Measurement of the Wear Scar method, exceed the following value in only one case in twenty:
Repeatability = 50 µm
12.1 Turn on the microscope light and position the upper
specimen holder in the staging area slot at 100× magnification. 15.1.2 The difference between two single and independent
results obtained by different operators working in different
12.2 Adjust the stage so that the wear scar in centered in the laboratories on identical test material would, in the long run, in
viewing field. the normal and correct operation of the test method, exceed the
12.3 Adjust the light intensity to obtain a clearly illuminated following value in only one case in twenty:
image. Reproducibility = 80 µm
12.4 Adjust the microscope stage until the edges of the wear 15.2 Bias—The procedure in this test method has no bias
scar come into focus. because lubricity is not a fundamental and measurable fluid
12.5 Capture the image using the camera. property and thus is evaluated in terms of this test method.
12.6 Identify and measure the x axis. 16. Keywords
12.7 Identify and measure the y axis.
16.1 boundary lubrication; diesel fuel; friction; HFRR; lu-
12.8 Record the measurement results. bricity; wear
NOTE 4—Refer to Annex A1, Measurement of HFRR Wear Scars, for
guidance to determine the boundaries of the wear scar.
13. Calculation 10
Nikanjam, M., Rutherford, J., “Improving the Precision of the HFRR Lubricity
13.1 Calculate the wear scar diameter as follows: Test,” SAE Paper No. 2006–01–3363.
11
WSD 5 ~ M1N ! /2 be obtained by requesting Research Report RR:D02-1718.
4
D6079 − 18
ANNEX
A1. MEASUREMENT OF HFRR WEAR SCARS
INTRODUCTION
Annex A of ISO 12156-1:2006 (E) Measurement of HFRR wear scars, used by permission from
ISO/CS.
A1.1 The appearance of the wear scar on the ball can vary scratched part of the scar is surrounded by a less distinct worn
with fuel type, particularly when lubricity additives are present. area, and there is no sharp boundary between the worn and
In general, the wear scar appears to be a series of scratches in unworn areas of the ball. In these cases, it can be more difficult
the direction of motion of the ball, somewhat larger in the x to see or measure the true scar shape; as shown in Fig. A1.1,
direction than in the y direction. the overall wear scar comprises the distinct and the less distinct
areas.
A1.2 In some cases, for example when low-lubricity refer-
ence fluids are tested, the boundary between the scar and the A1.3 Photographic examples of various wear scar shapes
discolored (but unworn) area of the ball is distinct, and it is are shown in Fig. A1.2, together with an assessment of the
easy to measure the scar size. In other cases, the central overall scar boundary.
5
D6079 − 18
FIG. A1.1 Example of a Wear Scar with an Indistinct Boundary
6
D6079 − 18
FIG. A1.2 Examples of Wear Scars
7
D6079 − 18
FIG. A1.2 Examples of Wear Scars (continued)
SUMMARY OF CHANGES
Subcommittee D02.E0has identified the location of selected changes to this standard since the last issue
(D6079 – 11 (2016)) that may impact the use of this standard. (Approved Aug. 1, 2018.)
(1) Revised subsections 7.8 and 7.9, adding new subsections (2) Added new Note 2.
7.8.1 and 7.9.1.
8
D6079 − 18
9

Boiling Point Distribution of Samples with Residues Such
as Crude Oils and Atmospheric and Vacuum Residues by
High Temperature Gas Chromatography1
1. Scope* 1.5 This test method is not applicable for the analysis of
1.1 This test method covers the determination of the boiling materials containing a heterogeneous component such as
point distribution and cut point intervals of crude oils and polyesters and polyolefins.
residues by using high temperature gas chromatography. The 1.6 The values stated in inch-pound units are to be regarded
amount of residue (or sample recovery) is determined using an as standard. The values given in parentheses are mathematical
external standard. conversions to SI units that are provided for information only
1.2 This test method extends the applicability of simulated and are not considered standard.
distillation to samples that do not elute completely from the 1.7 This standard does not purport to address all of the
chromatographic system. This test method is used to determine safety concerns, if any, associated with its use. It is the
the boiling point distribution through a temperature of 720 °C. responsibility of the user of this standard to establish appro-
This temperature corresponds to the elution of n-C100. priate safety, health, and environmental practices and deter-
1.3 This test method is used for the determination of boiling
Specific warning statements are given in Section 8.
point distribution of crude oils. This test method uses capillary
1.8 This international standard was developed in accor-
columns with thin films, which results in the incomplete
dance with internationally recognized principles on standard-
separation of C4-C8 in the presence of large amounts of carbon
disulfide, and thus yields an unreliable boiling point distribu- ization established in the Decision on Principles for the
tion corresponding to this elution interval. In addition, quench- Development of International Standards, Guides and Recom-
ing of the response of the detector employed to hydrocarbons mendations issued by the World Trade Organization Technical
eluting during carbon disulfide elution, results in unreliable Barriers to Trade (TBT) Committee.
quantitative analysis of the boiling distribution in the C4-C8
region. Since the detector does not quantitatively measure the
carbon disulfide, its subtraction from the sample using a 2.1 ASTM Standards:2
solvent-only injection and corrections to this region via D2887 Test Method for Boiling Range Distribution of Pe-
quenching factors, results in an approximate determination of troleum Fractions by Gas Chromatography
the net chromatographic area. A separate, higher resolution gas D2892 Test Method for Distillation of Crude Petroleum
chromatograph (GC) analysis of the light end portion of the (15-Theoretical Plate Column)
sample may be necessary in order to obtain a more accurate D4057 Practice for Manual Sampling of Petroleum and
description of the boiling point curve in the interval in question Petroleum Products
as described in Test Method D7900 (see Appendix X1). D6352 Test Method for Boiling Range Distribution of Pe-
troleum Distillates in Boiling Range from 174 °C to
1.4 This test method is also designed to obtain the boiling
700 °C by Gas Chromatography
point distribution of other incompletely eluting samples such as
D7500 Test Method for Determination of Boiling Range
atmospheric residues, vacuum residues, etc., that are charac-
Distribution of Distillates and Lubricating Base Oils—in
terized by the fact that the sample components are resolved
Boiling Range from 100 °C to 735 °C by Gas Chroma-
from the solvent.
tography
1
2
Subcommittee D02.04.0H on Chromatographic Distribution Methods. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Dec. 1, 2019. Published December 2019. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
10.1520/D7169-19. the ASTM website.

1
D7169 − 19
D7900 Test Method for Determination of Light Hydrocar- 3.1.12.1 Discussion—Normally 0.1 s is used. In cases where
bons in Stabilized Crude Oils by Gas Chromatography sample elutes immediately after injection, 0.05 s is used.
E594 Practice for Testing Flame Ionization Detectors Used 3.1.13 start elution temperature (SET), n—the temperature
in Gas or Supercritical Fluid Chromatography at which the first amount of hydrocarbon is detected by the
E1510 Practice for Installing Fused Silica Open Tubular flame ionization detector above a predetermined threshold.
Capillary Columns in Gas Chromatographs
3.1.14 %recovery (RC), n—percentage of the sample eluted.
3. Terminology 3.1.14.1 Discussion—%Recovery is calculated from the
sample area (ASMP), the response factor (RF), the sample mass,
3.1 Definitions of Terms Specific to This Standard:
(MSMP), and the solvent mass (MSLSMP) used in sample
3.1.1 cut point interval, n—the mass % obtained between
dissolution.
two selected temperatures of the interval.
3.1.15 %recovery threshold (Rt) , n—if the %recovery falls
3.1.2 data acquisition rate, n—the speed of conversion of
above a preset limit, the sample is considered fully eluted and
the analog signal to a digital signal, expressed in Hz (cycles/
its recovery is assumed to be 100 %.
second).
3.1.15.1 Discussion—If the %recovery values found for
3.1.3 final boiling point (FBP), n—the temperature, for fully duplicate analyses of a nearly completely eluting sample are
eluting samples (recovery = 100 %), at which 99.5 % of the 99.6 % and 101.2 %, the %recovery threshold (Rt) may be set
sample is eluted. to 99.6 % and thus either of these results may be considered as
3.1.4 final elution time (FEt), n—the retention time of the fully eluted and set to 100 %.
component of the reference time standard sample that elutes at 3.2 Symbols:
the end of the temperature ramp of the oven. 3.2.1 ASMP—net area of the sample
3.1.5 final elution temperature (FET), n—the boiling point 3.2.2 ASTD—net area of the response factor standard
of the normal paraffin that elutes at the time when the oven
reaches its final temperature. 3.2.3 MSL—mass of solvent used in preparing sample solu-
tion
3.1.6 initial boiling point (IBP), n—the temperature corre-
sponding to an accumulated 0.5 % of the total area of the eluted 3.2.4 MSLSTD—mass of solvent used in preparing the re-
sample after correcting for the percent of sample recovery. sponse factor standard solution
3.1.7 quenching factor (QF), n—a number that corrects for 3.2.5 MSMP—sample mass used in sample preparation
the diminished response due to the solvent profile co-eluting 3.2.6 MSTD—mass of the standard used in preparing the
with sample components. response factor solution
3.1.7.1 Discussion—Data acquired during the quenching
interval (QI) shall be corrected by applying the quenching 4. Summary of Test Method
factor. 4.1 This is a gas chromatographic method utilizing an inlet
3.1.8 quenching interval (QI), n—the time interval of the and a capillary column, both of which are subject to a
start and end of elution of the CS2 used as a solvent. temperature program. A flame ionization detector is used as a
3.1.8.1 Discussion—Sample components that elute during transducer that converts mass to an electrical signal A data
this time interval shall be corrected by a factor due to their acquisition system operating in the slice mode and chromatog-
diminished response resulting from the co-elution of the raphy software is used to accumulate the electronic signal. A
relatively large amount of solvent present in the sample with retention time calibration mixture is used to develop a retention
the light sample components. time versus boiling point curve. A solution of the Reference Oil
5010 or a gravimetric blend, which fully elutes from the
3.1.9 residue (R), n—the mass % of the sample that has not
column under the conditions of the test method and whose
eluted at the temperature of calculation.
boiling point distribution have been characterized in Test
3.1.9.1 Discussion—Residue is calculated from the %recov-
Method D6352 or D7500, is used to determine the detector
ery.
response factor. Solvent injections are made, and the resulting
3.1.10 response factor (RF), n—the factor used in order to signal is subtracted from both the response factor standard and
calculate the %recovery of the sample. the sample chromatogram. Finally, the sample solution is
3.1.10.1 Discussion—The response factor is determined injected and with the use of the response factor, the amount of
from the net area of the standard (ASTD), mass of standard sample recovered is calculated. After converting the retention
(MSTD), and mass of solvent (MSLSTD) used in the solution of times of the sample slices to temperature, the boiling point
the standard. A fully eluting sample, such as Reference Oil distribution can be calculated up to the recovered amount.
5010, is used in obtaining the response factor.
3.1.11 sample area obtained (ASMP) , n—the net chromato- 5. Significance and Use
graphic area (after baseline subtraction) obtained for the 5.1 The determination of the boiling point distribution of
sample at the final elution time or temperature. crude oils and vacuum residues, as well as other petroleum
3.1.12 slice, n—the reciprocal of the data acquisition rate; fractions, yields important information for refinery operation.
the time interval used to accumulate data, expressed in sec- These boiling point distributions provide information as to the
onds. potential mass percent yield of products. This test method may
2
D7169 − 19
provide useful information that can aid in establishing opera- 6.2 Carrier Gas Purification System—Gas purifiers are used
tional conditions in the refinery. Knowledge of the amount of in order to remove traces of oxygen as well as moisture and
residue produced is important in determining the economics of other impurities present in the carrier gas. The purification
the refining process. system should contain a hydrocarbon trap and an oxygen trap.
The latter should preferably have a visible indicator in order to
6. Apparatus assess the remaining capacity of the oxygen trap.
6.1 Gas Chromatograph—A gas chromatograph provided 6.3 Data System—A data system composed of a computer
with a cryogenic valve for cooling the oven to sub ambient and software for data acquisition, which digitizes the detector
temperatures is required. Typical conditions of operating the signal, is recommended. Some instrumentation digitizes the
Gas Chromatograph are given in Table 1. It shall also have the signal at the electrometer board in order to reduce noise. The
following components: data system is used at acquisition rates of about 10 Hz, which
6.1.1 Flame Ionization Detector (FID)—A flame ionization correspond to slices of 0.1 s. This rate of data acquisition is
detector capable of maintaining a temperature 5 °C to 10 °C necessary to obtain a minimum number of slices void of
higher than the highest column temperature. The flame ioniza- sample or solvent elution immediately after injection. Data
tion detector should possess a jet orifice of about 0.018 in. acquisition systems facilitate the inspection of the baseline
(0.45 mm) in order to delay the plugging of the orifice due to under high magnification and allow the inspection of the
column bleed. The FID should possess a sensitivity of retention time calibration mixture chromatogram. Retention
0.005 coulombs ⁄g (see Practice E594) and should have a linear time shifts can be measured. Overlaying chromatograms is also
range of 106. possible to ascertain similar signal amplitude.
6.1.2 Inlet—Either a temperature programmable inlet with a
6.4 Automatic Sample Injector—It is mandatory to use an
glass liner or a cool-on-column inlet can be used. The inlet
auto sampler since the external standard technique used in this
shall be capable of operating in a temperature-programmed
analysis requires identical volumes for all injections.
mode from 50 °C to the final temperature of the oven. It is
Additionally, small volumes (0.1 µL to 0.2 µL) shall be injected
important that the temperature of the inlet, at any time during
in a reproducible manner. Syringes of 5 µL to 10 µL having
the analysis, be either equal to or greater than the oven
needle gauges of size 23 to 26 are to be used.
temperature. With the use of either inlet, frequent replacement
of the liner or removal of a section of the column may be 6.5 Carrier Gas Control—The gas chromatograph shall be
required due to accumulation of non-volatile sample compo- operated under constant flow conditions. The flow rate at the
nents. It is important that a leak free seal be reestablished after beginning of the oven temperature program shall not differ by
replacement of the liner or the removal of a small section of the more than 1 % from the flow measured at the final oven
column. temperature. Electronic pneumatic control is highly recom-
mended.
7. Column and Column Performance Criteria
TABLE 1 Typical Gas Chromatographic ConditionsA
Initial Oven Temperature −20 °C
7.1 A 100 % bonded polydimethylsiloxane column having a
Initial Oven Time 0 min nominal inside diameter of 0.5 mm and a film thickness of
Oven Temperature Program 15 °C ⁄ min 0.09 µm to 0.17 µm is used.
Final Oven Temperature 425 °C to 435 °CB
Final Hold Time 10 min 7.2 The column used should be capable of sustaining
temperatures of 435 °C under temperature programming. Alu-
Inlet Initial TemperatureC 50 °C
Inlet Temperature Program 15 °C ⁄ min minum covered fused silica and metal columns have been
Inlet Final Temperature 425 °C successfully used.
Column 5 m × 0.53 mm × 0.09B 7.3 The column should be capable of eluting carbon number
-0.15 µm PDMS 100 at its highest temperature. It is important that C100 be
Column Flow 20 mL/min
Carrier Control Constant Flow eluted during the temperature program cycle of the oven.
7.4 Column resolution is determined from the separation of
DetectorD FID
Detector Temperature 435 °C carbons 50 and 52 in the retention time calibration mixture
Detector Gases: chromatogram. The resolution should be between 1.8 to 4.0.
Hydrogen 40 mL/min
Air 450 mL/min
See Eq 1 in 13.1.
Make-Up (N2, He) 15 mL/min 7.5 The column shall be capable of allowing the start of the
Volume Injected 0.2 µL-0.5 µL-1.0 µLB
elution of n-C5 prior to the solvent elution, which is CS2, at
Sample Concentration 2.0 % (m/m) −20 °C. The descending edge of the n-C5 peak co-elutes with
Data Acquisition Rate 10 Hz the solvent. It is to be noted that at these low temperatures
Total Acquisition Time 40 min to 50 min
A
liquid phases may turn solid, and retention shifts may be
Conditions used for the interlaboratory study.
B
Several participants used these conditions. Higher temperatures yield higher
observed during the elution of compounds at these low oven
recoveries. temperatures.
C
Use lowest temperature recommended by manufacturer.
D
Use GC manufacturer’s recommendations. 7.6 Column Overloading—The prevention of column over-
loading is carried out by determining the skewness of a
3
D7169 − 19
selected peak among the components of the retention time under a fume hood and heat with an infrared lamp (about
calibration mixture chromatogram. Any paraffin with a carbon 200 W) placed at a safe distance (about 15 cm to 20 cm) from
number between C12 and C24 may be chosen. The skewness the mixture for a period of 20 min or until the solution is clear.
should be between 0.8 and 2.0. See Eq 2 in 13.2. Other precautionary methods of dissolution are acceptable.
7.7 Column Flow—Helium is used as carrier. Column flow Careful attention should be given to avoid the ignition of the
rate is set to 20 mL ⁄min. CS2 (see 8.1).
8.4.4 Transfer a 2 mL aliquot of the final mixture obtained
8. Reagents and Materials in 8.4.3 into a 2 mL auto sampler vial and seal it firmly. This
8.1 Carbon Disulfide (CS2), 99+ % pure. (Warning— solution can be used for about one week if stored at 4 °C. The
Extremely flammable and toxic liquid.) Used as a solvent to contents of this vial are injected in order to obtain the retention
dilute the sample and standards as well. Use gloves and safety time–boiling point curve.
glasses when handling the CS2 in a well-ventilated area or NOTE 1—Polywax is a trademark of the Baker Petrolite Corporation
fume hood. It is recommended to use adjustable-volume bottle (Barnsdall, OK). This retention time calibration mixture is commercially
dispensers and/or pipettors to minimize direct handling and available from chromatographic supply houses as well as from companies
avoid cross-contamination of CS2. Wash vials containing CS2 that build simulated distillation analyzers. The retention time calibration
should be capped with a solvent resistant septa. mixture may differ among supply houses in that docosane, tetracosane and
hexacosane are also added to the Polywax 655 or Polywax 1000 in order
8.2 Polywax 655 or Polywax 1000—Used as a component to enhance the concentration of these hydrocarbons in the polywaxes.
of the retention time calibration mixture. Since these Poly-
waxes have carbon 22 as the first component, it shall be 8.5 Detector Relative Response Test Mixture—It is neces-
complemented with the mixture of paraffins described in 8.4.1 sary to initially validate the response of the entire gas chro-
and 8.4.3 so that the entire range of carbon numbers (C5-C100) matographic system. Since this test method assumes that all
is present in the sample. hydrocarbons have the same relative response regardless of
their retention time, a solution shall be prepared in order to
8.3 Paraffıns—The following normal paraffins are used in determine the relative response factors. An alternative proce-
the preparation of the retention time calibration mixture: dure is to use a gravimetric blend as specified in Test Method
pentane undecane heptadecane D7500.
hexane dodecane octadecane
heptane tridecane nonadecane 8.5.1 Prepare a solution containing the following normal
octane tetradecane eicosane paraffins:
nonane pentadecane tetracontane
decane hexadecane decane octacosane
tetradecane dotriacontane
8.3.1 The purities of these compounds should be 99 % or octadecane tetracontane
greater. eicosane pentacontane
8.4 Retention Time Calibration Standard—This standard 8.5.2 Weigh about 100 mg of each paraffin to the nearest
can be obtained from chromatography supply companies. This 0.1 mg into a 50 mL volumetric flask. Mix well and add CS2 to
standard is composed of a mixture of Polywax (either P655 or the mark. Ensure that the paraffins are completely dissolved.
P1000) as well as a mixture of paraffins. The addition of the Record the masses of the paraffins, which will be used in Eq 3
paraffin mixture is necessary to cover the range of C5-C20 since in order to calculate the relative response factor of each of the
these paraffins are absent in the Polywax. Furthermore the paraffins.
amounts of the paraffins are chosen so as to facilitate identi- 8.5.3 Record the assayed purity of each paraffin for use in
fying the carbons in the retention time calibration mixture Eq 3.
chromatogram. Alternatively, a successful mixture that has
8.5.4 Transfer an aliquot of the mixture prepared in 8.5.2 to
been used may be prepared by the procedure described in 8.4.1
a 2 mL injection vial. Ensure that the components are in
– 8.4.3 which requires the preparation first of the n -paraffin
solution prior to the transfer. Warm the vial if necessary. Inject
mixture (see 8.3) and then spiking an aliquot of this mix to a
weighed amount of Polywax 655 or 1000. 0.1 µL to 0.2 µL.
8.4.1 Place approximately 20 mL of CS2 into a round 8.6 Reference Oil 5010—In order to determine the sample
bottom 50 mL flask. Transfer with care. recovery, the detector response factor has to be determined. For
8.4.2 Prepare a mixture of the paraffins listed in 8.3 as this purpose, utilize Reference Oil 5010 as an external stan-
follows. Weigh 500 mg of each component into a 20 mL vial. dard. This material is obtainable from various chromatography
Add an additional 500 mg for dodecane and about 20 mg of suppliers. A gravimetric blend, as described in Test Method
tetracontane. Store this mixture at 4 °C and use it as a spiking D7500, can also be used
mixture in the preparation of the Polywax 655 retention time
calibration mixture. These additional quantities are spiked to 8.7 Gases—The following compressed gases are utilized for
ease the identification of the n-paraffins; other n-paraffins may the operation of the gas chromatograph:
be chosen as peak markers. 8.7.1 Nitrogen, 99.999 %. (Warning—Compressed gas un-
8.4.3 Weigh about 25 mg of the Polywax 655 and add it to der high pressure.) Total impurities should not exceed
the vessel prepared in 8.4.1. Add approximately 10 mg of the 10 mL ⁄m3. This gas is used as detector makeup. Helium has
paraffin spiking mixture prepared in 8.4.2. Stir the solution also been used as makeup gas.
4
D7169 − 19
8.7.2 Hydrogen, 99.999 %. (Warning—Extremely flam- them into a weighed container. Only samples that are soluble in
mable gas under high pressure.) Total impurities should not carbon disulfide (CS2) can be analyzed by this test method.
exceed 10 mL ⁄m3. This gas is used as fuel for the operation of 10.3 Weigh 0.2 g to 0.25 g of the sample to the nearest
the detector. 0.1 mg. Add 10 mL of CS2. Record this weight also to the
8.7.3 Air, 99.999 %. (Warning—Compressed gas under nearest 0.1 mg. Enter these values in the data acquisition
high pressure and supports combustion.) Total impurities system if appropriate.
should not exceed 10 mL ⁄m3. This gas is used to sustain
combustion in the FID detector. 10.4 Store all prepared solutions at a temperature of 4 °C.
8.7.4 Helium, 99.999 %. (Warning—Compressed gas un- Care should be taken that the solution is prepared a short time
der high pressure.) This gas is used as carrier gas and should prior to running the analysis. Samples can be stored in the auto
not contain more than 5 mL ⁄m3 of O2. The total amount of sampler vials.
impurities should not exceed 10 mL ⁄m3. 10.5 Prepare as many vials of a sample as are necessary to
carry out multiple analyses of that sample. Do not use the same
9. Preparation of the Gas Chromatograph vial to run duplicates; use separate vials containing the same
9.1 A summary of the conditions used for developing the solution.
precision statement is given in Table 1.
11. Preparation of the Response Factor Standard
9.2 Column Installation—The column is installed using
graphite ferrules and an electronic leak detector is used to 11.1 Weigh 0.2 g to 0.25 g of Reference Oil 5010 to the
ascertain the absence of leaks. Follow the instructions given in nearest 0.1 mg. Add 10 mL of CS2 and record the weight of the
Test Method D2887 and Practice E1510 for the installation of solvent to the nearest 0.1 mg. Store this solution at 4 °C, if not
silica or aluminum clad silica columns. Metal columns require used immediately.
slightly different techniques in cutting and installation. Follow
the recommendations of the column supplier. 12. Preparation of the Apparatus and Data System
9.3 Detector Temperature—Select a detector temperature 12.1 After the column is installed and checked for leaks,
that is at least 5 °C to 10 °C higher than the highest oven prepare the gas chromatograph to analyze the sample according
temperature. to the typical conditions given in Table 1.
9.4 Initial Oven Temperature—The initial temperature of 12.2 Set the acquisition system to digitize the data at 10 Hz.
the oven is chosen according to the sample type to be analyzed This will result in a slice width of 0.1 s. This data acquisition
as follows: rate is kept constant for all samples, standards, and the solvent
blank in order to acquire the same number of slices. The
9.4.1 Crude Oil Samples—Crude oil samples may contain
baseline chromatogram may contain the same or larger number
hydrocarbons starting from methane, C2, C3, and C4 which
of slices than the sample chromatograms, depending on when
probably co-eleute with C5. Therefore, even at an initial
the data acquisition stops. Thus, various chromatograms taken
temperature of −20 °C, C5 and C6 are partially resolved from
in a sequence may differ by 5 to 10 slices. This fact is of no
the CS2. Further decreases in oven temperature do not increase
consequence with regard to the calculations.
the separation of C5 from C1-C4 hydrocarbons which co-elute
with n-C5. 12.3 Arrange to save the acquired data files. Build the
9.4.2 Residues and Samples Having Higher IBP—For sequence of samples to be injected by the gas chromatograph.
samples that have an initial boiling point of 100°C or greater,
such as vacuum residues or atmospheric residues, the initial 13. Verification of System Performance
oven temperature can be set to between 35 °C and 40 °C. 13.1 Column Resolution—Prepare the gas chromatograph
Ensure that the sample is resolved from the solvent peak at the for injection of the retention time calibration mixture prepared
initial oven temperature selected. If the light ends cannot be in 8.4. Inject 0.1 µL to 0.2 µL of this sample. Determine the
separated from the solvent, then proceed as in 9.4.1. If the user column resolution as follows:
does not know the type of sample to be analyzed, all samples
can be analyzed with an initial temperature of −20 °C. R 5 2 ~ t 2 2 t 1 ! / ~ 1.699! ~ W 2 1W 1 ! (1)
where:
10. Sample Preparation R = resolution,
10.1 Ensure that the sample is a representative sample. t2 = retention time (s) for the n-C50 paraffin,
Follow the guidelines established in Practice D4057. Samples t1 = retention time (s) for the n-C52 paraffin,
should be handled according to their content of volatile W1 = peak width (s) at half height of the n-C50 peak, and
components. If the sample is submitted for other analyses, W2 = peak width (s) at half height for the n-C52.
remove a small aliquot (~10 mL) early in the testing sequence 13.1.1 Ensure that the resolution, R, is between 1.8 to 4.0.
in order to avoid loss of volatile components. Allow sample to 13.2 Skewness Test for Column Overloading—Select a com-
warm to room temperature prior to weighing. ponent between C12-C24 of the previous chromatogram or of
10.2 Samples that are solid or semi-solid at room tempera- the chromatogram of the retention time calibration mixture
ture may require heating up to as high as 60 °C in order to pour prepared in 8.4. For the component selected, determine the
5
D7169 − 19
skewness as follows. The skewness, s, is calculated by Eq 2: 14.3 Retention Time Calibration Mixture—Insert the reten-
ILS participants reported skewness of 0.8 to 2.0 for peaks C7 to tion time calibration mixture vial prepared in 8.4 into the auto
C100. sampler for injection. A typical chromatogram of the retention
s 5 ~ a1b ! /2a (2) time calibration mixture is shown in Fig. A1.2. The insert in the
Fig. A1.2 shows the best separation possible for the C5, CS2,
where: C6, and C7 and shows good peak shape for the C6 and C7
s = skewness of the peak, hydrocarbons. Identify all carbons up to C100.
a = left time segment measured at 10 % of the peak height
14.4 Response Factor Standard—Insert the vial containing
and that intersects the perpendicular from the apex of the
Reference Oil 5010 prepared in 8.5, which is used as a
peak to the retention time axis, and
response factor standard. Inject this standard in duplicate. A
b = right time segment measured at 10 % of the peak height
typical chromatogram of the reference oil analyzed at an initial
and that intersects the perpendicular from the peak apex
oven temperature of −20 °C is shown in Fig. A1.3. Verify that
to the retention time axis. Ensure that the skewness is
the response factor calculated by Eq 4 does not vary by more
between 0.8 and 2.0. Data acquisition systems can
than 2 %.
calculate this parameter.
14.5 Sample Analysis—Insert the sample vials prepared in
13.3 Determination of Detector Relative Response 10.3. Inject samples. Analyzing a QC material with acceptable
Factors—Prepare the gas chromatograph for the injection of results before the analysis of unknown samples is strongly
the detector test mixture prepared in 8.5. Inject 0.1 µL to 0.2 µL recommended.
of this sample. Calculate the relative response factor, Fi, of
each paraffin relative to eicosane as follows: 14.6 Additional Blank Runs—Insert a vial containing CS2 in
order to obtain a second blank run. Carry out a blank run after
M i 3 P i 3 Ac20
Fi 5 (3) each sample injection, and verify the absence of carryover
A i 3 Mc20 3 Pc20 from the previous samples. An ambient temperature version of
where: the method with faster oven ramping can be employed for these
Mi = mass of the paraffin in mg, clean-out runs in between samples to reduce run time and use
Mc20 = mass of the eicosane in mg, of cryogenic fluids.
Ai = peak area of the paraffin,
Ac20 = peak area of the eicosane, 15. Verification of Acquired Data
Pi = % purity of the paraffin as recorded in 8.5.3, and 15.1 Inspect all chromatograms by loading the data files in
Pc20 = % purity of eicosane.
the data acquisition system. Observe that the signal magnitude
13.3.1 The relative response factor, Fi, should have a value for each sample injected is approximately the same as that for
of between 0.9 and 1.10. Failure to achieve this range may be the retention time calibration mixture and the Reference Oil
due to inlet problems, lack of constant flow, or partial blockage 5010 chromatograms.
of the flame tip orifice, or a combination thereof. 15.2 Verification of the Retention Time Calibration Mixture
Chromatogram—Inspect the chromatograms acquired during a
14. Analytical Sequence sequence run. Do not use a chromatogram where the peaks do
14.1 Set up a sequence of the samples to be analyzed. The not meet the criteria of skewness as defined in 13.2. Inspect the
sequence will contain the order of the samples to be injected chromatogram for the components C5-C7 and the solvent peak
into the column. This schedule should be designed to achieve as shown in the insert of Fig. A1.2. The peaks should not
maximum reproducibility. A suggested order of the samples to present peak splitting nor peak tailing.
be analyzed is described in 14.2 – 14.6. If time constraints 15.3 Sample Chromatograms—Inspect the sample chro-
require a shorter sequence, the user shall ensure that there is no matograms and verify that the chromatograms can be overlaid
carryover between samples and sample types. to a duplicate chromatogram and show that the profile is
reproducible. Fig. A1.4 shows a chromatogram of a 30°API
14.2 Blank Run—At the beginning of each sequence, after
crude oil where the solvent peak is not resolved from the
any column maintenance is performed, make a blank run. It
sample components. Fig. A1.5 shows a typical chromatogram
may take more than 2 blanks to show a stable plateau with no
of an atmospheric residue where the solvent peak is resolved
indication of residual elution. A blank run constitutes an
from the sample components.
identical solvent injection having the same volume as the
sample injection. An acceptable blank run should show a stable 15.3.1 It is recommended that a QC material be analyzed at
plateau at the highest temperature of the oven (see 15.3). the beginning and end of every sequence. The QC sample
Furthermore, it should not show any indication of carryover or should have the same matrix as the samples analyzed.
residual sample elution. It should also not contain any ghost 15.4 Baseline or Blank Runs—Inspect, in the data system,
peaks. A typical blank sample run is shown in Fig. A1.1. the chromatograms of the blank solvent injections to verify that
Several blanks may be necessary after column installation or the blank signal obtained does not differ substantially from that
after an idle period of the gas chromatograph. Verification of obtained during the sample analysis. Check that the baseline
acceptable blanks is obtained by analyzing the Reference Oil exhibits a gradual rise up to the isothermal section of the
5010 or a gravimetric blend and a QC material. chromatogram and ensure that there is a gradual transition back
6
D7169 − 19
to the plateau of the baseline. Disregard any baseline that Oil 5010 and from the sample chromatogram in order to obtain the net
shows material eluting near the highest temperature of the area as shown in 16.1.4.
column. Also disregard any baseline that shows ghost peaks. 16.1 Zeroing of the Reference Oil Chromatogram:
Overlay the baseline signal with the sample signal as shown in 16.1.1 Examine the chromatogram obtained for Reference
Fig. A1.6. Use only those sample signals that asymptotically Oil 5010 (external standard), and ensure, by visual inspection
approach the baseline signals. Reject any sample run where the of the chromatogram in the data system, that the first 5 slices
baseline signal at the end of the run exceeds in value the contain neither sample nor solvent elution.
sample run. Reject any sample run at which at the end of the
16.1.2 Set up an array that contains slices obtained from the
run the signal exceeds the baseline signal by 10 %. It is
Reference Oil 5010 chromatogram. Calculate the average of
recommended that a new full blank analysis be performed at
the first five area slices. Subtract the average slice area from
regular intervals (for example, after every 4 to 5 samples) in a
each slice in the Reference Oil 5010 chromatogram. Set
sequence of samples to ensure good baseline data for subse-
negative numbers to zero.
quent samples.
15.4.1 Determine the Quenching Interval—Select the time 16.1.3 Zero the blank baseline chromatogram by carrying
that the solvent peak starts to elute. Determine when the out an analogous calculation as in 16.1.2.
solvent peak has eluted. Note the times of this interval in 16.1.4 Blank Baseline Subtraction from the Reference Oil
minutes. An expanded time scale chromatogram of the solvent 5010 Chromatogram—Subtract each zeroed blank baseline
peak is shown in Fig. A1.7. slice from the corresponding zeroed Reference Oil 5010 slice.
15.4.2 Determine the Magnitude of Solvent Response— If there are negative slices, set the slice values to zero.
Using the data system, overlay the solvent chromatograms and 16.1.5 Determination of the End of Elution Time of Refer-
verify that the profiles are similar. Verify that the total areas do ence Oil 5010—Since it is a requirement that the sample
not differ by more than 3 % from each other. chosen to obtain a response factor shall fully elute prior to the
15.5 External Standard Response Factor Chromatogram— FEt time, the end of sample elution for this chromatogram is to
Inspect the external standard chromatogram obtained from the be determined as described in Test Method D6352, using the
injection of Reference Oil 5010. Verify that the boiling point algorithm to determine the time the signal of the completely
distribution is within the consensus values as indicated in Test eluted sample returns to baseline.
Method D6352. Typical boiling point distribution values for 16.1.6 Determination of the Area of the Chromatogram for
Reference Oil 5010, obtained with this test method, are shown Reference Oil 5010—Determine the end time of solvent elu-
in Table 2. Correct any chromatography errors if the consensus tion. Sum all of the slices from the end of solvent elution to the
values are not obtained (see 16.1.7). end of sample elution. This is the area of the standard, ASTD.
16.1.7 Calculation of the Boiling Point Distribution of
16. Calculations Reference Oil 5010—The resulting corrected slices obtained
NOTE 2—The calculations are listed in this section. The chromatogram for Reference Oil 5010 are submitted to a Test Method D6352
for the reference oil, the sample, and the baseline shall be zeroed as given
calculation for boiling point distribution. A comparison of the
in 16.1.2.
NOTE 3—The baseline chromatogram is subtracted from the Reference values obtained with the consensus values listed in Table 2
shall be made and all the boiling point values shall fall within
the specified windows. If this requirement is not met, correct
TABLE 2 Consensus Values Obtained for the Boiling Point any chromatographic problems prior to proceeding with
Distribution of Reference Oil 5010 Used as External StandardA sample analysis. Typical problems found in this step are:
%BP avg °C
Allowable
avg °F
Allowable contaminated solvent; problems in sample preparation; sample
Differences, °C Differences, °F residue in the inlet or column, or both; quality of the baseline
IBP 428 9 801 16 used, a partially blocked detector jet, or a combination thereof.
5 477 3 891 5
10 493 3 918 5 16.2 Zeroing of Sample Chromatograms:
15 502 3 936 5
20 510 3 950 6 16.2.1 In the case of crude oil analysis or samples in which
25 518 4 963 6 the solvent peak is not resolved from the sample components,
30 524 4 975 7
35 531 4 987 7
ensure, by visual inspection of the chromatogram in the data
40 537 4 998 8 system, that the first 5 slices contain neither sample nor solvent
45 543 4 1008 8 elution. If there is sample elution, decrease the number of slices
50 548 4 1019 8
55 554 4 1030 8 for the averaging to 3 or increase the digitization rate given in
60 560 4 1040 8 12.2.
65 566 4 1051 8
70 572 4 1062 8
16.2.2 Zeroing the Sample Chromatogram—Proceed in a
75 578 5 1073 9 manner analogous to that described in 16.1.2.
80 585 4 1086 8 16.2.3 Zeroing the Blank Baseline Chromatogram—Carry
85 593 4 1099 7
90 602 4 1116 8 out an analogous calculation as in 16.1.3.
95 616 4 1140 7
FBP 655 18 1213 32 16.3 Blank Baseline Subtraction from the Sample
A
As reported in Test Method D6352. Chromatogram—Carry out an analogous calculation as in
16.1.4.
7
D7169 − 19
16.4 Quenching Correction—For crude oil samples, a 16.8 Calculation of the %Recovery—The %recovery is
quenching factor is used to correct for the diminished FID defined as:
response when the CS2 co-elutes with sample components. ~ ME! ME 3 ~ M SMP1M SLSMP!
This factor is applied to the time segment corresponding to the %RC 5 3 100 5 3 100
elution of CS2. In the interlaboratory study, the factor of 1.930 S M SMP
~ M SMP1M SLSMP! D M SMP
was applied. This value is determined from experiments made (5)

by dissolving butane, pentane, and hexane in toluene. The
solution is analyzed by injecting it under conditions identical to where:
sample analysis. The areas for the components are compared to ME = mass, in grams, of the sample eluted,
the areas obtained by gradually adding weighed aliquots of CS2 MSMP = sample mass, in grams, and
to the original solution. Alternatively the quenching value can MSLSMP = mass of solvent, in grams, used in the sample
be checked by performing a glass distillation by Test Method solution.
D2892. Samples that do not have components that co-elute Since:
with solvent, for example, residues or the Reference Oil 5010,
ME 5 ~ A SMP! 3 ~ RF! (6)
do not require the quenching correction.
16.4.1 Determine the Quenching Interval—Select the time where:
that the solvent peak starts to elute. Determine when the ASMP = net sample area, and
solvent peak has eluted. Note the times of this interval in RF = response factor of the Reference Oil 5010.
minutes. An expanded time scale chromatogram of the solvent Substituting Eq 6 for the value of ME in Eq 5 yields:
peak is shown in Fig. A1.7.
A SMP 3 RF 3 ~ M SMP1M SLSMP!
16.4.2 Locate the slices of the quenching interval. For %RC 5 3 100 (7)
~ M SMP!
samples in which the solvent component co-elutes with the
sample chromatogram (that is, crude oils), determine the Substituting Eq 4 in Eq 7 for the value of RF yields:
quenching interval, Q.I., as described in 16.4.1. Find the ~ M STD! ~ M SMP1M SLSMP! A SMP
closest slice corresponding to the beginning of elution of the %RC 5 3 3 3 100 (8)
~ M STD1M SLSTD! M SMP A STD
solvent peak as well as the final slice corresponding to the end
of elution of the solvent peak. 16.8.1 Determine whether the %recovery, (%RC) falls be-
16.4.3 Correct the diminished response of the interval by low the recovery threshold (Rt) limits set. If it is less than or
multiplying each slice of this interval by the quenching factor, equal to the recovery threshold (Rt), use the %recovery (%RC)
Q.F. Use the value as discussed in 16.4. determined in 16.8. If the %recovery is greater than the
recovery threshold (Rt), then the recovery is set to 100 %. If the
16.5 Determination of the Sample Final Elution Time— %recovery is larger than 102 % (1 standard deviation of the
Determine the time at which the oven reaches the isothermal residue), repeat the analysis or determine the chromatographic
portion of the temperature program. This is usually recognized problem.
as an inflection point in the baseline. This point is called the
16.9 Determination of the Boiling Point Distribution:
final elution time (FEt). The conversion of this slice to
temperature will yield the final elution temperature, FET. This 16.9.1 Multiply each slice of the sample chromatogram by
conversion is carried out in 16.9.4. the %recovery as established in 16.8.1. Divide each slice by the
total area of the sample obtained in 16.6. This will express the
16.6 Determination of the Sample Area—The net sample slices in a percent scale.
area is obtained by adding all slices from time t = 0 to the final 16.9.2 Add the slices that will yield 0.5 %, 1 %, 2 %, . . .
elution time, FEt. This net area is the ASMP. %recovery. Determine, at 1 % intervals, the time of the slice
16.7 Calculate the Response Factor, RF, as follows: yielding exactly 0.5, 1 %, 2 %, ...%recovery. Use an interpo-
lation procedure to find the fractional slices required to yield
~ M STD! 1 exactly 0.5, 1 %, ...2 %, ...%recovery.
RF 5 3 (4)
~ M STD1M SLSTD! A STD 16.9.3 Stop the calculation carried out in 16.9.2 when
where: obtaining a slice summation equal to the nearest whole integer
RF = response factor, of the %recovery.
ASTD = net area obtained for the Reference Oil 5010 16.9.4 Convert the retention times to boiling points as
chromatogram after baseline subtraction and after outlined in the Test Method D6352 algorithm. Use the boiling
excluding the solvent peak (this area was deter- point temperatures listed in Table 3. For each retention time
mined in 16.1.6), obtained in 16.9.2, find the corresponding temperature from the
MSLSTD = solvent mass, in grams, used for Reference Oil Boiling Point vs. Retention Time function as shown in Fig.
dissolution, and A1.8. Calculate the corresponding boiling points as determined
MSTD = mass, in grams, of Reference Oil 5010 used in in the Test Method D2887 algorithm.
preparing the response factor solution.
16.10 Calculation of Cut Point Intervals:
16.7.1 The mass term in Eq 4 has been expressed as a 16.10.1 For the two temperatures that define the cut point
fraction of the mass of solute and solvent. interval, find the two corresponding slices.
8
D7169 − 19
TABLE 3 Boiling Points Of ParaffinsA
Carbon Boiling Boiling Carbon Boiling Boiling
Number Point °C Point °F Number Point °C Point °F
1 –162 –259 51 579 1074
2 –89 –129 52 584 1083
3 –42 –44 53 588 1090
4 0 31 54 592 1098
5 36 97 55 596 1105
6 69 156 56 600 1112
7 98 209 57 604 1119
8 126 258 58 608 1126
9 151 303 59 612 1134
10 174 345 60 615 1139
11 196 385 61 619 1146
12 216 421 62 622 1152
13 235 456 63 625 1157
14 254 488 64 629 1164
15 271 519 65 632 1170
16 287 548 66 635 1175
17 302 576 67 638 1180
18 316 601 68 641 1186
19 330 626 69 644 1191
20 344 651 70 647 1197
21 356 674 71 650 1202
22 369 695 72 653 1207
23 380 716 73 655 1211
24 391 736 74 658 1216
25 402 755 75 661 1222
26 412 774 76 664 1227
27 422 791 77 667 1233
28 431 808 78 670 1238
29 440 825 79 673 1243
30 449 840 80 675 1247
31 458 856 81 678 1252
32 466 870 82 681 1258
33 474 885 83 683 1261
34 481 898 84 686 1267
35 489 912 85 688 1270
36 496 925 86 691 1276
37 503 937 87 693 1279
38 509 948 88 695 1283
39 516 961 89 697 1287
40 522 972 90 700 1292
41 528 982 91 702 1296
42 534 993 92 704 1299
43 540 1004 93 706 1303
44 545 1013 94 708 1306
45 550 1022 95 710 1310
46 556 1033 96 712 1314
47 561 1042 97 714 1317
48 566 1051 98 716 1321
49 570 1058 99 718 1324
50 575 1067 100 720 1328
A
Boiling Points from C1-C92 are taken from Test Method D6352.For carbons C92-C100 taken from reference in Annex 1 of Test Method D6352.
NOTE 1—API Project 44, October 31, 1972 is believed to have provided the original normal paraffin boiling point data that are listed in Table 3.
However, over the years some of the data contained in both API Project 44 (Thermodynamics Research Center Hydrocarbon Project) and Test Method
D6352 have changed and they are no longer equivalent. Table 3 represents the current normal paraffin boiling point values accepted by Subcommittee
D02.04 and found in all test methods under the jurisdiction of Section D02.04.0H.
NOTE 2—Test Method D6352 has traditionally used n-paraffin boiling points rounded to the nearest whole degree for calibration. The boiling points
listed in Table 3 are correct to the nearest whole number in both degrees Celsius and degrees Fahrenheit. However, if a conversion is made from one
unit to the other and then rounded to a whole number, the results will not agree with the table values for a few carbon numbers. For example, the boiling
point of n-heptane is 98.425 °C, which is correctly rounded to 98 °C in the table. However, converting 98.425 °C gives 209.165 °F, which rounds to
209 °F, while converting 98 °C gives 208.4 °F, which rounds to 208 °F. Carbon numbers 2, 4, 7, 8, 9, 13, 14, 15, 16, 25, 27, and 32 are affected by
rounding.
16.10.2 Using the calibration curve, convert this tempera- 16.10.4 Sum the normalized slices, starting with the initial
ture range to a time range. slice of the cut and terminating with the last slice after the cut.
16.10.3 Convert the time range to a slice number range by This sum will be equal to the %mass of the cut.
multiplying by 60 and dividing by the slice width in seconds.
9
D7169 − 19
16.10.5 The %recovery, RC, determined at a temperature test results for five crude oils and five residues. It is important
TRC that is equal to or less than FET, can be determined at a to note that the Results for the precision statement as shown in
new temperature TN by using the following equation: Tables 4-6 are to be used only within the ranges shown in the
~ RC 2 R C21% ! tables. Additional studies are required to expand the precision
~ T RC 2 T RC21% ! ~
E RC 5 3 T 2 T RC21% ! 1R C21% (9) to the ranges not listed in Tables 4-6, respectively.
where: test results obtained by the same operator with the same
ERC = estimated recovery at temperature T, apparatus under constant operating conditions on identical test
%RC = %recovery determined at temperature TRC in Material would, in the long run, in the normal and correct
16.8.1, Operation of the test method, exceed the values in only one
%RC-1% = %recovery determined at 1 % below the %RC, case in twenty as shown in Table 4 (Residues), Table 5 (Crude
and Oil), and Table 6 for Cuts (as used in the ASTM Crosscheck for
TRC-1% = temperature corresponding to RC-1%. Crude Oils).
16.10.5.1 The use of this equation for values TN > FET is 18.1.2 Reproducibility—The difference between two single
not recommended. and independent test results obtained by different operators
17. Report would, in the long run, in the normal and correct operation of
17.1 Report the temperatures to the nearest 0.5 °C (1 °F) at the test method, exceed the values shown in Table 4
1 % intervals between 1 % and up to the nearest integer of the (Residues), Table 5 (Crude Oil), and Table 6 for Cuts (as used
lower boundary of the %RC. Report also the initial boiling in the ASTM Crosscheck for Crude Oils).
point (IBP). Report the selected cut point intervals.
18.2 Bias—The bias in results of this test method cannot be
18. Precision and Bias3 determined because the boiling range distribution is defined by
the test method.
18.1 Precision—The precision of this test method was
determined by the statistical examination of the interlaboratory
19. Keywords
3
19.1 boiling point distribution; crude oils; cut point inter-
be obtained by requesting Research Report RR:D02-1724. Contact ASTM Customer vals; distillation residues; lubricants; residues; simulated
Service at service@astm.org. distillation
TABLE 4 Repeatability and Reproducibility for ResiduesA

Repeatability, r Reproducibility, R Range Covered
% (mass/mass) °C °F °C °F °C °F
recovered
IBP 5.72 10.3 13.7 24.7 246 to 504 474 to 939
5 3.39 6.1 5.75 10.4 315 to 547 599 to 1017
10 3.19 5.7 5.39 9.7 346 to 563 654 to 1045
15 2.88 5.2 5.2 9.4 368 to 575 694 to 1067
20 3.42 6.2 6.5 11.7 388 to 585 730 to 1085
25 3.55 6.4 6.71 12.1 405 to 595 761 to 1103
30 3.93 7.1 7.6 13.7 420 to 604 788 to 1119
35 4.38 7.9 8.9 16.0 434 to 614 813 to 1137
40 5.22 9.4 11 19.8 447 to 624 836 to 1155
45 6.27 11.3 13.5 24.3 462 to 634 863 to 1173
50 7.18 12.9 16.4 29.5 477 to 645 890 to 1193
55 8.64 15.6 19.9 35.8 493 to 656 919 to 1213
60 10.1 18.2 22.6 40.7 509 to 670 948 to 1238
65 11.7 21.1 24.7 44.5 529 to 684 984 to 1263
70 15.2 27.4 27.4 49.3 550 to 699 1022 to 1290
75 16.6 29.9 30.9 55.6 574 to 716 1065 to 1321
A
Do not extrapolate outside of the above reported data.
10
D7169 − 19
TABLE 5 Repeatability and Reproducibility for Crude OilA
recovered
IBP 1.35 2.4 2.49 4.5 30 to 31 86 to 88
5 8.94 16.1 19.6 35.3 76 to 97 169 to 207
10 11.4 20.5 19.5 35.1 109 to 154 228 to 309
15 8.23 14.8 15.1 27.2 134 to 217 273 to 423
20 7.51 13.5 13.1 23.6 160 to 259 320 to 498
25 8.7 15.7 13.6 24.5 184 to 295 363 to 563
30 8.22 14.8 13.1 23.6 210 to 327 410 to 621
35 8.52 15.3 14 25.2 231 to 358 448 to 676
40 8.83 15.9 14.9 26.8 249 to 398 480 to 748
45 8.99 16.2 15.1 27.2 265 to 436 509 to 817
50 9.88 17.8 16.4 29.5 285 to 325 545 to 887
55 10.8 19.4 18.6 33.5 304 to 517 579 to 963
60 12.4 22.3 21.5 38.7 326 to 563 619 to 1045
65 13.8 24.8 24.3 43.7 351 to 608 664 to 1126
70 14.3 25.7 21.2 38.2 379 to 608 714 to 1126
75 15.1 27.2 28.24 50.8 410 to 700 770 to 1292
A
TABLE 6 Repeatability and Reproducibility for Cut PointsA

Cut from Set Cut Temperature, Cut Temperature, Repeatability, r Reproducubility, R
to Temperature °C °F Mass % Mass %
Crude Cut 1 82.2 180 1.24 1.74
Crude Cut 2 193.3 380 1.42 1.92
Crude Cut 3 248.9 480 1.48 2.05
Crude Cut 4 343.3 650 1.63 2.28
Crude Cut 5 426.7 800 1.78 2.58
Crude Cut 6 565.6 1050 2.1 3.03
Crude Cut 7 596.1 1105 2.03 3.12
Crude Cut 8 720 1328 2.52 3.17
Residue Cut 1 330 626 0.0748 X 0.126 X
Residue Cut 2 450 842 0.0767 X 0.109 X
Residue Cut 3 600 1112 0.0338 (X + 30) 0.0726 (X + 30)
Residue Cut 4 720 1328 5.36 7.16
A
X= % mass recovered at the cut. Do not extrapolate outside of the above reported data.
ANNEX
A1. CHROMATOGRAMS AND FIGURES
11
D7169 − 19
FIG. A1.1 Typical Blank Run (Initial Temperature −20 °C)
FIG. A1.2 Chromatogram of the Retention Time Calibration Mixture C5-C100 Injected at −20 °C,
Insert Expands View of C5-C7 Region
12
D7169 − 19
FIG. A1.3 Chromatogram (Baseline Corrected) of Reference Oil 5010 Injected at −20 °C
FIG. A1.4 Chromatogram (Baseline Corrected) of a Crude Oil (Injected at −20 °C)
13
D7169 − 19
FIG. A1.5 Chromatogram (Baseline Corrected) of an Atmospheric Residue
14
D7169 − 19
FIG. A1.6 Correct and Incorrect Relative Position of Baseline and Sample Signal
FIG. A1.7 Expanded Chromatogram of a CS2 Injection for Selecting the Quenching Interval
15
D7169 − 19
FIG. A1.8 Boiling Point versus Retention Time Plot
APPENDIX
X1. ALGORITHM FOR MERGING BOILING POINT DISTRIBUTION RESULTS OF D7900 AND D7169
X1.1 The resulting data from Test Methods D7900 and without such interference. This algorithm generates boiling
D7169 can be used to perform a merge of the D7900 light ends point distribution results that correct this anomaly in the light
boiling point curve with that of D7169, using a variety of end portion of Test Method D7169 by merging the more
mathematical means. accurate results of Test Method D7900.
X1.2 This appendix outlines an algorithm to aid in merging X1.4 Summary of the Procedure
the results of D7900 with those of D7169 to result in a more X1.4.1 The boiling point distribution results from Test
accurate boiling point distribution of the crude oil sample. The Methods D7900 and D7169 for the same sample are collected
algorithm does not attempt to smooth or otherwise alter the in value arrays. They are merged together at a fixed boiling
results of the merged boiling point distribution, relying solely point temperature not to exceed the boiling point of n-nonane
on the original results from Test Methods D7900 and D7169. (the current limit of Test Method D7900 results). A new boiling
Additional mathematical smoothing or fitting is left to the point distribution result is calculated from the merged data.
individual user and his requirements. Recoveries greater than 100 % by mass after the merge are
X1.3 Significance and Use normalized through the D7169-only contribution to the final
results, as the D7900 results are assumed to be accurate as
X1.3.1 The scope of Test Method D7169 includes a caveat reported.
that results for the light end portion of the analysis may be
inaccurate due to the co-elution of the required carbon disulfide
solvent with light hydrocarbons. This results in a diminished or
quenched FID response to those hydrocarbons, resulting in
lower recoveries in this region. Test Method D7900 was
developed to more accurately determine the boiling point
distribution of the front end portion of a crude oil sample
16
D7169 − 19
NOTE X1.1—In a situation such as a heavy crude where there is no TABLE X1.1 Value Array D7900 Cumulative Mass Percent (CMP)
significant amount of light ends at or below C9, then the D7169 data versus BP Degrees Celsius (BP, °C) in 0.01 % by Mass Intervals
should be taken as reported with no merge or light ends correction. Array Row CMP BP (°C)
1 0.50 % –42.04
X1.5 D7900 and D7169 Data Accuracy Determination 2 0.51 % –11.72
3 0.52 % –0.50
X1.5.1 To ensure that the initial D7900 and D7169 data is ... ... ...
comparable in accuracy, determine the cumulative mass per- ... ... ...
cent recovery at the boiling point where the merge is to be C9 21.30 % 150.76
made from each of the D7900 and D7169 results. Calculate the
absolute difference as:
DIFFx 5 ABS~ M 1 2 M 2 ! (X1.1) D7169. For example, a sample containing 5 % by mass n-pentane would
have five successive whole mass percentages occurring at the boiling point
where: of n-pentane (36.06 °C). See Fig. X1.1.
DIFFx = absolute difference in cumulative mass recovery X1.6.1.2 D7169 Mass Percent by BP Data Array, N
between D7900 and D7169 at the merge boiling Elements—Create a two-dimensional value array from the
point, D7169 results (D7169VA) where:
M1 = cumulative mass percent recovered to the merge
D7169VA(i,1) = cumulative percent by mass from D7169 results in percent by
point temperature from D7900, and mass increments no greater than 0.1, and
point temperature from D7169. D7169VA(i,2) = boiling point, in °C, at this cumulative percent by mass.
X1.5.2 The absolute difference (DIFFx) in most cases will Begin the array at 0.50 % by mass (defined as initial boiling
not exceed 5.0 % by mass. Values above this may indicate point or IBP) and end the array at the final D7169 cumulative
possible errors in the D7900 or D7169 analyses, or both mass percent recovered. As an example, for a n-nonane merge
(weighing errors, response factor errors, etc.). Further review point using 0.01 % by mass increments, such an array would
of these analytical results and possible re-analysis of the appear as indicated in Table X1.2.
sample may be required.
NOTE X1.4—Anecdotal studies performed by various labs performing
NOTE X1.2—It is possible in very light condensates containing a this merge algorithm found that by using 0.01 % by mass increments for
significant amount of hexanes and lighter that the application of the D7169 the D7900 and D7169 results initially, the need for interpolation is
quench factor could cause marked differences in the two results. In this reduced and the accuracy of the merge point and final result comparability
case, or when the D7900 and D7169 results are determined to be accurate to physical distillation was improved.
within themselves, the D7900 result should be assumed to be the most
accurate, as it is not affected by solvent quenching. X1.7 Data Merging Procedure
X1.6 Elements Required to Perform Merge of D7900 and X1.7.1 The following procedure is used to prepare a result
D7169 at the Merge Point value array (RVA) containing the merged results.
X1.6.1 The following elements must be prepared from the X1.7.1.1 Create a two-dimensional result value array (RVA)
results of Test Methods D7900 and D7169 for the sample. The where:
selected merge point shall not exceed the boiling point of RVA(i,1) = cumulative mass percent in no greater than 0.1 % by mass
increments, and
n-nonane (the boiling point limit of Test Method D7900).
X1.6.1.1 D7900 Mass Percent by BP Value Array, N RVA(i,2) = boiling point, in °C, at that cumulative percent by mass.
Elements—Create a two-dimensional value array from the
D7900 results (D7900VA) where: Initially populate the array with all the elements of the
D7900VA(i,1) = cumulative mass percent from D7900 results in percent by D7900VA (see X1.6.1.1). Store the final row number after all
mass increments of at least 0.1, and D7900 data is added to the RVA, as this may be needed later if
D7900VA(i,2) = boiling point, in °C, at this cumulative percent by mass.
normalization is required (see X1.9).
X1.7.1.2 Search the D7169 cumulative percent by mass
Begin the array at 0.5 % by mass (defined as initial boiling versus BP value array until the row containing the cumulative
point or IBP) and end the array at the cumulative mass percent percent by mass at the merge point is found. Append percent by
recovered at the merge point’s boiling point. As an example, mass values from the D7169 value array to the result value
such an array would appear as indicated in Table X1.1 if array from the first row just after the merge point of the D7169
n-nonane’s boiling point was selected as the merge point and value array as follows:
0.01 % by mass increments are used. For i 5 x to N (X1.2)
NOTE X1.3—There may be elements of the array where multiple RVA~ i , 1 ! 5 RVA~ i 2 1 , 1 ! 1z
cumulative percentages occur at the exact same temperature. This is due RVA~ i , 2 ! 5 D7169VA~ m , 2 !
to the fact that Test Method D7900 is a component-based boiling point
distribution as opposed to the slice-based distribution used in Test Method m 5 m11
17
D7169 − 19
FIG. X1.1 Example of Light End Component Boiling Distribution Showing Multiple Cumulative Percentages at the Boiling Point of Iso-
pentane and Pentane
TABLE X1.2 Value Array D7169 Cumulative Mass Percent (CMP) m = initialized at the array element row num-
versus BP Degrees Celsius (BP, °C) In 0.01 % by Mass Intervals
ber of first D7169VA element just after the
Array Row CMP BP (°C)
1 0.50 % 36.06
merge point from search of array,
2 0.51 % 39.20 RVA(i,1) = result value array cumulative percent by
3 0.52 % 43.55 mass at row i,
... ... ... RVA(i,2) = result value array boiling point (in °C) at
... ... ...
999 23.00 % 150.76 (n-nonane BP) row i,
... ... ... D7169VA(m,1) = D7169 cumulative percent by mass at row
... ... ... m, and
N 94.30 % 712.00
D7169VA(m,2) = D7169 boiling point (in °C) at row m.
X1.8 Reporting Merged Results
Next i X1.8.1 Using the completed result value array (RVA, see
X1.7.1.2), extract the cumulative percent by mass by boiling
where:
point in the desired percent by mass intervals and report.
N = the total number of rows in the D7169VA, Report the initial boiling point (IBP) as the temperature at
x = array element row number for next value which 0.5 % by mass of the sample has eluted, and (if
pair from D7169VA that is just after the applicable) report the final boiling point (FBP) as the tempera-
row at the merge point, ture at which 99.5 % by mass of the sample has eluted. If the
z = increment of mass percentages (for
final RVA recovery is less than or equal to 100.0 % by mass,
example, 0.1, 0.01),
end the report at the last full cumulative percent by mass off.
18
D7169 − 19
The actual final percent by mass recovery and temperature may X1.9.2 Normalize the D7169 mass percentages using the
be reported also, if desired. If the final percent by mass following procedure:
recovery exceeds 100.0 % by mass, follow the procedure in For i 5 x to N (X1.4)
X1.9 to renormalize only the array elements taken from the
D7169 results to give exactly 100.0 % by mass recovery. The RVA~ i , 1 ! 5 RVA~ i 2 1 , 1 ! 1 ~ P 3 D 7169 NF!
D7900 result values should NOT be normalized as these are Next i
assumed to be accurate as reported. Fig. X1.2 demonstrates an
example report. where:
x = array element just after the last D7900 contrib-
NOTE X1.5—For clarity and comparison, it is also suggested to report uted mass percentage,
the original D7169 percent by mass recovery, and the final merged percent
by mass recovery. The difference here again should be less than 5 % by
N = last element of the RVA array,
mass absolute. If higher, see X1.5. P = increment of the cumulative mass percentages
(0.1, 0.01, etc.), and
X1.9 Normalizing Results for Recoveries in Excess of 100 D7169NF = normalization factor to be applied to all D7169
% by Mass After Merging cumulative percent by mass results in the RVA.
X1.9.1 If the chromatographic results for Test Methods X1.9.2.1 The final sum of all cumulative mass percentages
D7900 and D7169 have been verified, and the recovery is in in the RVA (D7900 and D7169 contributed) should now equal
excess of 100.0 % by mass or is greater than a predetermined exactly 100.0 % by mass. Use the normalized RVA to report the
recovery threshold, the following procedure should be used to results (as an example see Fig. X1.2).
normalize the D7169 data only:
~ 100 2 R D7900! NOTE X1.6—Un-normalized percent by mass recovery of the result
D7169NF 5 (X1.3) value array in excess of 105.0 % by mass should be considered suspect.
~ RVA ~ y , 1 ! 2 R D7900! An excess recovery of this magnitude may indicate inaccuracies in the
where: D7900 results, the D7169 results, or both. See X1.5.
D7169NF = normalization factor to be applied to all D7169
cumulative percent by mass results in the RVA,
RD7900 = cumulative percent by mass recovery at the
merge point from D7900, and
y = last row element of the D7169 portion of the
RVA (final percent by mass recovery).
19
D7169 − 19
FIG. X1.2 Example Final Merged Boiling Point Distribution Report
SUMMARY OF CHANGES
(1) Revised Table 2.
(1) Replaced former Appendix X1 with new Appendix X1

(Appendix X3 from Test Method D7900).
20

Boiling Point Distribution of Samples with Residues Such
as Crude Oils and Atmospheric and Vacuum Residues by
High Temperature Gas Chromatography1
1. Scope* 1.5 This test method is not applicable for the analysis of
1.1 This test method covers the determination of the boiling materials containing a heterogeneous component such as
point distribution and cut point intervals of crude oils and polyesters and polyolefins.
residues by using high temperature gas chromatography. The 1.6 The values stated in inch-pound units are to be regarded
amount of residue (or sample recovery) is determined using an as standard. The values given in parentheses are mathematical
external standard. conversions to SI units that are provided for information only
1.2 This test method extends the applicability of simulated and are not considered standard.
distillation to samples that do not elute completely from the 1.7 This standard does not purport to address all of the
chromatographic system. This test method is used to determine safety concerns, if any, associated with its use. It is the
the boiling point distribution through a temperature of 720 °C. responsibility of the user of this standard to establish appro-
This temperature corresponds to the elution of n-C100. priate safety, health, and environmental practices and deter-
1.3 This test method is used for the determination of boiling
Specific warning statements are given in Section 8.
point distribution of crude oils. This test method uses capillary
columns with thin films, which results in the incomplete
separation of C4-C8 in the presence of large amounts of carbon
disulfide, and thus yields an unreliable boiling point distribu- ization established in the Decision on Principles for the
tion corresponding to this elution interval. In addition, quench- Development of International Standards, Guides and Recom-
ing of the response of the detector employed to hydrocarbons mendations issued by the World Trade Organization Technical
eluting during carbon disulfide elution, results in unreliable Barriers to Trade (TBT) Committee.
quantitative analysis of the boiling distribution in the C4-C8
region. Since the detector does not quantitatively measure the
carbon disulfide, its subtraction from the sample using a 2.1 ASTM Standards:2
solvent-only injection and corrections to this region via D2887 Test Method for Boiling Range Distribution of Pe-
quenching factors, results in an approximate determination of troleum Fractions by Gas Chromatography
the net chromatographic area. A separate, higher resolution gas D2892 Test Method for Distillation of Crude Petroleum
chromatograph (GC) analysis of the light end portion of the (15-Theoretical Plate Column)
sample may be necessary in order to obtain a more accurate D4057 Practice for Manual Sampling of Petroleum and
description of the boiling point curve in the interval in question Petroleum Products
as described in Test Method D7900 (see Appendix X1). D6352 Test Method for Boiling Range Distribution of Pe-
troleum Distillates in Boiling Range from 174 °C to
1.4 This test method is also designed to obtain the boiling
point distribution of other incompletely eluting samples such as
D7500 Test Method for Determination of Boiling Range
atmospheric residues, vacuum residues, etc., that are charac-
Distribution of Distillates and Lubricating Base Oils—in
terized by the fact that the sample components are resolved
Boiling Range from 100 °C to 735 °C by Gas Chroma-
from the solvent.
tography
1
2

1
D7169 − 19
D7900 Test Method for Determination of Light Hydrocar- 3.1.12.1 Discussion—Normally 0.1 s is used. In cases where
bons in Stabilized Crude Oils by Gas Chromatography sample elutes immediately after injection, 0.05 s is used.
E594 Practice for Testing Flame Ionization Detectors Used 3.1.13 start elution temperature (SET), n—the temperature
in Gas or Supercritical Fluid Chromatography at which the first amount of hydrocarbon is detected by the
E1510 Practice for Installing Fused Silica Open Tubular flame ionization detector above a predetermined threshold.
3.1.14 %recovery (RC), n—percentage of the sample eluted.
3. Terminology 3.1.14.1 Discussion—%Recovery is calculated from the
sample area (ASMP), the response factor (RF), the sample mass,
3.1 Definitions of Terms Specific to This Standard:
(MSMP), and the solvent mass (MSLSMP) used in sample
3.1.1 cut point interval, n—the mass % obtained between
dissolution.
two selected temperatures of the interval.
3.1.15 %recovery threshold (Rt) , n—if the %recovery falls
3.1.2 data acquisition rate, n—the speed of conversion of
above a preset limit, the sample is considered fully eluted and
the analog signal to a digital signal, expressed in Hz (cycles/
its recovery is assumed to be 100 %.
second).
3.1.15.1 Discussion—If the %recovery values found for
3.1.3 final boiling point (FBP), n—the temperature, for fully duplicate analyses of a nearly completely eluting sample are
eluting samples (recovery = 100 %), at which 99.5 % of the 99.6 % and 101.2 %, the %recovery threshold (Rt) may be set
sample is eluted. to 99.6 % and thus either of these results may be considered as
3.1.4 final elution time (FEt), n—the retention time of the fully eluted and set to 100 %.
component of the reference time standard sample that elutes at 3.2 Symbols:
the end of the temperature ramp of the oven. 3.2.1 ASMP—net area of the sample
3.1.5 final elution temperature (FET), n—the boiling point 3.2.2 ASTD—net area of the response factor standard
of the normal paraffin that elutes at the time when the oven
reaches its final temperature. 3.2.3 MSL—mass of solvent used in preparing sample solu-
tion
3.1.6 initial boiling point (IBP), n—the temperature corre-
sponding to an accumulated 0.5 % of the total area of the eluted 3.2.4 MSLSTD—mass of solvent used in preparing the re-
sample after correcting for the percent of sample recovery. sponse factor standard solution
3.1.7 quenching factor (QF), n—a number that corrects for 3.2.5 MSMP—sample mass used in sample preparation
the diminished response due to the solvent profile co-eluting 3.2.6 MSTD—mass of the standard used in preparing the
with sample components. response factor solution
3.1.7.1 Discussion—Data acquired during the quenching
interval (QI) shall be corrected by applying the quenching 4. Summary of Test Method
factor. 4.1 This is a gas chromatographic method utilizing an inlet
3.1.8 quenching interval (QI), n—the time interval of the and a capillary column, both of which are subject to a
start and end of elution of the CS2 used as a solvent. temperature program. A flame ionization detector is used as a
3.1.8.1 Discussion—Sample components that elute during transducer that converts mass to an electrical signal A data
this time interval shall be corrected by a factor due to their acquisition system operating in the slice mode and chromatog-
diminished response resulting from the co-elution of the raphy software is used to accumulate the electronic signal. A
relatively large amount of solvent present in the sample with retention time calibration mixture is used to develop a retention
the light sample components. time versus boiling point curve. A solution of the Reference Oil
5010 or a gravimetric blend, which fully elutes from the
3.1.9 residue (R), n—the mass % of the sample that has not
column under the conditions of the test method and whose
eluted at the temperature of calculation.
boiling point distribution have been characterized in Test
3.1.9.1 Discussion—Residue is calculated from the %recov-
Method D6352 or D7500, is used to determine the detector
ery.
response factor. Solvent injections are made, and the resulting
3.1.10 response factor (RF), n—the factor used in order to signal is subtracted from both the response factor standard and
calculate the %recovery of the sample. the sample chromatogram. Finally, the sample solution is
3.1.10.1 Discussion—The response factor is determined injected and with the use of the response factor, the amount of
from the net area of the standard (ASTD), mass of standard sample recovered is calculated. After converting the retention
(MSTD), and mass of solvent (MSLSTD) used in the solution of times of the sample slices to temperature, the boiling point
the standard. A fully eluting sample, such as Reference Oil distribution can be calculated up to the recovered amount.
5010, is used in obtaining the response factor.
3.1.11 sample area obtained (ASMP) , n—the net chromato- 5. Significance and Use
graphic area (after baseline subtraction) obtained for the 5.1 The determination of the boiling point distribution of
sample at the final elution time or temperature. crude oils and vacuum residues, as well as other petroleum
3.1.12 slice, n—the reciprocal of the data acquisition rate; fractions, yields important information for refinery operation.
the time interval used to accumulate data, expressed in sec- These boiling point distributions provide information as to the
onds. potential mass percent yield of products. This test method may
2
D7169 − 19
provide useful information that can aid in establishing opera- 6.2 Carrier Gas Purification System—Gas purifiers are used
tional conditions in the refinery. Knowledge of the amount of in order to remove traces of oxygen as well as moisture and
residue produced is important in determining the economics of other impurities present in the carrier gas. The purification
the refining process. system should contain a hydrocarbon trap and an oxygen trap.
The latter should preferably have a visible indicator in order to
6. Apparatus assess the remaining capacity of the oxygen trap.
6.1 Gas Chromatograph—A gas chromatograph provided 6.3 Data System—A data system composed of a computer
with a cryogenic valve for cooling the oven to sub ambient and software for data acquisition, which digitizes the detector
temperatures is required. Typical conditions of operating the signal, is recommended. Some instrumentation digitizes the
Gas Chromatograph are given in Table 1. It shall also have the signal at the electrometer board in order to reduce noise. The
following components: data system is used at acquisition rates of about 10 Hz, which
6.1.1 Flame Ionization Detector (FID)—A flame ionization correspond to slices of 0.1 s. This rate of data acquisition is
detector capable of maintaining a temperature 5 °C to 10 °C necessary to obtain a minimum number of slices void of
higher than the highest column temperature. The flame ioniza- sample or solvent elution immediately after injection. Data
tion detector should possess a jet orifice of about 0.018 in. acquisition systems facilitate the inspection of the baseline
(0.45 mm) in order to delay the plugging of the orifice due to under high magnification and allow the inspection of the
column bleed. The FID should possess a sensitivity of retention time calibration mixture chromatogram. Retention
0.005 coulombs ⁄g (see Practice E594) and should have a linear time shifts can be measured. Overlaying chromatograms is also
range of 106. possible to ascertain similar signal amplitude.
6.1.2 Inlet—Either a temperature programmable inlet with a
6.4 Automatic Sample Injector—It is mandatory to use an
glass liner or a cool-on-column inlet can be used. The inlet
auto sampler since the external standard technique used in this
shall be capable of operating in a temperature-programmed
analysis requires identical volumes for all injections.
mode from 50 °C to the final temperature of the oven. It is
Additionally, small volumes (0.1 µL to 0.2 µL) shall be injected
important that the temperature of the inlet, at any time during
in a reproducible manner. Syringes of 5 µL to 10 µL having
the analysis, be either equal to or greater than the oven
needle gauges of size 23 to 26 are to be used.
temperature. With the use of either inlet, frequent replacement
of the liner or removal of a section of the column may be 6.5 Carrier Gas Control—The gas chromatograph shall be
required due to accumulation of non-volatile sample compo- operated under constant flow conditions. The flow rate at the
nents. It is important that a leak free seal be reestablished after beginning of the oven temperature program shall not differ by
replacement of the liner or the removal of a small section of the more than 1 % from the flow measured at the final oven
column. temperature. Electronic pneumatic control is highly recom-
mended.
7. Column and Column Performance Criteria
TABLE 1 Typical Gas Chromatographic ConditionsA
Initial Oven Temperature −20 °C
7.1 A 100 % bonded polydimethylsiloxane column having a
Initial Oven Time 0 min nominal inside diameter of 0.5 mm and a film thickness of
Oven Temperature Program 15 °C ⁄ min 0.09 µm to 0.17 µm is used.
Final Oven Temperature 425 °C to 435 °CB
Final Hold Time 10 min 7.2 The column used should be capable of sustaining
temperatures of 435 °C under temperature programming. Alu-
Inlet Initial TemperatureC 50 °C
Inlet Temperature Program 15 °C ⁄ min minum covered fused silica and metal columns have been
Inlet Final Temperature 425 °C successfully used.
Column 5 m × 0.53 mm × 0.09B 7.3 The column should be capable of eluting carbon number
-0.15 µm PDMS 100 at its highest temperature. It is important that C100 be
Column Flow 20 mL/min
Carrier Control Constant Flow eluted during the temperature program cycle of the oven.
7.4 Column resolution is determined from the separation of
DetectorD FID
Detector Temperature 435 °C carbons 50 and 52 in the retention time calibration mixture
Detector Gases: chromatogram. The resolution should be between 1.8 to 4.0.
Hydrogen 40 mL/min
Air 450 mL/min
See Eq 1 in 13.1.
Make-Up (N2, He) 15 mL/min 7.5 The column shall be capable of allowing the start of the
Volume Injected 0.2 µL-0.5 µL-1.0 µLB
elution of n-C5 prior to the solvent elution, which is CS2, at
Sample Concentration 2.0 % (m/m) −20 °C. The descending edge of the n-C5 peak co-elutes with
Data Acquisition Rate 10 Hz the solvent. It is to be noted that at these low temperatures
Total Acquisition Time 40 min to 50 min
A
liquid phases may turn solid, and retention shifts may be
Conditions used for the interlaboratory study.
B
Several participants used these conditions. Higher temperatures yield higher
observed during the elution of compounds at these low oven
recoveries. temperatures.
C
Use lowest temperature recommended by manufacturer.
D
Use GC manufacturer’s recommendations. 7.6 Column Overloading—The prevention of column over-
loading is carried out by determining the skewness of a
3
D7169 − 19
selected peak among the components of the retention time under a fume hood and heat with an infrared lamp (about
calibration mixture chromatogram. Any paraffin with a carbon 200 W) placed at a safe distance (about 15 cm to 20 cm) from
number between C12 and C24 may be chosen. The skewness the mixture for a period of 20 min or until the solution is clear.
should be between 0.8 and 2.0. See Eq 2 in 13.2. Other precautionary methods of dissolution are acceptable.
7.7 Column Flow—Helium is used as carrier. Column flow Careful attention should be given to avoid the ignition of the
rate is set to 20 mL ⁄min. CS2 (see 8.1).
8.4.4 Transfer a 2 mL aliquot of the final mixture obtained
8. Reagents and Materials in 8.4.3 into a 2 mL auto sampler vial and seal it firmly. This
8.1 Carbon Disulfide (CS2), 99+ % pure. (Warning— solution can be used for about one week if stored at 4 °C. The
Extremely flammable and toxic liquid.) Used as a solvent to contents of this vial are injected in order to obtain the retention
dilute the sample and standards as well. Use gloves and safety time–boiling point curve.
glasses when handling the CS2 in a well-ventilated area or NOTE 1—Polywax is a trademark of the Baker Petrolite Corporation
fume hood. It is recommended to use adjustable-volume bottle (Barnsdall, OK). This retention time calibration mixture is commercially
dispensers and/or pipettors to minimize direct handling and available from chromatographic supply houses as well as from companies
avoid cross-contamination of CS2. Wash vials containing CS2 that build simulated distillation analyzers. The retention time calibration
should be capped with a solvent resistant septa. mixture may differ among supply houses in that docosane, tetracosane and
hexacosane are also added to the Polywax 655 or Polywax 1000 in order
8.2 Polywax 655 or Polywax 1000—Used as a component to enhance the concentration of these hydrocarbons in the polywaxes.
of the retention time calibration mixture. Since these Poly-
waxes have carbon 22 as the first component, it shall be 8.5 Detector Relative Response Test Mixture—It is neces-
complemented with the mixture of paraffins described in 8.4.1 sary to initially validate the response of the entire gas chro-
and 8.4.3 so that the entire range of carbon numbers (C5-C100) matographic system. Since this test method assumes that all
is present in the sample. hydrocarbons have the same relative response regardless of
their retention time, a solution shall be prepared in order to
8.3 Paraffıns—The following normal paraffins are used in determine the relative response factors. An alternative proce-
the preparation of the retention time calibration mixture: dure is to use a gravimetric blend as specified in Test Method
pentane undecane heptadecane D7500.
hexane dodecane octadecane
heptane tridecane nonadecane 8.5.1 Prepare a solution containing the following normal
octane tetradecane eicosane paraffins:
nonane pentadecane tetracontane
decane hexadecane decane octacosane
tetradecane dotriacontane
8.3.1 The purities of these compounds should be 99 % or octadecane tetracontane
greater. eicosane pentacontane
8.4 Retention Time Calibration Standard—This standard 8.5.2 Weigh about 100 mg of each paraffin to the nearest
can be obtained from chromatography supply companies. This 0.1 mg into a 50 mL volumetric flask. Mix well and add CS2 to
standard is composed of a mixture of Polywax (either P655 or the mark. Ensure that the paraffins are completely dissolved.
P1000) as well as a mixture of paraffins. The addition of the Record the masses of the paraffins, which will be used in Eq 3
paraffin mixture is necessary to cover the range of C5-C20 since in order to calculate the relative response factor of each of the
these paraffins are absent in the Polywax. Furthermore the paraffins.
amounts of the paraffins are chosen so as to facilitate identi- 8.5.3 Record the assayed purity of each paraffin for use in
fying the carbons in the retention time calibration mixture Eq 3.
chromatogram. Alternatively, a successful mixture that has
8.5.4 Transfer an aliquot of the mixture prepared in 8.5.2 to
been used may be prepared by the procedure described in 8.4.1
a 2 mL injection vial. Ensure that the components are in
– 8.4.3 which requires the preparation first of the n -paraffin
solution prior to the transfer. Warm the vial if necessary. Inject
mixture (see 8.3) and then spiking an aliquot of this mix to a
weighed amount of Polywax 655 or 1000. 0.1 µL to 0.2 µL.
8.4.1 Place approximately 20 mL of CS2 into a round 8.6 Reference Oil 5010—In order to determine the sample
bottom 50 mL flask. Transfer with care. recovery, the detector response factor has to be determined. For
8.4.2 Prepare a mixture of the paraffins listed in 8.3 as this purpose, utilize Reference Oil 5010 as an external stan-
follows. Weigh 500 mg of each component into a 20 mL vial. dard. This material is obtainable from various chromatography
Add an additional 500 mg for dodecane and about 20 mg of suppliers. A gravimetric blend, as described in Test Method
tetracontane. Store this mixture at 4 °C and use it as a spiking D7500, can also be used
mixture in the preparation of the Polywax 655 retention time
calibration mixture. These additional quantities are spiked to 8.7 Gases—The following compressed gases are utilized for
ease the identification of the n-paraffins; other n-paraffins may the operation of the gas chromatograph:
be chosen as peak markers. 8.7.1 Nitrogen, 99.999 %. (Warning—Compressed gas un-
8.4.3 Weigh about 25 mg of the Polywax 655 and add it to der high pressure.) Total impurities should not exceed
the vessel prepared in 8.4.1. Add approximately 10 mg of the 10 mL ⁄m3. This gas is used as detector makeup. Helium has
paraffin spiking mixture prepared in 8.4.2. Stir the solution also been used as makeup gas.
4
D7169 − 19
8.7.2 Hydrogen, 99.999 %. (Warning—Extremely flam- them into a weighed container. Only samples that are soluble in
mable gas under high pressure.) Total impurities should not carbon disulfide (CS2) can be analyzed by this test method.
exceed 10 mL ⁄m3. This gas is used as fuel for the operation of 10.3 Weigh 0.2 g to 0.25 g of the sample to the nearest
the detector. 0.1 mg. Add 10 mL of CS2. Record this weight also to the
8.7.3 Air, 99.999 %. (Warning—Compressed gas under nearest 0.1 mg. Enter these values in the data acquisition
high pressure and supports combustion.) Total impurities system if appropriate.
should not exceed 10 mL ⁄m3. This gas is used to sustain
combustion in the FID detector. 10.4 Store all prepared solutions at a temperature of 4 °C.
8.7.4 Helium, 99.999 %. (Warning—Compressed gas un- Care should be taken that the solution is prepared a short time
der high pressure.) This gas is used as carrier gas and should prior to running the analysis. Samples can be stored in the auto
not contain more than 5 mL ⁄m3 of O2. The total amount of sampler vials.
impurities should not exceed 10 mL ⁄m3. 10.5 Prepare as many vials of a sample as are necessary to
carry out multiple analyses of that sample. Do not use the same
9. Preparation of the Gas Chromatograph vial to run duplicates; use separate vials containing the same
9.1 A summary of the conditions used for developing the solution.
precision statement is given in Table 1.
11. Preparation of the Response Factor Standard
9.2 Column Installation—The column is installed using
graphite ferrules and an electronic leak detector is used to 11.1 Weigh 0.2 g to 0.25 g of Reference Oil 5010 to the
ascertain the absence of leaks. Follow the instructions given in nearest 0.1 mg. Add 10 mL of CS2 and record the weight of the
Test Method D2887 and Practice E1510 for the installation of solvent to the nearest 0.1 mg. Store this solution at 4 °C, if not
silica or aluminum clad silica columns. Metal columns require used immediately.
slightly different techniques in cutting and installation. Follow
the recommendations of the column supplier. 12. Preparation of the Apparatus and Data System
9.3 Detector Temperature—Select a detector temperature 12.1 After the column is installed and checked for leaks,
that is at least 5 °C to 10 °C higher than the highest oven prepare the gas chromatograph to analyze the sample according
temperature. to the typical conditions given in Table 1.
9.4 Initial Oven Temperature—The initial temperature of 12.2 Set the acquisition system to digitize the data at 10 Hz.
the oven is chosen according to the sample type to be analyzed This will result in a slice width of 0.1 s. This data acquisition
as follows: rate is kept constant for all samples, standards, and the solvent
blank in order to acquire the same number of slices. The
9.4.1 Crude Oil Samples—Crude oil samples may contain
baseline chromatogram may contain the same or larger number
hydrocarbons starting from methane, C2, C3, and C4 which
of slices than the sample chromatograms, depending on when
probably co-eleute with C5. Therefore, even at an initial
the data acquisition stops. Thus, various chromatograms taken
temperature of −20 °C, C5 and C6 are partially resolved from
in a sequence may differ by 5 to 10 slices. This fact is of no
the CS2. Further decreases in oven temperature do not increase
consequence with regard to the calculations.
the separation of C5 from C1-C4 hydrocarbons which co-elute
with n-C5. 12.3 Arrange to save the acquired data files. Build the
9.4.2 Residues and Samples Having Higher IBP—For sequence of samples to be injected by the gas chromatograph.
samples that have an initial boiling point of 100°C or greater,
such as vacuum residues or atmospheric residues, the initial 13. Verification of System Performance
oven temperature can be set to between 35 °C and 40 °C. 13.1 Column Resolution—Prepare the gas chromatograph
Ensure that the sample is resolved from the solvent peak at the for injection of the retention time calibration mixture prepared
initial oven temperature selected. If the light ends cannot be in 8.4. Inject 0.1 µL to 0.2 µL of this sample. Determine the
separated from the solvent, then proceed as in 9.4.1. If the user column resolution as follows:
does not know the type of sample to be analyzed, all samples
can be analyzed with an initial temperature of −20 °C. R 5 2 ~ t 2 2 t 1 ! / ~ 1.699! ~ W 2 1W 1 ! (1)
where:
10. Sample Preparation R = resolution,
10.1 Ensure that the sample is a representative sample. t2 = retention time (s) for the n-C50 paraffin,
Follow the guidelines established in Practice D4057. Samples t1 = retention time (s) for the n-C52 paraffin,
should be handled according to their content of volatile W1 = peak width (s) at half height of the n-C50 peak, and
components. If the sample is submitted for other analyses, W2 = peak width (s) at half height for the n-C52.
remove a small aliquot (~10 mL) early in the testing sequence 13.1.1 Ensure that the resolution, R, is between 1.8 to 4.0.
in order to avoid loss of volatile components. Allow sample to 13.2 Skewness Test for Column Overloading—Select a com-
warm to room temperature prior to weighing. ponent between C12-C24 of the previous chromatogram or of
10.2 Samples that are solid or semi-solid at room tempera- the chromatogram of the retention time calibration mixture
ture may require heating up to as high as 60 °C in order to pour prepared in 8.4. For the component selected, determine the
5
D7169 − 19
skewness as follows. The skewness, s, is calculated by Eq 2: 14.3 Retention Time Calibration Mixture—Insert the reten-
ILS participants reported skewness of 0.8 to 2.0 for peaks C7 to tion time calibration mixture vial prepared in 8.4 into the auto
C100. sampler for injection. A typical chromatogram of the retention
s 5 ~ a1b ! /2a (2) time calibration mixture is shown in Fig. A1.2. The insert in the
Fig. A1.2 shows the best separation possible for the C5, CS2,
where: C6, and C7 and shows good peak shape for the C6 and C7
s = skewness of the peak, hydrocarbons. Identify all carbons up to C100.
a = left time segment measured at 10 % of the peak height
14.4 Response Factor Standard—Insert the vial containing
and that intersects the perpendicular from the apex of the
Reference Oil 5010 prepared in 8.5, which is used as a
peak to the retention time axis, and
response factor standard. Inject this standard in duplicate. A
b = right time segment measured at 10 % of the peak height
typical chromatogram of the reference oil analyzed at an initial
and that intersects the perpendicular from the peak apex
oven temperature of −20 °C is shown in Fig. A1.3. Verify that
to the retention time axis. Ensure that the skewness is
the response factor calculated by Eq 4 does not vary by more
between 0.8 and 2.0. Data acquisition systems can
than 2 %.
calculate this parameter.
14.5 Sample Analysis—Insert the sample vials prepared in
13.3 Determination of Detector Relative Response 10.3. Inject samples. Analyzing a QC material with acceptable
Factors—Prepare the gas chromatograph for the injection of results before the analysis of unknown samples is strongly
the detector test mixture prepared in 8.5. Inject 0.1 µL to 0.2 µL recommended.
of this sample. Calculate the relative response factor, Fi, of
each paraffin relative to eicosane as follows: 14.6 Additional Blank Runs—Insert a vial containing CS2 in
order to obtain a second blank run. Carry out a blank run after
M i 3 P i 3 Ac20
Fi 5 (3) each sample injection, and verify the absence of carryover
A i 3 Mc20 3 Pc20 from the previous samples. An ambient temperature version of
where: the method with faster oven ramping can be employed for these
Mi = mass of the paraffin in mg, clean-out runs in between samples to reduce run time and use
Mc20 = mass of the eicosane in mg, of cryogenic fluids.
Ai = peak area of the paraffin,
Ac20 = peak area of the eicosane, 15. Verification of Acquired Data
Pi = % purity of the paraffin as recorded in 8.5.3, and 15.1 Inspect all chromatograms by loading the data files in
Pc20 = % purity of eicosane.
the data acquisition system. Observe that the signal magnitude
13.3.1 The relative response factor, Fi, should have a value for each sample injected is approximately the same as that for
of between 0.9 and 1.10. Failure to achieve this range may be the retention time calibration mixture and the Reference Oil
due to inlet problems, lack of constant flow, or partial blockage 5010 chromatograms.
of the flame tip orifice, or a combination thereof. 15.2 Verification of the Retention Time Calibration Mixture
Chromatogram—Inspect the chromatograms acquired during a
14. Analytical Sequence sequence run. Do not use a chromatogram where the peaks do
14.1 Set up a sequence of the samples to be analyzed. The not meet the criteria of skewness as defined in 13.2. Inspect the
sequence will contain the order of the samples to be injected chromatogram for the components C5-C7 and the solvent peak
into the column. This schedule should be designed to achieve as shown in the insert of Fig. A1.2. The peaks should not
maximum reproducibility. A suggested order of the samples to present peak splitting nor peak tailing.
be analyzed is described in 14.2 – 14.6. If time constraints 15.3 Sample Chromatograms—Inspect the sample chro-
require a shorter sequence, the user shall ensure that there is no matograms and verify that the chromatograms can be overlaid
carryover between samples and sample types. to a duplicate chromatogram and show that the profile is
reproducible. Fig. A1.4 shows a chromatogram of a 30°API
14.2 Blank Run—At the beginning of each sequence, after
crude oil where the solvent peak is not resolved from the
any column maintenance is performed, make a blank run. It
sample components. Fig. A1.5 shows a typical chromatogram
may take more than 2 blanks to show a stable plateau with no
of an atmospheric residue where the solvent peak is resolved
indication of residual elution. A blank run constitutes an
from the sample components.
identical solvent injection having the same volume as the
sample injection. An acceptable blank run should show a stable 15.3.1 It is recommended that a QC material be analyzed at
plateau at the highest temperature of the oven (see 15.3). the beginning and end of every sequence. The QC sample
Furthermore, it should not show any indication of carryover or should have the same matrix as the samples analyzed.
residual sample elution. It should also not contain any ghost 15.4 Baseline or Blank Runs—Inspect, in the data system,
peaks. A typical blank sample run is shown in Fig. A1.1. the chromatograms of the blank solvent injections to verify that
Several blanks may be necessary after column installation or the blank signal obtained does not differ substantially from that
after an idle period of the gas chromatograph. Verification of obtained during the sample analysis. Check that the baseline
acceptable blanks is obtained by analyzing the Reference Oil exhibits a gradual rise up to the isothermal section of the
5010 or a gravimetric blend and a QC material. chromatogram and ensure that there is a gradual transition back
6
D7169 − 19
to the plateau of the baseline. Disregard any baseline that Oil 5010 and from the sample chromatogram in order to obtain the net
shows material eluting near the highest temperature of the area as shown in 16.1.4.
column. Also disregard any baseline that shows ghost peaks. 16.1 Zeroing of the Reference Oil Chromatogram:
Overlay the baseline signal with the sample signal as shown in 16.1.1 Examine the chromatogram obtained for Reference
Fig. A1.6. Use only those sample signals that asymptotically Oil 5010 (external standard), and ensure, by visual inspection
approach the baseline signals. Reject any sample run where the of the chromatogram in the data system, that the first 5 slices
baseline signal at the end of the run exceeds in value the contain neither sample nor solvent elution.
sample run. Reject any sample run at which at the end of the
16.1.2 Set up an array that contains slices obtained from the
run the signal exceeds the baseline signal by 10 %. It is
Reference Oil 5010 chromatogram. Calculate the average of
recommended that a new full blank analysis be performed at
the first five area slices. Subtract the average slice area from
regular intervals (for example, after every 4 to 5 samples) in a
each slice in the Reference Oil 5010 chromatogram. Set
sequence of samples to ensure good baseline data for subse-
negative numbers to zero.
quent samples.
15.4.1 Determine the Quenching Interval—Select the time 16.1.3 Zero the blank baseline chromatogram by carrying
that the solvent peak starts to elute. Determine when the out an analogous calculation as in 16.1.2.
solvent peak has eluted. Note the times of this interval in 16.1.4 Blank Baseline Subtraction from the Reference Oil
minutes. An expanded time scale chromatogram of the solvent 5010 Chromatogram—Subtract each zeroed blank baseline
peak is shown in Fig. A1.7. slice from the corresponding zeroed Reference Oil 5010 slice.
15.4.2 Determine the Magnitude of Solvent Response— If there are negative slices, set the slice values to zero.
Using the data system, overlay the solvent chromatograms and 16.1.5 Determination of the End of Elution Time of Refer-
verify that the profiles are similar. Verify that the total areas do ence Oil 5010—Since it is a requirement that the sample
not differ by more than 3 % from each other. chosen to obtain a response factor shall fully elute prior to the
15.5 External Standard Response Factor Chromatogram— FEt time, the end of sample elution for this chromatogram is to
Inspect the external standard chromatogram obtained from the be determined as described in Test Method D6352, using the
injection of Reference Oil 5010. Verify that the boiling point algorithm to determine the time the signal of the completely
distribution is within the consensus values as indicated in Test eluted sample returns to baseline.
Method D6352. Typical boiling point distribution values for 16.1.6 Determination of the Area of the Chromatogram for
Reference Oil 5010, obtained with this test method, are shown Reference Oil 5010—Determine the end time of solvent elu-
in Table 2. Correct any chromatography errors if the consensus tion. Sum all of the slices from the end of solvent elution to the
values are not obtained (see 16.1.7). end of sample elution. This is the area of the standard, ASTD.
16.1.7 Calculation of the Boiling Point Distribution of
16. Calculations Reference Oil 5010—The resulting corrected slices obtained
NOTE 2—The calculations are listed in this section. The chromatogram for Reference Oil 5010 are submitted to a Test Method D6352
for the reference oil, the sample, and the baseline shall be zeroed as given
calculation for boiling point distribution. A comparison of the
in 16.1.2.
NOTE 3—The baseline chromatogram is subtracted from the Reference values obtained with the consensus values listed in Table 2
shall be made and all the boiling point values shall fall within
the specified windows. If this requirement is not met, correct
TABLE 2 Consensus Values Obtained for the Boiling Point any chromatographic problems prior to proceeding with
Distribution of Reference Oil 5010 Used as External StandardA sample analysis. Typical problems found in this step are:
%BP avg °C
Allowable
avg °F
Allowable contaminated solvent; problems in sample preparation; sample
Differences, °C Differences, °F residue in the inlet or column, or both; quality of the baseline
IBP 428 9 801 16 used, a partially blocked detector jet, or a combination thereof.
5 477 3 891 5
10 493 3 918 5 16.2 Zeroing of Sample Chromatograms:
15 502 3 936 5
20 510 3 950 6 16.2.1 In the case of crude oil analysis or samples in which
25 518 4 963 6 the solvent peak is not resolved from the sample components,
30 524 4 975 7
35 531 4 987 7
ensure, by visual inspection of the chromatogram in the data
40 537 4 998 8 system, that the first 5 slices contain neither sample nor solvent
45 543 4 1008 8 elution. If there is sample elution, decrease the number of slices
50 548 4 1019 8
55 554 4 1030 8 for the averaging to 3 or increase the digitization rate given in
60 560 4 1040 8 12.2.
65 566 4 1051 8
70 572 4 1062 8
16.2.2 Zeroing the Sample Chromatogram—Proceed in a
75 578 5 1073 9 manner analogous to that described in 16.1.2.
80 585 4 1086 8 16.2.3 Zeroing the Blank Baseline Chromatogram—Carry
85 593 4 1099 7
90 602 4 1116 8 out an analogous calculation as in 16.1.3.
95 616 4 1140 7
FBP 655 18 1213 32 16.3 Blank Baseline Subtraction from the Sample
A
As reported in Test Method D6352. Chromatogram—Carry out an analogous calculation as in
16.1.4.
7
D7169 − 19
16.4 Quenching Correction—For crude oil samples, a 16.8 Calculation of the %Recovery—The %recovery is
quenching factor is used to correct for the diminished FID defined as:
response when the CS2 co-elutes with sample components. ~ ME! ME 3 ~ M SMP1M SLSMP!
This factor is applied to the time segment corresponding to the %RC 5 3 100 5 3 100
elution of CS2. In the interlaboratory study, the factor of 1.930 S M SMP
~ M SMP1M SLSMP! D M SMP
was applied. This value is determined from experiments made (5)

by dissolving butane, pentane, and hexane in toluene. The
solution is analyzed by injecting it under conditions identical to where:
sample analysis. The areas for the components are compared to ME = mass, in grams, of the sample eluted,
the areas obtained by gradually adding weighed aliquots of CS2 MSMP = sample mass, in grams, and
to the original solution. Alternatively the quenching value can MSLSMP = mass of solvent, in grams, used in the sample
be checked by performing a glass distillation by Test Method solution.
D2892. Samples that do not have components that co-elute Since:
with solvent, for example, residues or the Reference Oil 5010,
ME 5 ~ A SMP! 3 ~ RF! (6)
do not require the quenching correction.
16.4.1 Determine the Quenching Interval—Select the time where:
that the solvent peak starts to elute. Determine when the ASMP = net sample area, and
solvent peak has eluted. Note the times of this interval in RF = response factor of the Reference Oil 5010.
minutes. An expanded time scale chromatogram of the solvent Substituting Eq 6 for the value of ME in Eq 5 yields:
peak is shown in Fig. A1.7.
A SMP 3 RF 3 ~ M SMP1M SLSMP!
16.4.2 Locate the slices of the quenching interval. For %RC 5 3 100 (7)
~ M SMP!
samples in which the solvent component co-elutes with the
sample chromatogram (that is, crude oils), determine the Substituting Eq 4 in Eq 7 for the value of RF yields:
quenching interval, Q.I., as described in 16.4.1. Find the ~ M STD! ~ M SMP1M SLSMP! A SMP
closest slice corresponding to the beginning of elution of the %RC 5 3 3 3 100 (8)
~ M STD1M SLSTD! M SMP A STD
solvent peak as well as the final slice corresponding to the end
of elution of the solvent peak. 16.8.1 Determine whether the %recovery, (%RC) falls be-
16.4.3 Correct the diminished response of the interval by low the recovery threshold (Rt) limits set. If it is less than or
multiplying each slice of this interval by the quenching factor, equal to the recovery threshold (Rt), use the %recovery (%RC)
Q.F. Use the value as discussed in 16.4. determined in 16.8. If the %recovery is greater than the
recovery threshold (Rt), then the recovery is set to 100 %. If the
16.5 Determination of the Sample Final Elution Time— %recovery is larger than 102 % (1 standard deviation of the
Determine the time at which the oven reaches the isothermal residue), repeat the analysis or determine the chromatographic
portion of the temperature program. This is usually recognized problem.
as an inflection point in the baseline. This point is called the
16.9 Determination of the Boiling Point Distribution:
final elution time (FEt). The conversion of this slice to
temperature will yield the final elution temperature, FET. This 16.9.1 Multiply each slice of the sample chromatogram by
conversion is carried out in 16.9.4. the %recovery as established in 16.8.1. Divide each slice by the
total area of the sample obtained in 16.6. This will express the
16.6 Determination of the Sample Area—The net sample slices in a percent scale.
area is obtained by adding all slices from time t = 0 to the final 16.9.2 Add the slices that will yield 0.5 %, 1 %, 2 %, . . .
elution time, FEt. This net area is the ASMP. %recovery. Determine, at 1 % intervals, the time of the slice
16.7 Calculate the Response Factor, RF, as follows: yielding exactly 0.5, 1 %, 2 %, ...%recovery. Use an interpo-
lation procedure to find the fractional slices required to yield
~ M STD! 1 exactly 0.5, 1 %, ...2 %, ...%recovery.
RF 5 3 (4)
~ M STD1M SLSTD! A STD 16.9.3 Stop the calculation carried out in 16.9.2 when
where: obtaining a slice summation equal to the nearest whole integer
RF = response factor, of the %recovery.
ASTD = net area obtained for the Reference Oil 5010 16.9.4 Convert the retention times to boiling points as
chromatogram after baseline subtraction and after outlined in the Test Method D6352 algorithm. Use the boiling
excluding the solvent peak (this area was deter- point temperatures listed in Table 3. For each retention time
mined in 16.1.6), obtained in 16.9.2, find the corresponding temperature from the
MSLSTD = solvent mass, in grams, used for Reference Oil Boiling Point vs. Retention Time function as shown in Fig.
dissolution, and A1.8. Calculate the corresponding boiling points as determined
MSTD = mass, in grams, of Reference Oil 5010 used in in the Test Method D2887 algorithm.
preparing the response factor solution.
16.10 Calculation of Cut Point Intervals:
16.7.1 The mass term in Eq 4 has been expressed as a 16.10.1 For the two temperatures that define the cut point
fraction of the mass of solute and solvent. interval, find the two corresponding slices.
8
D7169 − 19
TABLE 3 Boiling Points Of ParaffinsA
Carbon Boiling Boiling Carbon Boiling Boiling
Number Point °C Point °F Number Point °C Point °F
1 –162 –259 51 579 1074
2 –89 –129 52 584 1083
3 –42 –44 53 588 1090
4 0 31 54 592 1098
5 36 97 55 596 1105
6 69 156 56 600 1112
7 98 209 57 604 1119
8 126 258 58 608 1126
9 151 303 59 612 1134
10 174 345 60 615 1139
11 196 385 61 619 1146
12 216 421 62 622 1152
13 235 456 63 625 1157
14 254 488 64 629 1164
15 271 519 65 632 1170
16 287 548 66 635 1175
17 302 576 67 638 1180
18 316 601 68 641 1186
19 330 626 69 644 1191
20 344 651 70 647 1197
21 356 674 71 650 1202
22 369 695 72 653 1207
23 380 716 73 655 1211
24 391 736 74 658 1216
25 402 755 75 661 1222
26 412 774 76 664 1227
27 422 791 77 667 1233
28 431 808 78 670 1238
29 440 825 79 673 1243
30 449 840 80 675 1247
31 458 856 81 678 1252
32 466 870 82 681 1258
33 474 885 83 683 1261
34 481 898 84 686 1267
35 489 912 85 688 1270
36 496 925 86 691 1276
37 503 937 87 693 1279
38 509 948 88 695 1283
39 516 961 89 697 1287
40 522 972 90 700 1292
41 528 982 91 702 1296
42 534 993 92 704 1299
43 540 1004 93 706 1303
44 545 1013 94 708 1306
45 550 1022 95 710 1310
46 556 1033 96 712 1314
47 561 1042 97 714 1317
48 566 1051 98 716 1321
49 570 1058 99 718 1324
50 575 1067 100 720 1328
A
Boiling Points from C1-C92 are taken from Test Method D6352.For carbons C92-C100 taken from reference in Annex 1 of Test Method D6352.
NOTE 1—API Project 44, October 31, 1972 is believed to have provided the original normal paraffin boiling point data that are listed in Table 3.
However, over the years some of the data contained in both API Project 44 (Thermodynamics Research Center Hydrocarbon Project) and Test Method
D6352 have changed and they are no longer equivalent. Table 3 represents the current normal paraffin boiling point values accepted by Subcommittee
D02.04 and found in all test methods under the jurisdiction of Section D02.04.0H.
NOTE 2—Test Method D6352 has traditionally used n-paraffin boiling points rounded to the nearest whole degree for calibration. The boiling points
listed in Table 3 are correct to the nearest whole number in both degrees Celsius and degrees Fahrenheit. However, if a conversion is made from one
unit to the other and then rounded to a whole number, the results will not agree with the table values for a few carbon numbers. For example, the boiling
point of n-heptane is 98.425 °C, which is correctly rounded to 98 °C in the table. However, converting 98.425 °C gives 209.165 °F, which rounds to
209 °F, while converting 98 °C gives 208.4 °F, which rounds to 208 °F. Carbon numbers 2, 4, 7, 8, 9, 13, 14, 15, 16, 25, 27, and 32 are affected by
rounding.
16.10.2 Using the calibration curve, convert this tempera- 16.10.4 Sum the normalized slices, starting with the initial
ture range to a time range. slice of the cut and terminating with the last slice after the cut.
16.10.3 Convert the time range to a slice number range by This sum will be equal to the %mass of the cut.
multiplying by 60 and dividing by the slice width in seconds.
9
D7169 − 19
16.10.5 The %recovery, RC, determined at a temperature test results for five crude oils and five residues. It is important
TRC that is equal to or less than FET, can be determined at a to note that the Results for the precision statement as shown in
new temperature TN by using the following equation: Tables 4-6 are to be used only within the ranges shown in the
~ RC 2 R C21% ! tables. Additional studies are required to expand the precision
~ T RC 2 T RC21% ! ~
E RC 5 3 T 2 T RC21% ! 1R C21% (9) to the ranges not listed in Tables 4-6, respectively.
where: test results obtained by the same operator with the same
ERC = estimated recovery at temperature T, apparatus under constant operating conditions on identical test
%RC = %recovery determined at temperature TRC in Material would, in the long run, in the normal and correct
16.8.1, Operation of the test method, exceed the values in only one
%RC-1% = %recovery determined at 1 % below the %RC, case in twenty as shown in Table 4 (Residues), Table 5 (Crude
and Oil), and Table 6 for Cuts (as used in the ASTM Crosscheck for
TRC-1% = temperature corresponding to RC-1%. Crude Oils).
16.10.5.1 The use of this equation for values TN > FET is 18.1.2 Reproducibility—The difference between two single
not recommended. and independent test results obtained by different operators
17. Report would, in the long run, in the normal and correct operation of
17.1 Report the temperatures to the nearest 0.5 °C (1 °F) at the test method, exceed the values shown in Table 4
1 % intervals between 1 % and up to the nearest integer of the (Residues), Table 5 (Crude Oil), and Table 6 for Cuts (as used
lower boundary of the %RC. Report also the initial boiling in the ASTM Crosscheck for Crude Oils).
point (IBP). Report the selected cut point intervals.
18.2 Bias—The bias in results of this test method cannot be
18. Precision and Bias3 determined because the boiling range distribution is defined by
the test method.
18.1 Precision—The precision of this test method was
determined by the statistical examination of the interlaboratory
19. Keywords
3
19.1 boiling point distribution; crude oils; cut point inter-
be obtained by requesting Research Report RR:D02-1724. Contact ASTM Customer vals; distillation residues; lubricants; residues; simulated
Service at service@astm.org. distillation
TABLE 4 Repeatability and Reproducibility for ResiduesA

recovered
IBP 5.72 10.3 13.7 24.7 246 to 504 474 to 939
5 3.39 6.1 5.75 10.4 315 to 547 599 to 1017
10 3.19 5.7 5.39 9.7 346 to 563 654 to 1045
15 2.88 5.2 5.2 9.4 368 to 575 694 to 1067
20 3.42 6.2 6.5 11.7 388 to 585 730 to 1085
25 3.55 6.4 6.71 12.1 405 to 595 761 to 1103
30 3.93 7.1 7.6 13.7 420 to 604 788 to 1119
35 4.38 7.9 8.9 16.0 434 to 614 813 to 1137
40 5.22 9.4 11 19.8 447 to 624 836 to 1155
45 6.27 11.3 13.5 24.3 462 to 634 863 to 1173
50 7.18 12.9 16.4 29.5 477 to 645 890 to 1193
55 8.64 15.6 19.9 35.8 493 to 656 919 to 1213
60 10.1 18.2 22.6 40.7 509 to 670 948 to 1238
65 11.7 21.1 24.7 44.5 529 to 684 984 to 1263
70 15.2 27.4 27.4 49.3 550 to 699 1022 to 1290
75 16.6 29.9 30.9 55.6 574 to 716 1065 to 1321
A
10
D7169 − 19
TABLE 5 Repeatability and Reproducibility for Crude OilA
recovered
IBP 1.35 2.4 2.49 4.5 30 to 31 86 to 88
5 8.94 16.1 19.6 35.3 76 to 97 169 to 207
10 11.4 20.5 19.5 35.1 109 to 154 228 to 309
15 8.23 14.8 15.1 27.2 134 to 217 273 to 423
20 7.51 13.5 13.1 23.6 160 to 259 320 to 498
25 8.7 15.7 13.6 24.5 184 to 295 363 to 563
30 8.22 14.8 13.1 23.6 210 to 327 410 to 621
35 8.52 15.3 14 25.2 231 to 358 448 to 676
40 8.83 15.9 14.9 26.8 249 to 398 480 to 748
45 8.99 16.2 15.1 27.2 265 to 436 509 to 817
50 9.88 17.8 16.4 29.5 285 to 325 545 to 887
55 10.8 19.4 18.6 33.5 304 to 517 579 to 963
60 12.4 22.3 21.5 38.7 326 to 563 619 to 1045
65 13.8 24.8 24.3 43.7 351 to 608 664 to 1126
70 14.3 25.7 21.2 38.2 379 to 608 714 to 1126
75 15.1 27.2 28.24 50.8 410 to 700 770 to 1292
A
TABLE 6 Repeatability and Reproducibility for Cut PointsA

Cut from Set Cut Temperature, Cut Temperature, Repeatability, r Reproducubility, R
to Temperature °C °F Mass % Mass %
Crude Cut 1 82.2 180 1.24 1.74
Crude Cut 2 193.3 380 1.42 1.92
Crude Cut 3 248.9 480 1.48 2.05
Crude Cut 4 343.3 650 1.63 2.28
Crude Cut 5 426.7 800 1.78 2.58
Crude Cut 6 565.6 1050 2.1 3.03
Crude Cut 7 596.1 1105 2.03 3.12
Crude Cut 8 720 1328 2.52 3.17
Residue Cut 1 330 626 0.0748 X 0.126 X
Residue Cut 2 450 842 0.0767 X 0.109 X
Residue Cut 3 600 1112 0.0338 (X + 30) 0.0726 (X + 30)
Residue Cut 4 720 1328 5.36 7.16
A
X= % mass recovered at the cut. Do not extrapolate outside of the above reported data.
ANNEX
A1. CHROMATOGRAMS AND FIGURES
11
D7169 − 19
FIG. A1.1 Typical Blank Run (Initial Temperature −20 °C)
FIG. A1.2 Chromatogram of the Retention Time Calibration Mixture C5-C100 Injected at −20 °C,
Insert Expands View of C5-C7 Region
12
D7169 − 19
FIG. A1.3 Chromatogram (Baseline Corrected) of Reference Oil 5010 Injected at −20 °C
FIG. A1.4 Chromatogram (Baseline Corrected) of a Crude Oil (Injected at −20 °C)
13
D7169 − 19
FIG. A1.5 Chromatogram (Baseline Corrected) of an Atmospheric Residue
14
D7169 − 19
FIG. A1.6 Correct and Incorrect Relative Position of Baseline and Sample Signal
FIG. A1.7 Expanded Chromatogram of a CS2 Injection for Selecting the Quenching Interval
15
D7169 − 19
FIG. A1.8 Boiling Point versus Retention Time Plot
APPENDIX
X1. ALGORITHM FOR MERGING BOILING POINT DISTRIBUTION RESULTS OF D7900 AND D7169
X1.1 The resulting data from Test Methods D7900 and without such interference. This algorithm generates boiling
D7169 can be used to perform a merge of the D7900 light ends point distribution results that correct this anomaly in the light
boiling point curve with that of D7169, using a variety of end portion of Test Method D7169 by merging the more
mathematical means. accurate results of Test Method D7900.
X1.2 This appendix outlines an algorithm to aid in merging X1.4 Summary of the Procedure
the results of D7900 with those of D7169 to result in a more X1.4.1 The boiling point distribution results from Test
accurate boiling point distribution of the crude oil sample. The Methods D7900 and D7169 for the same sample are collected
algorithm does not attempt to smooth or otherwise alter the in value arrays. They are merged together at a fixed boiling
results of the merged boiling point distribution, relying solely point temperature not to exceed the boiling point of n-nonane
on the original results from Test Methods D7900 and D7169. (the current limit of Test Method D7900 results). A new boiling
Additional mathematical smoothing or fitting is left to the point distribution result is calculated from the merged data.
individual user and his requirements. Recoveries greater than 100 % by mass after the merge are
X1.3 Significance and Use normalized through the D7169-only contribution to the final
results, as the D7900 results are assumed to be accurate as
X1.3.1 The scope of Test Method D7169 includes a caveat reported.
that results for the light end portion of the analysis may be
inaccurate due to the co-elution of the required carbon disulfide
solvent with light hydrocarbons. This results in a diminished or
quenched FID response to those hydrocarbons, resulting in
lower recoveries in this region. Test Method D7900 was
developed to more accurately determine the boiling point
distribution of the front end portion of a crude oil sample
16
D7169 − 19
NOTE X1.1—In a situation such as a heavy crude where there is no TABLE X1.1 Value Array D7900 Cumulative Mass Percent (CMP)
significant amount of light ends at or below C9, then the D7169 data versus BP Degrees Celsius (BP, °C) in 0.01 % by Mass Intervals
should be taken as reported with no merge or light ends correction. Array Row CMP BP (°C)
1 0.50 % –42.04
X1.5 D7900 and D7169 Data Accuracy Determination 2 0.51 % –11.72
3 0.52 % –0.50
X1.5.1 To ensure that the initial D7900 and D7169 data is ... ... ...
comparable in accuracy, determine the cumulative mass per- ... ... ...
cent recovery at the boiling point where the merge is to be C9 21.30 % 150.76
made from each of the D7900 and D7169 results. Calculate the
absolute difference as:
DIFFx 5 ABS~ M 1 2 M 2 ! (X1.1) D7169. For example, a sample containing 5 % by mass n-pentane would
have five successive whole mass percentages occurring at the boiling point
where: of n-pentane (36.06 °C). See Fig. X1.1.
DIFFx = absolute difference in cumulative mass recovery X1.6.1.2 D7169 Mass Percent by BP Data Array, N
between D7900 and D7169 at the merge boiling Elements—Create a two-dimensional value array from the
point, D7169 results (D7169VA) where:
D7169VA(i,1) = cumulative percent by mass from D7169 results in percent by
point temperature from D7900, and mass increments no greater than 0.1, and
point temperature from D7169. D7169VA(i,2) = boiling point, in °C, at this cumulative percent by mass.
X1.5.2 The absolute difference (DIFFx) in most cases will Begin the array at 0.50 % by mass (defined as initial boiling
not exceed 5.0 % by mass. Values above this may indicate point or IBP) and end the array at the final D7169 cumulative
possible errors in the D7900 or D7169 analyses, or both mass percent recovered. As an example, for a n-nonane merge
(weighing errors, response factor errors, etc.). Further review point using 0.01 % by mass increments, such an array would
of these analytical results and possible re-analysis of the appear as indicated in Table X1.2.
sample may be required.
NOTE X1.4—Anecdotal studies performed by various labs performing
NOTE X1.2—It is possible in very light condensates containing a this merge algorithm found that by using 0.01 % by mass increments for
significant amount of hexanes and lighter that the application of the D7169 the D7900 and D7169 results initially, the need for interpolation is
quench factor could cause marked differences in the two results. In this reduced and the accuracy of the merge point and final result comparability
case, or when the D7900 and D7169 results are determined to be accurate to physical distillation was improved.
within themselves, the D7900 result should be assumed to be the most
accurate, as it is not affected by solvent quenching. X1.7 Data Merging Procedure
X1.6 Elements Required to Perform Merge of D7900 and X1.7.1 The following procedure is used to prepare a result
D7169 at the Merge Point value array (RVA) containing the merged results.
X1.6.1 The following elements must be prepared from the X1.7.1.1 Create a two-dimensional result value array (RVA)
results of Test Methods D7900 and D7169 for the sample. The where:
selected merge point shall not exceed the boiling point of RVA(i,1) = cumulative mass percent in no greater than 0.1 % by mass
increments, and
n-nonane (the boiling point limit of Test Method D7900).
X1.6.1.1 D7900 Mass Percent by BP Value Array, N RVA(i,2) = boiling point, in °C, at that cumulative percent by mass.
Elements—Create a two-dimensional value array from the
D7900 results (D7900VA) where: Initially populate the array with all the elements of the
D7900VA(i,1) = cumulative mass percent from D7900 results in percent by D7900VA (see X1.6.1.1). Store the final row number after all
mass increments of at least 0.1, and D7900 data is added to the RVA, as this may be needed later if
D7900VA(i,2) = boiling point, in °C, at this cumulative percent by mass.
normalization is required (see X1.9).
X1.7.1.2 Search the D7169 cumulative percent by mass
Begin the array at 0.5 % by mass (defined as initial boiling versus BP value array until the row containing the cumulative
point or IBP) and end the array at the cumulative mass percent percent by mass at the merge point is found. Append percent by
recovered at the merge point’s boiling point. As an example, mass values from the D7169 value array to the result value
such an array would appear as indicated in Table X1.1 if array from the first row just after the merge point of the D7169
n-nonane’s boiling point was selected as the merge point and value array as follows:
0.01 % by mass increments are used. For i 5 x to N (X1.2)
NOTE X1.3—There may be elements of the array where multiple RVA~ i , 1 ! 5 RVA~ i 2 1 , 1 ! 1z
cumulative percentages occur at the exact same temperature. This is due RVA~ i , 2 ! 5 D7169VA~ m , 2 !
to the fact that Test Method D7900 is a component-based boiling point
distribution as opposed to the slice-based distribution used in Test Method m 5 m11
17
D7169 − 19
FIG. X1.1 Example of Light End Component Boiling Distribution Showing Multiple Cumulative Percentages at the Boiling Point of Iso-
pentane and Pentane
TABLE X1.2 Value Array D7169 Cumulative Mass Percent (CMP) m = initialized at the array element row num-
versus BP Degrees Celsius (BP, °C) In 0.01 % by Mass Intervals
ber of first D7169VA element just after the
Array Row CMP BP (°C)
1 0.50 % 36.06
merge point from search of array,
2 0.51 % 39.20 RVA(i,1) = result value array cumulative percent by
3 0.52 % 43.55 mass at row i,
... ... ... RVA(i,2) = result value array boiling point (in °C) at
... ... ...
999 23.00 % 150.76 (n-nonane BP) row i,
... ... ... D7169VA(m,1) = D7169 cumulative percent by mass at row
... ... ... m, and
N 94.30 % 712.00
D7169VA(m,2) = D7169 boiling point (in °C) at row m.
X1.8 Reporting Merged Results
Next i X1.8.1 Using the completed result value array (RVA, see
X1.7.1.2), extract the cumulative percent by mass by boiling
where:
point in the desired percent by mass intervals and report.
N = the total number of rows in the D7169VA, Report the initial boiling point (IBP) as the temperature at
x = array element row number for next value which 0.5 % by mass of the sample has eluted, and (if
pair from D7169VA that is just after the applicable) report the final boiling point (FBP) as the tempera-
row at the merge point, ture at which 99.5 % by mass of the sample has eluted. If the
z = increment of mass percentages (for
final RVA recovery is less than or equal to 100.0 % by mass,
example, 0.1, 0.01),
end the report at the last full cumulative percent by mass off.
18
D7169 − 19
The actual final percent by mass recovery and temperature may X1.9.2 Normalize the D7169 mass percentages using the
be reported also, if desired. If the final percent by mass following procedure:
recovery exceeds 100.0 % by mass, follow the procedure in For i 5 x to N (X1.4)
X1.9 to renormalize only the array elements taken from the
D7169 results to give exactly 100.0 % by mass recovery. The RVA~ i , 1 ! 5 RVA~ i 2 1 , 1 ! 1 ~ P 3 D 7169 NF!
D7900 result values should NOT be normalized as these are Next i
assumed to be accurate as reported. Fig. X1.2 demonstrates an
example report. where:
x = array element just after the last D7900 contrib-
NOTE X1.5—For clarity and comparison, it is also suggested to report uted mass percentage,
the original D7169 percent by mass recovery, and the final merged percent
by mass recovery. The difference here again should be less than 5 % by
N = last element of the RVA array,
mass absolute. If higher, see X1.5. P = increment of the cumulative mass percentages
(0.1, 0.01, etc.), and
X1.9 Normalizing Results for Recoveries in Excess of 100 D7169NF = normalization factor to be applied to all D7169
% by Mass After Merging cumulative percent by mass results in the RVA.
X1.9.1 If the chromatographic results for Test Methods X1.9.2.1 The final sum of all cumulative mass percentages
D7900 and D7169 have been verified, and the recovery is in in the RVA (D7900 and D7169 contributed) should now equal
excess of 100.0 % by mass or is greater than a predetermined exactly 100.0 % by mass. Use the normalized RVA to report the
recovery threshold, the following procedure should be used to results (as an example see Fig. X1.2).
normalize the D7169 data only:
~ 100 2 R D7900! NOTE X1.6—Un-normalized percent by mass recovery of the result
D7169NF 5 (X1.3) value array in excess of 105.0 % by mass should be considered suspect.
~ RVA ~ y , 1 ! 2 R D7900! An excess recovery of this magnitude may indicate inaccuracies in the
where: D7900 results, the D7169 results, or both. See X1.5.
D7169NF = normalization factor to be applied to all D7169
cumulative percent by mass results in the RVA,
RD7900 = cumulative percent by mass recovery at the
merge point from D7900, and
y = last row element of the D7169 portion of the
RVA (final percent by mass recovery).
19
D7169 − 19
FIG. X1.2 Example Final Merged Boiling Point Distribution Report
SUMMARY OF CHANGES
(1) Revised Table 2.
(1) Replaced former Appendix X1 with new Appendix X1

(Appendix X3 from Test Method D7900).
20
Designation: D7213 − 15 (Reapproved 2019)

Boiling Range Distribution of Petroleum Distillates in the
Boiling Range from 100 °C to 615 °C by Gas
Chromatography1
1. Scope 2. Referenced Documents

1.1 This test method covers the determination of the boiling 2.1 ASTM Standards:2
range distribution of petroleum products. This test method is D86 Test Method for Distillation of Petroleum Products and
applicable to petroleum distillates having an initial boiling Liquid Fuels at Atmospheric Pressure
point greater than 100 °C and a final boiling point less than D1160 Test Method for Distillation of Petroleum Products at
615 °C at atmospheric pressure as measured by this test Reduced Pressure
method. D2887 Test Method for Boiling Range Distribution of Pe-
1.2 The test method is not applicable for analysis of troleum Fractions by Gas Chromatography
petroleum distillates containing low molecular weight compo- D2892 Test Method for Distillation of Crude Petroleum
nents (for example, naphthas, reformates, gasolines, crude (15-Theoretical Plate Column)
oils). Materials containing heterogeneous components (for D4626 Practice for Calculation of Gas Chromatographic
example, alcohols, ethers, acids or esters) or residue are not to Response Factors
be analyzed by this test method. See Test Methods D7096, D6352 Test Method for Boiling Range Distribution of Pe-
D2887, D6352, or D7169. troleum Distillates in Boiling Range from 174 °C to
1.3 This test method uses the principles of simulated distil- D7096 Test Method for Determination of the Boiling Range
lation methodology. Distribution of Gasoline by Wide-Bore Capillary Gas
1.4 The values stated in SI units are to be regarded as Chromatography
standard. No other units of measurement are included in this D7169 Test Method for Boiling Point Distribution of
standard. Samples with Residues Such as Crude Oils and Atmo-
spheric and Vacuum Residues by High Temperature Gas
Chromatography
E355 Practice for Gas Chromatography Terms and Relation-
ships
priate safety, health, and environmental practices and deter-
E594 Practice for Testing Flame Ionization Detectors Used
in Gas or Supercritical Fluid Chromatography
E1510 Practice for Installing Fused Silica Open Tubular
ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom- 3. Terminology
mendations issued by the World Trade Organization Technical
3.1 Definitions—This test method makes reference to many
Barriers to Trade (TBT) Committee.
common gas chromatographic procedures, terms, and relation-
ships. Detailed definitions of these can be found in Practices
E355, E594, and E1510.
1
2
10.1520/D7213-15R19. the ASTM website.
1
D7213 − 15 (2019)
3.2 Definitions of Terms Specific to This Standard: tion detector. The detector signal integral is recorded as area
3.2.1 area slice, n—the area, resulting from the integration slices for consecutive retention time intervals during the
of the chromatographic detector signal, within a specified analysis.
retention time interval. In area slice mode (see 6.4.2), peak 4.4 Retention times of known normal paraffin hydrocarbons
detection parameters are bypassed and the detector signal spanning the scope of this test method (C5-C60) are determined
integral is recorded as area slices of consecutive, fixed duration and correlated to their boiling point temperatures. The normal-
time intervals. ized cumulative corrected sample areas for each consecutive
3.2.2 corrected area slice, n—an area slice corrected for recorded time interval are used to calculate the boiling range
baseline offset, by subtraction of the exactly corresponding distribution. The boiling point temperature at each reported
area slice in a previously recorded blank (non-sample) analy- percent off increment is calculated from the retention time
sis. calibration.
3.2.3 cumulative corrected area, n—the accumulated sum of 5. Significance and Use
corrected area slices from the beginning of the analysis through
a given retention time, ignoring any non-sample area (for 5.1 The boiling range distribution of light and medium
example, solvent). petroleum distillate fractions provides an insight into the
composition of feed stocks and products related to petroleum
3.2.4 final boiling point (FBP), n—the temperature (corre- refining process, This gas chromatographic determination of
sponding to the retention time) at which a cumulative corrected boiling range can be used to replace conventional distillation
area count equal to 99.5 % of the total sample area under the methods for control of refining operations. This test method
chromatogram is obtained. can be used for product specification testing with the mutual
3.2.5 initial boiling point (IBP), n—the temperature (corre- agreement of interested parties.
sponding to the retention time) at which a cumulative corrected 5.2 This test method extends the scope of boiling range
area count equal to 0.5 % of the total sample area under the determination by gas chromatography to include light and
chromatogram is obtained. medium petroleum distillate fractions beyond the scope of Test
3.2.6 slice rate, n—the time interval used to integrate the Method D2887 (538 °C) and below Test Method D6352
continuous (analog) chromatographic detector response during (700 °C).
an analysis. The slice rate is expressed in Hz (for example, 5.3 Boiling range distributions obtained by this test method
integrations or slices per second). are theoretically equivalent to those obtained by true boiling
3.2.7 slice time, n—the cumulative slice rate (analysis time) point (TBP) distillation (see Test Method D2892). They are not
associated with each area slice throughout the chromatographic equivalent to results from low efficiency distillation such as
analysis. The slice time is the time at the end of each those obtained with Test Method D86 or D1160.
contiguous area slice.
6. Apparatus
3.2.8 total sample area, n—the cumulative corrected area,
from the initial point to the final area point. 6.1 Chromatograph—The gas chromatographic system used
shall have the following performance characteristics:
3.3 Abbreviations—A common abbreviation of hydrocarbon 6.1.1 Column Oven—Capable of sustained and linear pro-
compounds is to designate the number of carbon atoms in the grammed temperature operation from near ambient (for
compound. A prefix is used to indicate the carbon chain form, example, 35 °C to 50 °C) up to 400 °C.
while a subscripted suffix denotes the number of carbon atoms 6.1.2 Column Temperature Programmer—The chromato-
(for example, normal decane n-Cl0; iso-tetradecane = i-Cl4). graph shall be capable of linear programmed temperature
operation up to 400 °C at selectable linear rates up to
4. Summary of Test Method 20 °C ⁄min. The programming rate shall be sufficiently repro-
4.1 The boiling range distribution by distillation is simu- ducible to obtain the retention time repeatability of 0.1 min
lated by the use of gas chromatography. The solvent should not (6 s) for each component in the calibration mixture described
interfere with measurement of the sample in the 100 °C to in 7.5.
615 °C range, and it should be apolar. A non-polar open tubular 6.1.3 Detector—This test method requires a flame ioniza-
(capillary) gas chromatographic column is used to elute the tion detector (FID). The detector shall meet or exceed the
hydrocarbon components of the sample in order of increasing following specifications as detailed in Practice E594. The
boiling point. flame jet should have an orifice of approximately 0.45 mm to
0.50 mm.
4.2 A sample aliquot is diluted with a viscosity reducing 6.1.3.1 Operating Temperature, 400 °C.
solvent and introduced into the chromatographic system. 6.1.3.2 Sensitivity, >0.005 coulombs/g carbon.
Sample vaporization is provided by separate heating of the 6.1.3.3 Minimum Detectability, 1 × 10-11 g carbon/s.
point of injection or in conjunction with column oven heating. 6.1.3.4 Linear Range, >106.
4.3 The column oven temperature is raised at a reproducible 6.1.3.5 Connection of the column to the detector shall be
linear rate to effect separation of the hydrocarbon components such that no temperature below the column temperature exists.
in order of increasing boiling point. The elution of sample Refer to Practice E1510 for proper installation and condition-
components is quantitatively determined using a flame ioniza- ing of the capillary column.
2
D7213 − 15 (2019)
6.1.4 Sample Inlet System—Any sample inlet system ca- 7. Reagents and Materials3
pable of meeting the performance specification in 7.6 may be 7.1 Carrier Gas—Helium or hydrogen of high purity.
used. Programmed temperature vaporization (PTV) and pro- (Warning—Helium and hydrogen are compressed gases under
grammable cool on-column injection systems have been used high pressure; hydrogen is an extremely flammable gas under
successfully. high pressure.) These gases may be used as the carrier gas and
6.1.5 Carrier Gas Flow Control—The chromatograph shall should not contain more than 5 mL/m3 of oxygen. The total
be equipped with carrier gas pressure or flow control capable of amount of impurities should not exceed 10 mL/m3. Additional
maintaining constant carrier gas flow control through the purification is recommended by the use of molecular sieves or
column throughout the column temperature program cycle. other suitable agents to remove water, oxygen, and hydrocar-
6.2 Microsyringe—A microsyringe with a 23 gauge or bons. Available pressure shall be sufficient to ensure a constant
smaller stainless steel needle is used for on-column sample carrier gas flow rate.
introduction. Syringes of 0.1 µL to 10 µL capacity are avail- 7.2 Hydrogen—Hydrogen of high purity (for example,
able. hydrocarbon-free) is used as fuel for the flame ionization
6.2.1 Automatic syringe injection is recommended to detector (FID). (Warning—Hydrogen is an extremely flam-
achieve best precision. mable gas under high pressure.)
7.3 Air—High purity (for example, hydrocarbon-free) com-
6.3 Column—This test method is limited to the use of
pressed air is used as the oxidant for the flame ionization
non-polar wall coated open tubular (WCOT) columns of high
detector (FID). (Warning—Compressed air is a gas under high
thermal stability. Glass, fused silica, and stainless steel
pressure and supports combustion.)
columns, with a 0.53 mm diameter have been successfully
used. Cross-linked or bonded 100 % dimethyl-polysiloxane 7.4 Solvents—Unless otherwise indicated, it is intended that
stationary phases with film thickness of 0.5 µm to 1.0 µm have all solvents conform to the specifications of the committee on
been used. The column length and liquid phase film thickness analytical Reagents of the American Chemical Society where
shall allow the elution of at least C60 n-paraffin (BP = 615 °C). such specifications are available.3 Other grades may be used
The column and conditions shall provide separation of typical provided it is first ascertained that the solvent is of sufficiently
petroleum hydrocarbons in order of increasing boiling point high purity to permit its use without lessening the accuracy of
and meet the column resolution requirements of 8.2.1. The the determination.
column shall provide a resolution between one and ten using 7.4.1 Carbon Disulfide (CS2)—(99+ % pure) may be used as
this test method’s operating conditions. a viscosity reducing solvent and as a means of reducing mass
of sample introduced onto the column to ensure linear detector
6.4 Data Acquisition System: response and reduced peak skewness. It is miscible with
6.4.1 Recorder—A 0 mV to 1 mV range recording potenti- asphaltic hydrocarbons and provides a relatively small re-
ometer or equivalent, with a full-scale response time of 2 s or sponse with the FID. The quality (hydrocarbon content) should
less may be used to provide a graphical display. be determined by this test method prior to use as a sample
6.4.2 Integrator—Means shall be provided for determining diluent. (Warning— Carbon disulfide is extremely flammable
the accumulated area under the chromatogram. This can be and toxic.)
done by means of an electronic integrator or computer-based 7.5 Cyclohexane (C6H12)—(99+ % pure) may be used as a
chromatography data system. The integrator/computer system viscosity reducing solvent. It is miscible with asphaltic
shall have normal chromatographic software for measuring the hydrocarbons, however, it responds well to the FID. The
retention time and areas of eluting peaks (peak detection quality (hydrocarbon content) should be determined by this test
mode). In addition, the system shall be capable of converting method prior to use as a sample diluent. (Warning—
the continuously integrated detector signal into area slices of Cyclohexane is flammable.)
fixed duration (area slice mode). These contiguous area slices,
7.6 Calibration Mixture—A qualitative mixture of
collected for the entire analysis, are stored for later processing.
n-paraffins (nominally C5 to C60) dissolved in a suitable
The electronic range of the integrator/computer (for example, 1
solvent. The final concentration should be approximately one
V, 10 V) shall be operated within the linear range of the
part of n-paraffin mixture to one hundred parts of solvent. At
detector/electrometer system used.
NOTE 1—Some gas chromatographs have an algorithm built into their 3
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
operating software that allows a mathematical model of the baseline Standard-Grade Reference Materials, American Chemical Society, Washington,
profile to be stored in memory. This profile is automatically subtracted DC. For suggestions on the testing of reagents not listed by the American Chemical
from the detector signal on subsequent sample runs to compensate for the Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
column bleed. Some integration systems also store and automatically U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
subtract a blank analysis from subsequent analytical determinations. copeial Convention, Inc. (USPC), Rockville, MD.
3
D7213 − 15 (2019)
least one compound in the mixture shall have a boiling point NOTE 2—A suitable calibration mixture can be obtained by dissolving
lower than the initial boiling point of the sample being a polyolefin wax (for example, Polywax 5004) in a volatile solvent (for
example, carbon disulfide or cyclohexane). Solutions of one part Polywax
analyzed, as defined in the scope of this test method (1.1). The to one hundred parts solvent can be prepared. Lower boiling point
calibration mixture shall contain at least 13 known n-paraffins
(for example, C6, C7, C8, C9, C10, C12, C16, C20, C30, C40, C50,
C52, C60). Boiling points of n-paraffins are listed in Table 1. 4
Polywax is a trademark of the Baker Petrolite Corporation, Barnsdall, OK.
TABLE 1 Boiling Points of n-ParaffinsA,B

Carbon Boiling Boiling
Number Point °C Point °F
5 36 97
6 69 156
7 98 209
8 126 258
9 151 303
10 174 345
11 196 385
12 216 421
13 235 456
14 254 488
15 271 519
16 287 548
17 302 576
18 316 601
19 330 626
20 344 651
21 356 674
22 369 695
23 380 716
24 391 736
25 402 755
26 412 774
27 422 791
28 431 808
29 440 825
30 449 840
31 458 856
32 466 870
33 474 885
34 481 898
35 489 912
36 496 925
37 503 937
38 509 948
39 516 961
40 522 972
41 528 982
42 534 993
43 540 1004
44 545 1013
45 550 1022
46 556 1033
47 561 1042
48 566 1051
49 570 1058
50 575 1067
51 579 1074
52 584 1083
53 588 1090
54 592 1098
55 596 1105
56 600 1112
57 604 1119
58 608 1126
59 612 1134
60 615 1139
A
API Project 44, 72-10-31, is believed to have provided the original normal paraffin boiling point data that are listed in Table 1. However, over the years some of the data
contained in both API Project 44 (Thermodynamics Research Center Hydrocarbon Project) and Test Method D7213 have changed, and they are no longer equivalent. Table
1 represents the current normal paraffin boiling point values accepted by Subcommittee D02.04 and found in all test methods under the jurisdiction of Section D02.04.H.
B
Test Method D7213 has traditionally used n-paraffin boiling points rounded to the nearest whole degree for calibration. The boiling points listed in Table 1 are correct to
the nearest whole number in both degrees Celsius and degrees Fahrenheit. However, if a conversion is made from one unit to the other and then rounded to a whole
number, the results will not agree with the table values for a few carbon numbers. For example, the boiling point of n-heptane is 98.425 °C which is correctly rounded to
98 °C in the table. However, converting 98.425 °C gives 209.165 °F, which rounds to 208 °F, while converting 98 °C gives 208.4 °F, which rounds to 208 °F. Carbon
numbers 2, 4, 7, 8, 9, 13, 14, 15, 16, 25, 27, and 32 are affected by rounding.
4
D7213 − 15 (2019)
paraffins will have to be added to insure conformance with 7.6. Fig. 1 7.8 Reference Material—A reference sample that has been
illustrates a typical calibration mixture chromatogram. analyzed by laboratories participating in the test method
7.7 Response Linearity Mixture—Prepare a quantitatively cooperative study. Consensus values for the boiling range
weighed mixture of at least ten individual paraffins (>99 % distribution of this sample are being determined.
purity), covering the boiling range of the test method. The
highest boiling point component should be at least n-C60 . The 8. Preparation of Apparatus
mixture shall contain n-C40. Use a suitable solvent to provide
a solution of each component at approximately 0.5 % to 2.0 % 8.1 Gas Chromatograph Setup:
by mass.
FIG. 1 Typical Calibration Curve with Plot
5
D7213 − 15 (2019)
8.1.1 Place the gas chromatograph and ancillary equipment where:
into operation in accordance with the manufacturers instruc- R = resolution,
tions. Recommended operating conditions are shown in Table t1 = time for the n-C50 peak maximum,
2. t2 = time for the n-C52 peak maximum,
8.1.2 When attaching the column to the detector inlet, w1 = peak width, at half height, of the n-C50 peak and,
ensure that the end of the column terminates as close as w2 = peak width, at half height, of the n-C52 peak.
possible to the FID jet. Follow the instructions in Practice
8.2.2 Detector Response Calibration—This test method as-
E1510.
sumes that the FID response to petroleum hydrocarbons is
8.1.3 The FID should be periodically inspected and, if
necessary, remove any foreign deposits formed in the detector proportional to the mass of individual components. This shall
from combustion of silicone liquid phase or other materials. be verified when the system is put in service, and whenever any
Such deposits will change the response characteristics of the changes are made to the system or operational parameters.
detector. Analyze the response linearity mixture (see 7.7) using the
8.1.4 The inlet liner and initial portion of the column shall identical procedure to be used for the analysis of samples (see
be periodically inspected and replaced if necessary to remove Section 9). Calculate the relative response factor for each
extraneous deposits or sample residue. n-paraffin (relative to n-tetracontane) as per Practice D4626
8.1.5 Column Conditioning—A new column will require and Eq 2:
conditioning at the upper test method operating temperature to F n 5 ~ M n /A n ! / ~ M 40/A 40! (2)
reduce or eliminate significant liquid phase bleed, resulting in
a stable chromatographic baseline. Follow the guidelines where:
outlined in Practice E1510. Fn = relative response factor,
Mn = mass of the n-paraffin in the mixture,
8.2 System Performance Specification:
An = peak area of the n-paraffin in the mixture,
8.2.1 Column Resolution—The column resolution, influ- M40 = mass of the n-tetracontane in the mixture, and
enced by both the column physical parameters and operating A40 = peak area of the n-tetracontane in the mixture.
conditions, affects the overall determination of boiling range
distribution. Resolution is therefore specified to maintain 8.2.2.1 The relative response factor (Fn) of each n-paraffin
equivalence between different systems (laboratories) employ- shall not deviate from unity by more than 65 %.
ing this test method. Resolution is determined using Eq 1 and 8.2.3 Column Temperature—The column temperature pro-
the C50 and C52 paraffins from a calibration mixture analysis gram profile is selected such that the C5 peak can be differen-
(or a polywax retention time boiling point mixture) (see 7.6). tiated from the solvent and that the maximum boiling point
Resolution (R) should be at least one and not more than ten, (615 °C) n-paraffin (C60) is eluted from the column before
using the identical conditions employed for sample analyses. reaching the end of the temperature program. The actual
R 5 2 ~ t 2 2 t 1 ! / ~ 1.699 ~ w 2 1w 1 !! (1) program rate used will be influenced by other operating
TABLE 2 Recommended Operating ConditionsA

Injector Cool on-column. Temperature Programmable Inlet (no Split)
Injection temperature Oven-track mode
Auto sampler Required for best precision
Data collection Data is collected as independent area slices
(average data collection rate is 1.0 Hz or
3.3 slices per second)
Column Capillary, 5 m by 0.53 mm id
film thickness; 0.1 µm to 1.0 µm (polymethylsiloxane) 0.8 µm – 1.0 µm
was used in the ILS study
Flow conditions UHP helium at 12 mL/min (constant flow)
Carrier: He and Hydrogen were used in the ILS Study (make-up gas helium at 18 mL/min)
Detector Flame Ionization;
Temperature: 390 °C
Oven program Initial oven temperature 35 °C – 50 °C,
initial hold 0 min,
program rate 10 °C/min.,
final oven temperature 380 °C,
final hold 12 min,
equilibration time 2 min
Sample size 1 µL
Sample dilution 2 mass percent in carbon disulfide
Calibration dilution 1 mass percent in carbon disulfide
A
Hydrogen was used in the precision study. Results were found to be “statistically equivalent.” See Research Report RR:D02-1725.
6
D7213 − 15 (2019)
variables such as column dimensions, liquid phase film deviate from zero, subtract the average of these corrected area slices from
thickness, carrier gas and flow rate, and sample size. each corrected area slice in the analysis.
8.2.4 Column Elution Characteristics—The recommended 9.3 Retention Time versus Boiling Point Calibration—A
column liquid phase is a non-polar phase such as 100 % retention time versus boiling point calibration shall be per-
dimethyl-polysiloxane. formed on the same day that analyses are performed. Inject an
appropriate aliquot (0.2 µL to 2.0 µL) of the calibration mixture
9. Procedure (see 7.6) into the chromatograph, using the analysis sequence
9.1 Analysis Sequence Protocol—Define and use a predeter- protocol. Obtain a normal (peak detection) data record in order
mined schedule of analysis events designed to achieve maxi- to determine the peak retention times and the peak areas for
mum reproducibility for these determinations. The schedule each component. Collect a time slice area record if a boiling
will include cooling the column oven and injector to the initial range distribution report is desired. Fig. 1 illustrates a graphical
starting temperature, equilibration time, sample injection and plot of a calibration analysis.
system start, analysis, and final temperature hold time. 9.3.1 Inspect the chromatogram of the calibration mixture
9.1.1 After chromatographic conditions have been set to for evidence of skewed (non-Gaussian shaped) peaks. Skew-
meet performance requirements, program the column tempera- ness is often an indication of overloading the sample capacity
ture upward to the maximum temperature to be used and hold of the column, which will result in displacement of the peak
that temperature for the selected time. Following the analysis apex relative to non-overloaded peaks. Distortion in retention
sequence protocol, cool the column to the initial starting time measurement and hence errors in boiling point tempera-
temperature. ture calibration will be likely if column overloading occurs.
9.1.2 During the cool down and equilibration time, ready The column liquid phase loading has a direct bearing on
the integrator/computer system. If a retention time calibration acceptable sample size. Reanalyze the calibration mixture
is being performed, use the peak detection mode. For samples using a smaller sample size or a more dilute solution to avoid
and baseline compensation (with or without solvent injection), peak distortion.
use the area slice mode operation. The recommended slice rate 9.3.1.1 Skewness Calculation—Calculate the ratio A/B on
for this test method is 1.0 Hz (3.3 slices per second). Other specified peaks in the calibration mixture as indicated by the
slice rates may be used if within the limits of 0.02 % and 0.2 % designations in Fig. 2. A is the width in seconds of the portion
of the retention time of the final calibration component (C60). of the peak eluting prior to the time of the peak apex and
Faster slice rates may be used, as may be required for other measured at 10 % of peak height (0.10-H), and B is the width
reasons, if provision is made to accumulate (bunch) the slice in seconds of the portion of the peak eluting after the time of
data to within these limits prior to determination of the boiling the peak apex at 10 % of peak height (0.10-H). This ratio for
range distribution. n-pentacontane (n-C50) peak in the calibration mixture shall
9.1.3 At the exact time set by the schedule, inject either the not be less than 0.5 nor more than 2.0.
calibration mixture, solvent, or sample into the chromatograph;
or make no injection (baseline blank). At the time of injection,
start the chromatograph time cycle and the integrator/computer
data acquisition. Follow the analysis protocol for all subse-
quent repetitive analyses or calibrations. Since complete reso-
lution of sample peaks is not expected, do not change the
sensitivity setting during the analysis.
9.2 Baseline Blank—Perform a blank analysis (baseline
blank) at least once per day. The blank analysis may be without
injection or by injection of an equivalent solvent volume as
used with sample injections, depending upon the subsequent
data handling capabilities for baseline/solvent compensation.
The blank analysis is typically performed prior to sample
analyses, but may be useful if determined between samples or
at the end of a sample sequence to provide additional data
regarding instrument operation or residual sample carryover
from previous sample analyses.
NOTE 3—If automatic baseline correction (see Note 1) is provided by
the gas chromatograph, further correction of area slices may not be
required. However, if an electronic offset is added to the signal after
baseline compensation, additional area slice correction may be required in
the form of offset subtraction. Consult the specific instrumentation
instructions to determine if an offset is applied to the signal. If the
algorithm used is unclear, the slice area data can be examined to determine
if further correction is necessary. Determine if any offset has been added
to the compensated signal by examining the corrected area slices of those
time slices which precede the elution of any chromatographic unretained FIG. 2 Designation of Parameters for Calculation of Peak Skew-
substance. If these corrected area slices (representing the true baseline) ness
7
D7213 − 15 (2019)
9.3.2 Prepare a calibration table based upon the results of maximum calibration signal amplitude. A sample chromato-
the analysis of the calibration mixture by recording the time of gram is found in Fig. 3.
each peak maximum and the boiling point temperature in
degrees Celsius (or Fahrenheit) for every component in the 10. Calculations
mixture. Normal paraffin boiling point temperatures (atmo-
10.1 Acquisition Rate Requirements:
spheric equivalent temperatures) are listed in Table 1. An
10.1.1 The number of slices required at the beginning of
example of a typical calibration report, showing retention times
data acquisition depends on chromatographic variables such as
and boiling points for each n-paraffin, is found in Table 3.
the column flow, column film thickness, and initial column
9.4 Sample Preparation—Sample aliquots are introduced temperature as well as column length. In addition, the detector
into the gas chromatograph as solutions in a suitable solvent signal level has to be as low as possible at the initial
(for example, carbon disulfide or cyclohexane). temperature of the analysis. The detector signal level for both
9.4.1 Dilute the sample to approximately 2 % by weight the sample signal and the blank at the beginning of the run has
with the solvent. to be similar for proper zeroing of the signals.
9.4.2 Seal (cap) the vial, and mix the contents thoroughly to 10.1.2 The sampling frequency has to be adjusted so that at
provide a homogeneous mixture. It may be necessary to warm least a significant number of slices are acquired prior to the
the mixture initially to effect complete solution of the sample. start of elution of sample or solvent. For example, if the time
However, the sample shall be in stable solution at room for start of sample elution is 0.06 min (3.6 s), a sampling rate
temperature prior to injection. of 5 Hz would acquire 18 slices. However, a rate of 1 Hz would
9.5 Sample Analysis—Using the analysis sequence protocol only acquire 3.6 slices which would not be sufficient for
inject a diluted sample aliquot into the gas chromatograph. zeroing the signals. Rather than specifying number of slices, it
Collect a contiguous time slice record of the entire analysis is important to select an initial time segment, that is, one or two
(area slice mode). seconds. Insure that the smallest number of slices is 5 or
9.5.1 Be careful that the injection size chosen does not greater.
exceed the linear range of the detector. The typical sample size 10.1.3 Verify that the slice width used to acquire the sample
ranges from 0.2 µL to 2.0 µL of the diluted sample. The chromatogram is the same used to acquire the blank run
maximum sample signal amplitude should not exceed the chromatogram.
TABLE 3 Calibration Table

# Name RT (min) BP (°C)
1 n-C5 0.11 36.1
2 n-C6 0.14 68.7
3 N-C7 0.21 98.4
4 N-C8 0.34 125.7
5 N-C9 0.61 150.8
6 N-C10 1.11 174.1
7 N-C11 1.89 195.9
8 N-C12 2.91 216.3
9 N-C13 4.02 235.4
10 N-C14 5.17 253.9
11 N-C15 6.30 270.6
12 N-C16 7.39 287.2
13 N-C17 8.42 301.9
14 N-C18 9.42 316.1
15 N-C20 11.27 343.9
16 N-C22 12.94 368.3
17 N-C24 14.51 391.1
18 N-C26 15.97 412.2
19 N-C2S 17.33 431.1
20 N-C30 18.60 449.7
21 N-C32 19.79 466.1
22 N-C34 20.92 481.1
23 N-C36 21.98 496.1
24 N-C38 22.98 508.9
25 N-C40 23.96 522.2
26 N-C42 24.84 533.9
27 N-C44 25.70 545.0
28 N-C46 26.52 556.1
29 N-C48 27.30 566.1
30 N-C50 28.06 575.0
31 N-C52 28.78 583.9
32 N-C54 29.48 592.2
33 N-C56 30.15 600.0
34 N-C58 30.81 807.8
35 N-C60 31.47 615.0
36 n-C62 32.06 622.2
37 n-C64 32.65 628.9
8
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FIG. 3 Typical Chromatogram
10.2 Chromatograms Offset for Sample and Blank— 10.2.1.1 Calculate the average slice offset of sample chro-
Perform a slice offset for the sample chromatogram and blank matogram using the first second of acquired slices. Insure that
chromatogram. This operation is necessary so that the signal is no sample has eluted during this time and that the number of
corrected from its displacement from the origin. This is slices acquired is at least 5. Throw out any of the first N slices
achieved by determining an average slice offset from the slices selected that are not within one standard deviation of the
accumulated in the first segment (that is, first s) and performing average and recompute the average. This eliminates any area
a standard deviation calculation for the first N slices accumu- that is due to possible baseline upset from injection.
lated. It is carried out for both sample signal and baseline 10.2.1.2 Subtract the average slice offset from all the slices
signal. of the sample chromatogram. Set negative slices to zero. This
10.2.1 Sample Offset: will zero the chromatogram.
9
D7213 − 15 (2019)
10.2.2 Blank Offset: algorithm in 10.9.1) to determine the time that will generate the
exact 99.5 % of the area. Calculate the boiling point tempera-
NOTE 4—If you are using electronic baseline compensation proceed to
10.4. It is strongly recommended that a blank baseline be acquired with or ture corresponding to this slice time using the calibration table.
without solvent according to how the sample was prepared for injection. Use interpolation when required (refer to the algorithm in
The slice by slice offset is a preferred method for offset the signals. 10.9.2).
10.2.2.1 Repeat 10.2.1 using the blank run table. 10.8.3 Intermediate Boiling Point—For each point between
1 % and 99 %, find the time where the cumulative sum is equal
10.3 Offset the Sample Chromatogram with Blank
to or greater than the area percent being analyzed. As in 10.8.1
Chromatogram—Subtract from each slice in the sample chro-
and 10.8.2, use interpolation when the accumulated sum
matogram table with its correspondent slice in the blank run
exceeds the area percent to be estimated (refer to the algorithm
chromatogram table. Set negative slices to zero.
in 10.9.1). Use the calibration table to assign the boiling point.
10.4 Determine the Start of Sample Elution Time.
10.9 Calculation Algorithm:
10.4.1 Calculate the Total Area—Add all the corrected
10.9.1 Calculations to determine the exact point in time that
slices in the table. If the sample to be analyzed has a solvent
will generate the X percent of total area, where X = 0.5, 1, 2, ...,
peak, start counting area from the point at which the solvent
99.5 %.
peak has eluted completely. Otherwise, start at the first cor-
rected slice. 10.9.1.1 Record the time of the slice just prior to the slice
that will generate an accumulative slice area larger than the X
10.4.2 Calculate the Rate of Change Between Each Two
percent of the total area. Let us call this time, Ts, and the
Consecutive Area Slices—Begin at the slice set in 10.4.1 and
accumulative area at this point, Ac.
work forward. The rate of change is obtained by subtracting the
area of a slice from the area of the immediately preceding slice 10.9.1.2 Calculate the fraction of the slice required to
and dividing by the slice width. The time where the rate of produce the exact X percent of the total area:
change first exceeds 0.0001 % per second of the total area (see X 2 Ac
Ax 5 (3)
10.4.1) is defined as the start of sample elution time. To reduce A c11 2 A c
the possibility of noise or an electronic spike falsely indicating
where:
the start of sample elution time, a 1 s slice average can be used
instead of a single slice. For noisier baselines, a slice average Ax = fraction of the slice that will yield the exact percent,
larger than 3 s may be required Ac = cumulative percent up to the slice prior to X,
Ac + 1 = cumulative percent up to the slice right after X, and
10.5 Determine the End of Sample Elution Time. X = desired cumulative percent.
10.9.1.3 Calculate the time required to generate the fraction
Consecutive Area Slices—Begin at the end of run and work
of area Ax:
backwards. The rate of change is obtained by subtracting the
area of a slice from the area of the immediately preceding slice T f 5 A x ·W (4)
and dividing by the slice width. The time where the rate of where:
change first exceeds 0.00001 % per second of the total area
W = the slice width,
(see 10.4.1) is defined as the end of sample elution time. To Ax = fraction of the slice that will yield the exact percent,
reduce the possibility of noise or an electronic spike falsely and
indicating the end of sample elution time, a 1 s slice average Tf = fraction of time that will yield Ax.
can be used instead of a single slice. For noisier baselines, a
slice average larger than 1 s may be required. 10.9.1.4 Record the exact time where the accumulative area
is equal to the X percent of the total area:
10.6 Calculate the Sample Total Area—Add all the slices
from the slice corresponding to the start of sample elution time T t 5 T s 1T f (5)
to the slice corresponding to the end of sample elution time. where:
10.7 Normalize to Area Percent—Divide each slice in the Ts = fraction of the slice that yields the cumulative percent
sample chromatogram table by the total area (see 10.6) and up to the slice prior to X,
multiply it by 100. Tf = fraction of time that will yield Ax, and
Tt = time where the cumulative area is equal to X percent of
10.8 Calculate the Boiling Point Distribution Table:
the total area.
10.8.1 Initial Boiling Point—Add slices in the sample chro-
matogram until the sum is equal to or greater than 0.5 %. If the 10.9.2 Interpolate to determine the exact boiling point given
sum is greater than 0.5 %, interpolate (refer to the algorithm in the retention time corresponding to the cumulative slice area.
10.9.1) to determine the time that will generate the exact 0.5 % 10.9.2.1 Compare the given time against each retention time
of the area. Calculate the boiling point temperature correspond- in the calibration table. Select the nearest standard having a
ing to this slice time using the calibration table. Use interpo- retention time equal to or larger than the interpolation time.
lation when required (refer to the algorithm in 10.9.2). (Warning—The retention time table shall be sorted in ascend-
10.8.2 Final Boiling Point—Add slices in the sample chro- ing order.)
matogram until the sum is equal to or greater than 99.5 %. If 10.9.2.2 If the interpolation time is equal to the retention
the sum is greater than 99.5 %, interpolate (refer to the time of the standard, record the corresponding boiling point.
10
D7213 − 15 (2019)
10.9.2.3 If the retention time is not equal to a retention time where:
of the standards (see 9.3), interpolate the boiling point tem- mn = (BPn − BPn-1) / (RTn − RTn-1)
perature as follows: BPx = boiling point extrapolated,
10.9.2.4 If the interpolation time is less than the first RTx = retention time to be extrapolated,
retention time in the calibration table, then extrapolate using RTn-1 = retention time of the standard component eluting
the first two components in the table: prior to the last component in the calibration table,
BPx 5 m 1 · ~ RTx 2 RT1 ! 1BP1 (6)
BPn-1 = boiling point of the standard component eluting
prior to the last component in the calibration table,
where: RTn = retention time of the last component in the calibra-
m1 = (BP2 − BP1) / (RT2 − RT1), tion table, and
BPx = boiling point extrapolated, BPn = boiling point of the standard component in the
RTx = retention time to be extrapolated, calibration table.
RT1 = retention time of the first component in the calibration
table, 11. Report
BP1 = boiling point of the first component in the calibration
table, 11.1 Report the temperature to the nearest 0.5 °C (1 °F) at
RT2 = retention time of the second component in the cali- 1 % intervals between 1 % and 99 % and at the IBP (0.5 %)
bration table, and and the FBP (99.5 %). Other report formats based upon users’
BP2 = boiling point of the second component in the calibra- needs may be employed.
tion table. NOTE 5—If a plot of the boiling point distribution curve is desired, use
10.9.2.5 If the interpolation time is between two retention a spreadsheet with uniform subdivisions and use either retention time or
temperature as the horizontal axis. The vertical axis will represent the
times in the calibration table, then interpolate using the upper
sample boiling range distribution from 0 % to 100 %. Plot each boiling
and lower standard components: point temperature against its corresponding accumulated percent slice
BPx 5 m u · ~ RTx 2 RT1 ! 1BP1 (7) area. Draw a smooth curve connecting the points.

mu = (BPu − BP1) / (RTu − RT1),
BPx = boiling point extrapolated, 12.1 Precision—The precision of this test method as deter-
RTx = retention time to be extrapolated, mined by the statistical examination of the Interlaboratory
RT1 = retention time of the lower bound component in the Study (ILS) is as follows:
calibration table, 12.1.1 Repeatability—The difference between successive
BP1 = boiling point of the lower bound component in the test results obtained by the same operator with the same
calibration table,
RTu = retention time of the upper bound component in the
calibration table, and material would, in the long run, in the normal and correct
BPu = boiling point of the upper bound component in the operation of the test method, exceed the following values by
calibration table. only one case in twenty (see Table 4).
10.9.2.6 If the interpolation time is larger than the last
retention time in the calibration table, then extrapolate using
5
the last two standard components in the table: Supporting data have been filed at ASTM International Headquarters and may
BPx 5 m n · ~ RTx 2 RTn21 ! 1BPn21 (8) Service at service@astm.org.
TABLE 4 Repeatability (r) and Reproducibility (R)

X = Temperature Obtained in (°C)A
(°C) Temperature
% m/m r (°C) R (°C) Range
RR Samples
0.5 (IBP) 2.2844 9.3886 142 to 419
5 1.4949E03 * X ^ (-1.1741) 4.6038E03 * X ^ (-1.1741) 201 to 458
10 1.6442 4.2859 232 to 465
20 8.753E-03 * (588.151 - X) 2.152E-02 * (588.151 - X) 272 to 487
30 6.157E-03 * (637.8967 - X) 1.835E-02 * (637.8967 - X) 303 to 497
40 1.114E-02 * (568.737 - X) 2.956E-02 * ( 568.737- X) 329 to 505
50 1.2821 3.3963 354 to 512
60 1.2853 2.8556 382 to 519
70 1.0698 * (528.001 - X) ^ 0.0664 2.367 * (528.001 - X) ^ 0.0664 414 to 526
80 1.5749 3.0534 435 to 536
90 2.4209 *(560.6001 - X) ^ -0.1658 4.9104* (560.6001 - X) ^ -0.1658 449 to 557
95 1.8112 5.0888 462 to 563
99.5 (FBP) 7.259E-04 * X ^ 1.4248 2.517E-03 * X ^ 1.4248 508 to 612
A
Round boiling point to the nearest 0.5 °C.
11
D7213 − 15 (2019)
12.1.2 Reproducibility—The difference between two single 12.2.1 A rigorous, theoretical definition of the boiling range
and independent results obtained by different operators work- distribution of petroleum fractions is not possible due to the
ing in different laboratories on identical test material would, in complexity of the mixture as well as the unquantifiable
the long run, exceed the following values only one case in interactions among the components (for example, azeotropic
twenty (see Table 4). behavior). Any other means used to define the distribution
12.1.3 Example calculations on the precision is shown in would require the use of a physical process, such as conven-
Table 5. tional physical distillation or gas chromatographic character-
NOTE 6—This precision estimate is based on the analysis of 10 samples ization. This would therefore result in a method-dependent
by 10 laboratories. definition and would not constitute a true value from which
12.2 Bias—Because the boiling point distribution can be bias can be calculated.
defined only in terms of a test method, no bias for these
procedures in Test Method D7213 for determining the boiling 13. Keywords
range distribution of light and middle petroleum fractions by 13.1 boiling range distribution; distillation; gas chromatog-
gas chromatography have been determined. raphy; petroleum; simulated distillation
12
D7213 − 15 (2019)
TABLE 5 Example of Precision at Selected Temperatures
% m/m T (°C) r (°C) R (°C)
0.5 (IBP) 280.5 2.3 9.4
5 329.5 1.7 5.1
10 348.5 1.6 4.3
20 379.5 1.8 4.5
30 400 1.5 4.4
40 435.5 1.5 3.9
50 433 1.3 3.4
60 450.5 1.3 2.9
70 470 1.4 3.1
80 485.5 1.6 3.0
90 503 1.2 2.5
95 512.5 1.8 5.0
99.5 (FBP) 560 6.0 20.7
APPENDIXES
X1. BOILING POINTS OF NONPARAFFINIC HYDROCARBONS
X1.1 There is an apparent discrepancy in the boiling point atmospheric boiling points are plotted against the observed
of multiple ring-type compounds. When the retention time of retention times. If columns contained different percentages of
these compounds are compared to n-paraffins of equivalent stationary phase or different temperature programming rates
atmospheric boiling point, these ring compounds appear to be are used, the slope and curvature on the n-paraffin curve (solid
eluted early from methyl silicone columns. A plot showing 36 line) would change, but the relative relationships would remain
compounds other than n-paraffins plotted along the calibration essentially the same. Deviations of simulated distillation boil-
curve for n-paraffins alone is shown in Fig. X1.1. The ing points, as estimated from the curve, from actual boiling
numbered dots are identified in Table X1.1. In this figure the points for a few compounds are shown in Table X1.2. The
deviations obtained by plotting boiling points at 10 mm Hg
rather than 76 mm Hg are tabulated also. It is apparent that the
deviation is much less at 10 mm Hg pressure. This indicates
that the distillation data produced by gas chromatography
closely approximates those obtained in reduced pressure dis-
tillations. Since the vapor-pressure-temperature curves for
multiple-ring type compounds do not have the same slope or
curvature as those of n-paraffins, an apparent discrepancy
would exist when n-paraffin boiling points at atmospheric
pressure are used.
X1.2 However, this discrepancy does not introduce any
significant error when comparing with laboratory distillation
because the pressure shall be reduced in such procedures when
overhead temperature reach approximately 260 °C (500 °F) to
prevent cracking of the sample. Thus, distillation data are
FIG. X1.1 Boiling Point—Retention Time Relationships for Sev- subject to the same deviations experienced in simulated distil-
eral High-Boiling Multiple-Ring Type Compounds (see Table X1.1) lation by gas chromatography.
13
D7213 − 15 (2019)
TABLE X1.1 Compound Identification—Number Dots (see Fig. X1.1)
Boiling Point, Boiling Point,
Number Compound Number Compound
°C (°F) °C (°F)
2 80 (176) benzene 27 227 (441) di-n-amylsulfide
3 84 (183) thiophene 28 234 (453) tri-isopropylbenzene
5 111 (231) toluene 30 241 (466) 2-methlynaphthalene
6 116 (240) pyridine 31 295 (473) 1-methlynaphthalene
8 136 (277) 2,5-dimethlythiophene
9 139 (282) p-xylene 34 254 (894) indole
10 143 (289) di-n-propylsulfide 35 279 (534) acenaphthene
12 152 (306) cumene
13 159 (319) 1-hexahydroindan 38 298 (568) n-decylbenzene
14 171 (339) 1-decene 39 314 (598) 1-octadecene
15 173 (344) sec-butylbenzene
17 178 (352) 2,3-dihydroindene 41 339 (642) phenanthrene
18 183 (361) n-butylbenzene 42 342 (647) anthracene
19 186 (366) trans-decalin
20 194 (382) cis-decalin 44 346 (655) acridine
21 195 (383) di-n-propyldisulfide 45 395 (743) pyrene
23 231 (416) 1-dodecene 47 404 (496) triphenylene
25 218 (424) naphthalene 49 438 (820) naphthacene
26 221 (430) 2,3-benzothiophene 50 447 (837) chrysene
TABLE X1.2 Deviations of Simulated Distillation Boiling Points from Actual Boiling Points
Deviations from Deviations from
Boiling Point,
Compound Actual Boiling Point, Actual Boiling Point,
°C (°F) (760 mm)
°C (°F) (760 mm) °C (°F) (10 mm)
benzene 80 (176) +3 (+6) -2 (-4)
thiophene 84 (183) +4 (+7) +1 (+2)
toluene 111 (231) +2 (+3) -1 (-2)
p-xylene 139 (282) 0 (0) +2 (+4)
1-dodecene 213 (416) 0 (0) 0 (0)
naththalene 218 (424) -11 (-20) -4 (-8)
2,3-benzothiophene 221 (430) -13 (-23) 0 (0)
2-methylnaphthalene 241 (466) -12 (-21) -2 (-3)
dibenzothiophene 332 (630) -32 (-58) -6 (-10)
phenanthrene 339 (642) -35 (-63) -9 (-16)
athracene 342 (647) -36 (-64) -8 (-15)
pyrene 395 (743) -48 (-87) -16 (-29)
A
chrysene 447 (837) -60 (-108)
A
No data at 10 mm for chrysene.
X2. ALTERNATIVE CARRIER GASES TO HELIUM
NOTE X2.1—This appendix contains instrument conditions and results D7213 NITROGEN
obtained using nitrogen or hydrogen as an alternate carrier gas. At this Column: 5 m 0.5 3 mm-0.8 µ PDMS
time, because the test method precision and bias performance information Carrier: N2 20 mL/min
using the alternate carrier gases and conditions listed in this appendix have Oven: 40 °C to 390 °C at 10 °C ⁄min
hold -10 min
not been studied in accordance with the proper ASTM ILS process, this
FID: 400 °C
appendix is included only for information purposes. Results obtained Air: 450 mL/min H2: 45 mL/min
under the conditions described in this appendix are not considered to be Mup: N2: 15 mL/min
valid D2887 results, and shall not be represented as such. (Warning—Use SAMPLE: 0.1 µL 10 % to 20 % IN CS2
caution when hydrogen is used as the carrier gas. The use of a hydrogen D7213 HYDROGEN
sensor in the GC oven is strongly recommended in order to shut off the Column: 5 m 0.53 mm 0.8 µ PDMS
hydrogen source in case of a high concentration buildup of hydrogen Carrier: H2 20 mL/min
which exceeds the explosive limit.) Oven: 40 °C to 390 °C at 10 °C ⁄min
hold-5 min
FID: 400 °C
X2.1 This section lists the conditions for using alternative Air: 450 mL/min H2: 25 mL/min
carrier gases to helium. The data below shows the conditions: Mup: N2: 25 mL/min
SAMPLE : 0.1 µL 10 % to 20 % IN CS2
X2.2 Typical chromatogram obtained with hydrogen carrier

for the calibration is shown in Fig. X2.1. Fig. X2.2 is the
chromatogram of the reference gas oil #1–batch 2 utilizing H2
as carrier.
14
D7213 − 15 (2019)
FIG. X2.1 Typical Chromatogram Obtained with Hydrogen Carrier for Calibration
FIG. X2.2 Chromatogram of Reference Gas Oil #1–Batch 2 Utilizing H2 as Carrier
15
D7213 − 15 (2019)
TABLE X2.1 ASTM D2887 Reference Gas Oil #1 Batch 2 Boiling Point Distribution Values Obtained with H2 (left) and with N2 (right) Car-
rier Gases
% Off BP(°C) QC(°C) (-) Limit % Off BP(°C) QC(°C) (-) Limit
IBP 110.9 106.1 4.8 7 IBP 112.4 106.1 6.3 7
5 174.2 172.8 1.4 4.1 5 174.7 172.8 1.9 4.1
10 196.7 195.6 1.2 4.4 10 197.7 195.6 2.2 4.4
15 216.8 215.6 1.3 4.7 15 217.8 215.6 2.2 4.7
20 234.4 233.3 1 5 20 235.4 233.3 2.1 5
25 251.2 25 252.7
30 267.5 266.7 0.8 4.8 30 268.9 266.7 2.3 4.8
35 283.4 35 284.9
40 298.1 297.8 0.3 4.3 40 299.3 297.8 1.5 4.3
45 310.2 45 311.1
50 320.8 321.1 –0.3 4.3 50 321.8 321.1 0.7 4.3
55 331.4 55 332.2
60 341.1 341.7 –0.6 4.3 60 342 341.7 0.3 4.3
65 349.9 350 –0.1 4.3 65 350.6 350 0.6 4.3
70 358.1 358.3 –0.3 4.3 70 358.8 358.3 0.5 4.3
75 367.5 367.8 –0.3 4.3 75 368.1 367.8 0.4 4.3
80 377.4 377.8 –0.4 4.3 80 378.1 377.8 0.3 4.3
85 389.9 390 –0.1 4.3 85 390.6 390 0.6 4.3
90 406.3 406.1 0.2 4.3 90 407 406.1 0.9 4.3
95 430.9 431.1 –0.2 5 95 431.9 431.1 0.8 5
FBP 498 496.1 1.9 11.8 FBP 499.7 496.1 3.6 11.8
16
Designation: D7213 − 15 (Reapproved 2019)

Boiling Range Distribution of Petroleum Distillates in the
Boiling Range from 100 °C to 615 °C by Gas
Chromatography1
1. Scope 2. Referenced Documents

1.1 This test method covers the determination of the boiling 2.1 ASTM Standards:2
range distribution of petroleum products. This test method is D86 Test Method for Distillation of Petroleum Products and
applicable to petroleum distillates having an initial boiling Liquid Fuels at Atmospheric Pressure
point greater than 100 °C and a final boiling point less than D1160 Test Method for Distillation of Petroleum Products at
615 °C at atmospheric pressure as measured by this test Reduced Pressure
method. D2887 Test Method for Boiling Range Distribution of Pe-
1.2 The test method is not applicable for analysis of troleum Fractions by Gas Chromatography
petroleum distillates containing low molecular weight compo- D2892 Test Method for Distillation of Crude Petroleum
nents (for example, naphthas, reformates, gasolines, crude (15-Theoretical Plate Column)
oils). Materials containing heterogeneous components (for D4626 Practice for Calculation of Gas Chromatographic
example, alcohols, ethers, acids or esters) or residue are not to Response Factors
be analyzed by this test method. See Test Methods D7096, D6352 Test Method for Boiling Range Distribution of Pe-
D2887, D6352, or D7169. troleum Distillates in Boiling Range from 174 °C to
1.3 This test method uses the principles of simulated distil- D7096 Test Method for Determination of the Boiling Range
lation methodology. Distribution of Gasoline by Wide-Bore Capillary Gas
1.4 The values stated in SI units are to be regarded as Chromatography
standard. No other units of measurement are included in this D7169 Test Method for Boiling Point Distribution of
standard. Samples with Residues Such as Crude Oils and Atmo-
spheric and Vacuum Residues by High Temperature Gas
Chromatography
E355 Practice for Gas Chromatography Terms and Relation-
ships
priate safety, health, and environmental practices and deter-
E594 Practice for Testing Flame Ionization Detectors Used
in Gas or Supercritical Fluid Chromatography
E1510 Practice for Installing Fused Silica Open Tubular
Development of International Standards, Guides and Recom- 3. Terminology
mendations issued by the World Trade Organization Technical
3.1 Definitions—This test method makes reference to many
Barriers to Trade (TBT) Committee.
common gas chromatographic procedures, terms, and relation-
ships. Detailed definitions of these can be found in Practices
E355, E594, and E1510.
1
2
10.1520/D7213-15R19. the ASTM website.
1
D7213 − 15 (2019)
3.2 Definitions of Terms Specific to This Standard: tion detector. The detector signal integral is recorded as area
3.2.1 area slice, n—the area, resulting from the integration slices for consecutive retention time intervals during the
of the chromatographic detector signal, within a specified analysis.
retention time interval. In area slice mode (see 6.4.2), peak 4.4 Retention times of known normal paraffin hydrocarbons
detection parameters are bypassed and the detector signal spanning the scope of this test method (C5-C60) are determined
integral is recorded as area slices of consecutive, fixed duration and correlated to their boiling point temperatures. The normal-
time intervals. ized cumulative corrected sample areas for each consecutive
3.2.2 corrected area slice, n—an area slice corrected for recorded time interval are used to calculate the boiling range
baseline offset, by subtraction of the exactly corresponding distribution. The boiling point temperature at each reported
area slice in a previously recorded blank (non-sample) analy- percent off increment is calculated from the retention time
sis. calibration.
3.2.3 cumulative corrected area, n—the accumulated sum of 5. Significance and Use
corrected area slices from the beginning of the analysis through
a given retention time, ignoring any non-sample area (for 5.1 The boiling range distribution of light and medium
example, solvent). petroleum distillate fractions provides an insight into the
composition of feed stocks and products related to petroleum
3.2.4 final boiling point (FBP), n—the temperature (corre- refining process, This gas chromatographic determination of
sponding to the retention time) at which a cumulative corrected boiling range can be used to replace conventional distillation
area count equal to 99.5 % of the total sample area under the methods for control of refining operations. This test method
chromatogram is obtained. can be used for product specification testing with the mutual
3.2.5 initial boiling point (IBP), n—the temperature (corre- agreement of interested parties.
sponding to the retention time) at which a cumulative corrected 5.2 This test method extends the scope of boiling range
area count equal to 0.5 % of the total sample area under the determination by gas chromatography to include light and
chromatogram is obtained. medium petroleum distillate fractions beyond the scope of Test
3.2.6 slice rate, n—the time interval used to integrate the Method D2887 (538 °C) and below Test Method D6352
continuous (analog) chromatographic detector response during (700 °C).
an analysis. The slice rate is expressed in Hz (for example, 5.3 Boiling range distributions obtained by this test method
integrations or slices per second). are theoretically equivalent to those obtained by true boiling
3.2.7 slice time, n—the cumulative slice rate (analysis time) point (TBP) distillation (see Test Method D2892). They are not
associated with each area slice throughout the chromatographic equivalent to results from low efficiency distillation such as
analysis. The slice time is the time at the end of each those obtained with Test Method D86 or D1160.
contiguous area slice.
6. Apparatus
3.2.8 total sample area, n—the cumulative corrected area,
from the initial point to the final area point. 6.1 Chromatograph—The gas chromatographic system used
shall have the following performance characteristics:
3.3 Abbreviations—A common abbreviation of hydrocarbon 6.1.1 Column Oven—Capable of sustained and linear pro-
compounds is to designate the number of carbon atoms in the grammed temperature operation from near ambient (for
compound. A prefix is used to indicate the carbon chain form, example, 35 °C to 50 °C) up to 400 °C.
while a subscripted suffix denotes the number of carbon atoms 6.1.2 Column Temperature Programmer—The chromato-
(for example, normal decane n-Cl0; iso-tetradecane = i-Cl4). graph shall be capable of linear programmed temperature
operation up to 400 °C at selectable linear rates up to
4. Summary of Test Method 20 °C ⁄min. The programming rate shall be sufficiently repro-
4.1 The boiling range distribution by distillation is simu- ducible to obtain the retention time repeatability of 0.1 min
lated by the use of gas chromatography. The solvent should not (6 s) for each component in the calibration mixture described
interfere with measurement of the sample in the 100 °C to in 7.5.
615 °C range, and it should be apolar. A non-polar open tubular 6.1.3 Detector—This test method requires a flame ioniza-
(capillary) gas chromatographic column is used to elute the tion detector (FID). The detector shall meet or exceed the
hydrocarbon components of the sample in order of increasing following specifications as detailed in Practice E594. The
boiling point. flame jet should have an orifice of approximately 0.45 mm to
0.50 mm.
4.2 A sample aliquot is diluted with a viscosity reducing 6.1.3.1 Operating Temperature, 400 °C.
solvent and introduced into the chromatographic system. 6.1.3.2 Sensitivity, >0.005 coulombs/g carbon.
Sample vaporization is provided by separate heating of the 6.1.3.3 Minimum Detectability, 1 × 10-11 g carbon/s.
point of injection or in conjunction with column oven heating. 6.1.3.4 Linear Range, >106.
4.3 The column oven temperature is raised at a reproducible 6.1.3.5 Connection of the column to the detector shall be
linear rate to effect separation of the hydrocarbon components such that no temperature below the column temperature exists.
in order of increasing boiling point. The elution of sample Refer to Practice E1510 for proper installation and condition-
components is quantitatively determined using a flame ioniza- ing of the capillary column.
2
D7213 − 15 (2019)
6.1.4 Sample Inlet System—Any sample inlet system ca- 7. Reagents and Materials3
pable of meeting the performance specification in 7.6 may be 7.1 Carrier Gas—Helium or hydrogen of high purity.
used. Programmed temperature vaporization (PTV) and pro- (Warning—Helium and hydrogen are compressed gases under
grammable cool on-column injection systems have been used high pressure; hydrogen is an extremely flammable gas under
successfully. high pressure.) These gases may be used as the carrier gas and
6.1.5 Carrier Gas Flow Control—The chromatograph shall should not contain more than 5 mL/m3 of oxygen. The total
be equipped with carrier gas pressure or flow control capable of amount of impurities should not exceed 10 mL/m3. Additional
maintaining constant carrier gas flow control through the purification is recommended by the use of molecular sieves or
column throughout the column temperature program cycle. other suitable agents to remove water, oxygen, and hydrocar-
6.2 Microsyringe—A microsyringe with a 23 gauge or bons. Available pressure shall be sufficient to ensure a constant
smaller stainless steel needle is used for on-column sample carrier gas flow rate.
introduction. Syringes of 0.1 µL to 10 µL capacity are avail- 7.2 Hydrogen—Hydrogen of high purity (for example,
able. hydrocarbon-free) is used as fuel for the flame ionization
6.2.1 Automatic syringe injection is recommended to detector (FID). (Warning—Hydrogen is an extremely flam-
achieve best precision. mable gas under high pressure.)
7.3 Air—High purity (for example, hydrocarbon-free) com-
6.3 Column—This test method is limited to the use of
pressed air is used as the oxidant for the flame ionization
non-polar wall coated open tubular (WCOT) columns of high
detector (FID). (Warning—Compressed air is a gas under high
thermal stability. Glass, fused silica, and stainless steel
pressure and supports combustion.)
columns, with a 0.53 mm diameter have been successfully
used. Cross-linked or bonded 100 % dimethyl-polysiloxane 7.4 Solvents—Unless otherwise indicated, it is intended that
stationary phases with film thickness of 0.5 µm to 1.0 µm have all solvents conform to the specifications of the committee on
been used. The column length and liquid phase film thickness analytical Reagents of the American Chemical Society where
shall allow the elution of at least C60 n-paraffin (BP = 615 °C). such specifications are available.3 Other grades may be used
The column and conditions shall provide separation of typical provided it is first ascertained that the solvent is of sufficiently
petroleum hydrocarbons in order of increasing boiling point high purity to permit its use without lessening the accuracy of
and meet the column resolution requirements of 8.2.1. The the determination.
column shall provide a resolution between one and ten using 7.4.1 Carbon Disulfide (CS2)—(99+ % pure) may be used as
this test method’s operating conditions. a viscosity reducing solvent and as a means of reducing mass
of sample introduced onto the column to ensure linear detector
6.4 Data Acquisition System: response and reduced peak skewness. It is miscible with
6.4.1 Recorder—A 0 mV to 1 mV range recording potenti- asphaltic hydrocarbons and provides a relatively small re-
ometer or equivalent, with a full-scale response time of 2 s or sponse with the FID. The quality (hydrocarbon content) should
less may be used to provide a graphical display. be determined by this test method prior to use as a sample
6.4.2 Integrator—Means shall be provided for determining diluent. (Warning— Carbon disulfide is extremely flammable
the accumulated area under the chromatogram. This can be and toxic.)
done by means of an electronic integrator or computer-based 7.5 Cyclohexane (C6H12)—(99+ % pure) may be used as a
chromatography data system. The integrator/computer system viscosity reducing solvent. It is miscible with asphaltic
shall have normal chromatographic software for measuring the hydrocarbons, however, it responds well to the FID. The
retention time and areas of eluting peaks (peak detection quality (hydrocarbon content) should be determined by this test
mode). In addition, the system shall be capable of converting method prior to use as a sample diluent. (Warning—
the continuously integrated detector signal into area slices of Cyclohexane is flammable.)
fixed duration (area slice mode). These contiguous area slices,
7.6 Calibration Mixture—A qualitative mixture of
collected for the entire analysis, are stored for later processing.
n-paraffins (nominally C5 to C60) dissolved in a suitable
The electronic range of the integrator/computer (for example, 1
solvent. The final concentration should be approximately one
V, 10 V) shall be operated within the linear range of the
part of n-paraffin mixture to one hundred parts of solvent. At
detector/electrometer system used.
NOTE 1—Some gas chromatographs have an algorithm built into their 3
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
operating software that allows a mathematical model of the baseline Standard-Grade Reference Materials, American Chemical Society, Washington,
profile to be stored in memory. This profile is automatically subtracted DC. For suggestions on the testing of reagents not listed by the American Chemical
from the detector signal on subsequent sample runs to compensate for the Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
column bleed. Some integration systems also store and automatically U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
subtract a blank analysis from subsequent analytical determinations. copeial Convention, Inc. (USPC), Rockville, MD.
3
D7213 − 15 (2019)
least one compound in the mixture shall have a boiling point NOTE 2—A suitable calibration mixture can be obtained by dissolving
lower than the initial boiling point of the sample being a polyolefin wax (for example, Polywax 5004) in a volatile solvent (for
example, carbon disulfide or cyclohexane). Solutions of one part Polywax
analyzed, as defined in the scope of this test method (1.1). The to one hundred parts solvent can be prepared. Lower boiling point
calibration mixture shall contain at least 13 known n-paraffins
(for example, C6, C7, C8, C9, C10, C12, C16, C20, C30, C40, C50,
C52, C60). Boiling points of n-paraffins are listed in Table 1. 4
Polywax is a trademark of the Baker Petrolite Corporation, Barnsdall, OK.
TABLE 1 Boiling Points of n-ParaffinsA,B

Carbon Boiling Boiling
Number Point °C Point °F
5 36 97
6 69 156
7 98 209
8 126 258
9 151 303
10 174 345
11 196 385
12 216 421
13 235 456
14 254 488
15 271 519
16 287 548
17 302 576
18 316 601
19 330 626
20 344 651
21 356 674
22 369 695
23 380 716
24 391 736
25 402 755
26 412 774
27 422 791
28 431 808
29 440 825
30 449 840
31 458 856
32 466 870
33 474 885
34 481 898
35 489 912
36 496 925
37 503 937
38 509 948
39 516 961
40 522 972
41 528 982
42 534 993
43 540 1004
44 545 1013
45 550 1022
46 556 1033
47 561 1042
48 566 1051
49 570 1058
50 575 1067
51 579 1074
52 584 1083
53 588 1090
54 592 1098
55 596 1105
56 600 1112
57 604 1119
58 608 1126
59 612 1134
60 615 1139
A
API Project 44, 72-10-31, is believed to have provided the original normal paraffin boiling point data that are listed in Table 1. However, over the years some of the data
contained in both API Project 44 (Thermodynamics Research Center Hydrocarbon Project) and Test Method D7213 have changed, and they are no longer equivalent. Table
1 represents the current normal paraffin boiling point values accepted by Subcommittee D02.04 and found in all test methods under the jurisdiction of Section D02.04.H.
B
Test Method D7213 has traditionally used n-paraffin boiling points rounded to the nearest whole degree for calibration. The boiling points listed in Table 1 are correct to
the nearest whole number in both degrees Celsius and degrees Fahrenheit. However, if a conversion is made from one unit to the other and then rounded to a whole
number, the results will not agree with the table values for a few carbon numbers. For example, the boiling point of n-heptane is 98.425 °C which is correctly rounded to
98 °C in the table. However, converting 98.425 °C gives 209.165 °F, which rounds to 208 °F, while converting 98 °C gives 208.4 °F, which rounds to 208 °F. Carbon
numbers 2, 4, 7, 8, 9, 13, 14, 15, 16, 25, 27, and 32 are affected by rounding.
4
D7213 − 15 (2019)
paraffins will have to be added to insure conformance with 7.6. Fig. 1 7.8 Reference Material—A reference sample that has been
illustrates a typical calibration mixture chromatogram. analyzed by laboratories participating in the test method
7.7 Response Linearity Mixture—Prepare a quantitatively cooperative study. Consensus values for the boiling range
weighed mixture of at least ten individual paraffins (>99 % distribution of this sample are being determined.
purity), covering the boiling range of the test method. The
highest boiling point component should be at least n-C60 . The 8. Preparation of Apparatus
mixture shall contain n-C40. Use a suitable solvent to provide
a solution of each component at approximately 0.5 % to 2.0 % 8.1 Gas Chromatograph Setup:
by mass.
FIG. 1 Typical Calibration Curve with Plot
5
D7213 − 15 (2019)
8.1.1 Place the gas chromatograph and ancillary equipment where:
into operation in accordance with the manufacturers instruc- R = resolution,
tions. Recommended operating conditions are shown in Table t1 = time for the n-C50 peak maximum,
2. t2 = time for the n-C52 peak maximum,
8.1.2 When attaching the column to the detector inlet, w1 = peak width, at half height, of the n-C50 peak and,
ensure that the end of the column terminates as close as w2 = peak width, at half height, of the n-C52 peak.
possible to the FID jet. Follow the instructions in Practice
8.2.2 Detector Response Calibration—This test method as-
E1510.
sumes that the FID response to petroleum hydrocarbons is
8.1.3 The FID should be periodically inspected and, if
necessary, remove any foreign deposits formed in the detector proportional to the mass of individual components. This shall
from combustion of silicone liquid phase or other materials. be verified when the system is put in service, and whenever any
Such deposits will change the response characteristics of the changes are made to the system or operational parameters.
detector. Analyze the response linearity mixture (see 7.7) using the
8.1.4 The inlet liner and initial portion of the column shall identical procedure to be used for the analysis of samples (see
be periodically inspected and replaced if necessary to remove Section 9). Calculate the relative response factor for each
extraneous deposits or sample residue. n-paraffin (relative to n-tetracontane) as per Practice D4626
8.1.5 Column Conditioning—A new column will require and Eq 2:
conditioning at the upper test method operating temperature to F n 5 ~ M n /A n ! / ~ M 40/A 40! (2)
reduce or eliminate significant liquid phase bleed, resulting in
a stable chromatographic baseline. Follow the guidelines where:
outlined in Practice E1510. Fn = relative response factor,
Mn = mass of the n-paraffin in the mixture,
8.2 System Performance Specification:
An = peak area of the n-paraffin in the mixture,
8.2.1 Column Resolution—The column resolution, influ- M40 = mass of the n-tetracontane in the mixture, and
enced by both the column physical parameters and operating A40 = peak area of the n-tetracontane in the mixture.
conditions, affects the overall determination of boiling range
distribution. Resolution is therefore specified to maintain 8.2.2.1 The relative response factor (Fn) of each n-paraffin
equivalence between different systems (laboratories) employ- shall not deviate from unity by more than 65 %.
ing this test method. Resolution is determined using Eq 1 and 8.2.3 Column Temperature—The column temperature pro-
the C50 and C52 paraffins from a calibration mixture analysis gram profile is selected such that the C5 peak can be differen-
(or a polywax retention time boiling point mixture) (see 7.6). tiated from the solvent and that the maximum boiling point
Resolution (R) should be at least one and not more than ten, (615 °C) n-paraffin (C60) is eluted from the column before
using the identical conditions employed for sample analyses. reaching the end of the temperature program. The actual
R 5 2 ~ t 2 2 t 1 ! / ~ 1.699 ~ w 2 1w 1 !! (1) program rate used will be influenced by other operating
TABLE 2 Recommended Operating ConditionsA

Injector Cool on-column. Temperature Programmable Inlet (no Split)
Injection temperature Oven-track mode
Auto sampler Required for best precision
Data collection Data is collected as independent area slices
(average data collection rate is 1.0 Hz or
3.3 slices per second)
Column Capillary, 5 m by 0.53 mm id
film thickness; 0.1 µm to 1.0 µm (polymethylsiloxane) 0.8 µm – 1.0 µm
was used in the ILS study
Flow conditions UHP helium at 12 mL/min (constant flow)
Carrier: He and Hydrogen were used in the ILS Study (make-up gas helium at 18 mL/min)
Detector Flame Ionization;
Temperature: 390 °C
Oven program Initial oven temperature 35 °C – 50 °C,
initial hold 0 min,
program rate 10 °C/min.,
final oven temperature 380 °C,
final hold 12 min,
equilibration time 2 min
Sample size 1 µL
Sample dilution 2 mass percent in carbon disulfide
Calibration dilution 1 mass percent in carbon disulfide
A
Hydrogen was used in the precision study. Results were found to be “statistically equivalent.” See Research Report RR:D02-1725.
6
D7213 − 15 (2019)
variables such as column dimensions, liquid phase film deviate from zero, subtract the average of these corrected area slices from
thickness, carrier gas and flow rate, and sample size. each corrected area slice in the analysis.
8.2.4 Column Elution Characteristics—The recommended 9.3 Retention Time versus Boiling Point Calibration—A
column liquid phase is a non-polar phase such as 100 % retention time versus boiling point calibration shall be per-
dimethyl-polysiloxane. formed on the same day that analyses are performed. Inject an
appropriate aliquot (0.2 µL to 2.0 µL) of the calibration mixture
9. Procedure (see 7.6) into the chromatograph, using the analysis sequence
9.1 Analysis Sequence Protocol—Define and use a predeter- protocol. Obtain a normal (peak detection) data record in order
mined schedule of analysis events designed to achieve maxi- to determine the peak retention times and the peak areas for
mum reproducibility for these determinations. The schedule each component. Collect a time slice area record if a boiling
will include cooling the column oven and injector to the initial range distribution report is desired. Fig. 1 illustrates a graphical
starting temperature, equilibration time, sample injection and plot of a calibration analysis.
system start, analysis, and final temperature hold time. 9.3.1 Inspect the chromatogram of the calibration mixture
9.1.1 After chromatographic conditions have been set to for evidence of skewed (non-Gaussian shaped) peaks. Skew-
meet performance requirements, program the column tempera- ness is often an indication of overloading the sample capacity
ture upward to the maximum temperature to be used and hold of the column, which will result in displacement of the peak
that temperature for the selected time. Following the analysis apex relative to non-overloaded peaks. Distortion in retention
sequence protocol, cool the column to the initial starting time measurement and hence errors in boiling point tempera-
temperature. ture calibration will be likely if column overloading occurs.
9.1.2 During the cool down and equilibration time, ready The column liquid phase loading has a direct bearing on
the integrator/computer system. If a retention time calibration acceptable sample size. Reanalyze the calibration mixture
is being performed, use the peak detection mode. For samples using a smaller sample size or a more dilute solution to avoid
and baseline compensation (with or without solvent injection), peak distortion.
use the area slice mode operation. The recommended slice rate 9.3.1.1 Skewness Calculation—Calculate the ratio A/B on
for this test method is 1.0 Hz (3.3 slices per second). Other specified peaks in the calibration mixture as indicated by the
slice rates may be used if within the limits of 0.02 % and 0.2 % designations in Fig. 2. A is the width in seconds of the portion
of the retention time of the final calibration component (C60). of the peak eluting prior to the time of the peak apex and
Faster slice rates may be used, as may be required for other measured at 10 % of peak height (0.10-H), and B is the width
reasons, if provision is made to accumulate (bunch) the slice in seconds of the portion of the peak eluting after the time of
data to within these limits prior to determination of the boiling the peak apex at 10 % of peak height (0.10-H). This ratio for
range distribution. n-pentacontane (n-C50) peak in the calibration mixture shall
9.1.3 At the exact time set by the schedule, inject either the not be less than 0.5 nor more than 2.0.
calibration mixture, solvent, or sample into the chromatograph;
or make no injection (baseline blank). At the time of injection,
start the chromatograph time cycle and the integrator/computer
data acquisition. Follow the analysis protocol for all subse-
quent repetitive analyses or calibrations. Since complete reso-
lution of sample peaks is not expected, do not change the
sensitivity setting during the analysis.
9.2 Baseline Blank—Perform a blank analysis (baseline
blank) at least once per day. The blank analysis may be without
injection or by injection of an equivalent solvent volume as
used with sample injections, depending upon the subsequent
data handling capabilities for baseline/solvent compensation.
The blank analysis is typically performed prior to sample
analyses, but may be useful if determined between samples or
at the end of a sample sequence to provide additional data
regarding instrument operation or residual sample carryover
from previous sample analyses.
NOTE 3—If automatic baseline correction (see Note 1) is provided by
the gas chromatograph, further correction of area slices may not be
required. However, if an electronic offset is added to the signal after
baseline compensation, additional area slice correction may be required in
the form of offset subtraction. Consult the specific instrumentation
instructions to determine if an offset is applied to the signal. If the
algorithm used is unclear, the slice area data can be examined to determine
if further correction is necessary. Determine if any offset has been added
to the compensated signal by examining the corrected area slices of those
time slices which precede the elution of any chromatographic unretained FIG. 2 Designation of Parameters for Calculation of Peak Skew-
substance. If these corrected area slices (representing the true baseline) ness
7
D7213 − 15 (2019)
9.3.2 Prepare a calibration table based upon the results of maximum calibration signal amplitude. A sample chromato-
the analysis of the calibration mixture by recording the time of gram is found in Fig. 3.
each peak maximum and the boiling point temperature in
degrees Celsius (or Fahrenheit) for every component in the 10. Calculations
mixture. Normal paraffin boiling point temperatures (atmo-
10.1 Acquisition Rate Requirements:
spheric equivalent temperatures) are listed in Table 1. An
10.1.1 The number of slices required at the beginning of
example of a typical calibration report, showing retention times
data acquisition depends on chromatographic variables such as
and boiling points for each n-paraffin, is found in Table 3.
the column flow, column film thickness, and initial column
9.4 Sample Preparation—Sample aliquots are introduced temperature as well as column length. In addition, the detector
into the gas chromatograph as solutions in a suitable solvent signal level has to be as low as possible at the initial
(for example, carbon disulfide or cyclohexane). temperature of the analysis. The detector signal level for both
9.4.1 Dilute the sample to approximately 2 % by weight the sample signal and the blank at the beginning of the run has
with the solvent. to be similar for proper zeroing of the signals.
9.4.2 Seal (cap) the vial, and mix the contents thoroughly to 10.1.2 The sampling frequency has to be adjusted so that at
provide a homogeneous mixture. It may be necessary to warm least a significant number of slices are acquired prior to the
the mixture initially to effect complete solution of the sample. start of elution of sample or solvent. For example, if the time
However, the sample shall be in stable solution at room for start of sample elution is 0.06 min (3.6 s), a sampling rate
temperature prior to injection. of 5 Hz would acquire 18 slices. However, a rate of 1 Hz would
9.5 Sample Analysis—Using the analysis sequence protocol only acquire 3.6 slices which would not be sufficient for
inject a diluted sample aliquot into the gas chromatograph. zeroing the signals. Rather than specifying number of slices, it
Collect a contiguous time slice record of the entire analysis is important to select an initial time segment, that is, one or two
(area slice mode). seconds. Insure that the smallest number of slices is 5 or
9.5.1 Be careful that the injection size chosen does not greater.
exceed the linear range of the detector. The typical sample size 10.1.3 Verify that the slice width used to acquire the sample
ranges from 0.2 µL to 2.0 µL of the diluted sample. The chromatogram is the same used to acquire the blank run
maximum sample signal amplitude should not exceed the chromatogram.
TABLE 3 Calibration Table

# Name RT (min) BP (°C)
1 n-C5 0.11 36.1
2 n-C6 0.14 68.7
3 N-C7 0.21 98.4
4 N-C8 0.34 125.7
5 N-C9 0.61 150.8
6 N-C10 1.11 174.1
7 N-C11 1.89 195.9
8 N-C12 2.91 216.3
9 N-C13 4.02 235.4
10 N-C14 5.17 253.9
11 N-C15 6.30 270.6
12 N-C16 7.39 287.2
13 N-C17 8.42 301.9
14 N-C18 9.42 316.1
15 N-C20 11.27 343.9
16 N-C22 12.94 368.3
17 N-C24 14.51 391.1
18 N-C26 15.97 412.2
19 N-C2S 17.33 431.1
20 N-C30 18.60 449.7
21 N-C32 19.79 466.1
22 N-C34 20.92 481.1
23 N-C36 21.98 496.1
24 N-C38 22.98 508.9
25 N-C40 23.96 522.2
26 N-C42 24.84 533.9
27 N-C44 25.70 545.0
28 N-C46 26.52 556.1
29 N-C48 27.30 566.1
30 N-C50 28.06 575.0
31 N-C52 28.78 583.9
32 N-C54 29.48 592.2
33 N-C56 30.15 600.0
34 N-C58 30.81 807.8
35 N-C60 31.47 615.0
36 n-C62 32.06 622.2
37 n-C64 32.65 628.9
8
D7213 − 15 (2019)
FIG. 3 Typical Chromatogram
10.2 Chromatograms Offset for Sample and Blank— 10.2.1.1 Calculate the average slice offset of sample chro-
Perform a slice offset for the sample chromatogram and blank matogram using the first second of acquired slices. Insure that
chromatogram. This operation is necessary so that the signal is no sample has eluted during this time and that the number of
corrected from its displacement from the origin. This is slices acquired is at least 5. Throw out any of the first N slices
achieved by determining an average slice offset from the slices selected that are not within one standard deviation of the
accumulated in the first segment (that is, first s) and performing average and recompute the average. This eliminates any area
a standard deviation calculation for the first N slices accumu- that is due to possible baseline upset from injection.
lated. It is carried out for both sample signal and baseline 10.2.1.2 Subtract the average slice offset from all the slices
signal. of the sample chromatogram. Set negative slices to zero. This
10.2.1 Sample Offset: will zero the chromatogram.
9
D7213 − 15 (2019)
10.2.2 Blank Offset: algorithm in 10.9.1) to determine the time that will generate the
exact 99.5 % of the area. Calculate the boiling point tempera-
NOTE 4—If you are using electronic baseline compensation proceed to
10.4. It is strongly recommended that a blank baseline be acquired with or ture corresponding to this slice time using the calibration table.
without solvent according to how the sample was prepared for injection. Use interpolation when required (refer to the algorithm in
The slice by slice offset is a preferred method for offset the signals. 10.9.2).
10.2.2.1 Repeat 10.2.1 using the blank run table. 10.8.3 Intermediate Boiling Point—For each point between
1 % and 99 %, find the time where the cumulative sum is equal
10.3 Offset the Sample Chromatogram with Blank
to or greater than the area percent being analyzed. As in 10.8.1
Chromatogram—Subtract from each slice in the sample chro-
and 10.8.2, use interpolation when the accumulated sum
matogram table with its correspondent slice in the blank run
exceeds the area percent to be estimated (refer to the algorithm
chromatogram table. Set negative slices to zero.
in 10.9.1). Use the calibration table to assign the boiling point.
10.4 Determine the Start of Sample Elution Time.
10.9 Calculation Algorithm:
10.4.1 Calculate the Total Area—Add all the corrected
10.9.1 Calculations to determine the exact point in time that
slices in the table. If the sample to be analyzed has a solvent
will generate the X percent of total area, where X = 0.5, 1, 2, ...,
peak, start counting area from the point at which the solvent
99.5 %.
peak has eluted completely. Otherwise, start at the first cor-
rected slice. 10.9.1.1 Record the time of the slice just prior to the slice
that will generate an accumulative slice area larger than the X
percent of the total area. Let us call this time, Ts, and the
Consecutive Area Slices—Begin at the slice set in 10.4.1 and
accumulative area at this point, Ac.
work forward. The rate of change is obtained by subtracting the
area of a slice from the area of the immediately preceding slice 10.9.1.2 Calculate the fraction of the slice required to
and dividing by the slice width. The time where the rate of produce the exact X percent of the total area:
change first exceeds 0.0001 % per second of the total area (see X 2 Ac
Ax 5 (3)
10.4.1) is defined as the start of sample elution time. To reduce A c11 2 A c
the possibility of noise or an electronic spike falsely indicating
where:
the start of sample elution time, a 1 s slice average can be used
instead of a single slice. For noisier baselines, a slice average Ax = fraction of the slice that will yield the exact percent,
larger than 3 s may be required Ac = cumulative percent up to the slice prior to X,
Ac + 1 = cumulative percent up to the slice right after X, and
10.5 Determine the End of Sample Elution Time. X = desired cumulative percent.
10.9.1.3 Calculate the time required to generate the fraction
Consecutive Area Slices—Begin at the end of run and work
of area Ax:
backwards. The rate of change is obtained by subtracting the
area of a slice from the area of the immediately preceding slice T f 5 A x ·W (4)
and dividing by the slice width. The time where the rate of where:
change first exceeds 0.00001 % per second of the total area
W = the slice width,
(see 10.4.1) is defined as the end of sample elution time. To Ax = fraction of the slice that will yield the exact percent,
reduce the possibility of noise or an electronic spike falsely and
indicating the end of sample elution time, a 1 s slice average Tf = fraction of time that will yield Ax.
can be used instead of a single slice. For noisier baselines, a
slice average larger than 1 s may be required. 10.9.1.4 Record the exact time where the accumulative area
is equal to the X percent of the total area:
10.6 Calculate the Sample Total Area—Add all the slices
from the slice corresponding to the start of sample elution time T t 5 T s 1T f (5)
to the slice corresponding to the end of sample elution time. where:
10.7 Normalize to Area Percent—Divide each slice in the Ts = fraction of the slice that yields the cumulative percent
sample chromatogram table by the total area (see 10.6) and up to the slice prior to X,
multiply it by 100. Tf = fraction of time that will yield Ax, and
Tt = time where the cumulative area is equal to X percent of
10.8 Calculate the Boiling Point Distribution Table:
the total area.
10.8.1 Initial Boiling Point—Add slices in the sample chro-
matogram until the sum is equal to or greater than 0.5 %. If the 10.9.2 Interpolate to determine the exact boiling point given
sum is greater than 0.5 %, interpolate (refer to the algorithm in the retention time corresponding to the cumulative slice area.
10.9.1) to determine the time that will generate the exact 0.5 % 10.9.2.1 Compare the given time against each retention time
of the area. Calculate the boiling point temperature correspond- in the calibration table. Select the nearest standard having a
ing to this slice time using the calibration table. Use interpo- retention time equal to or larger than the interpolation time.
lation when required (refer to the algorithm in 10.9.2). (Warning—The retention time table shall be sorted in ascend-
10.8.2 Final Boiling Point—Add slices in the sample chro- ing order.)
matogram until the sum is equal to or greater than 99.5 %. If 10.9.2.2 If the interpolation time is equal to the retention
the sum is greater than 99.5 %, interpolate (refer to the time of the standard, record the corresponding boiling point.
10
D7213 − 15 (2019)
10.9.2.3 If the retention time is not equal to a retention time where:
of the standards (see 9.3), interpolate the boiling point tem- mn = (BPn − BPn-1) / (RTn − RTn-1)
perature as follows: BPx = boiling point extrapolated,
10.9.2.4 If the interpolation time is less than the first RTx = retention time to be extrapolated,
retention time in the calibration table, then extrapolate using RTn-1 = retention time of the standard component eluting
the first two components in the table: prior to the last component in the calibration table,
BPx 5 m 1 · ~ RTx 2 RT1 ! 1BP1 (6)
BPn-1 = boiling point of the standard component eluting
prior to the last component in the calibration table,
where: RTn = retention time of the last component in the calibra-
m1 = (BP2 − BP1) / (RT2 − RT1), tion table, and
BPx = boiling point extrapolated, BPn = boiling point of the standard component in the
RTx = retention time to be extrapolated, calibration table.
RT1 = retention time of the first component in the calibration
table, 11. Report
BP1 = boiling point of the first component in the calibration
table, 11.1 Report the temperature to the nearest 0.5 °C (1 °F) at
RT2 = retention time of the second component in the cali- 1 % intervals between 1 % and 99 % and at the IBP (0.5 %)
bration table, and and the FBP (99.5 %). Other report formats based upon users’
BP2 = boiling point of the second component in the calibra- needs may be employed.
tion table. NOTE 5—If a plot of the boiling point distribution curve is desired, use
10.9.2.5 If the interpolation time is between two retention a spreadsheet with uniform subdivisions and use either retention time or
temperature as the horizontal axis. The vertical axis will represent the
times in the calibration table, then interpolate using the upper
sample boiling range distribution from 0 % to 100 %. Plot each boiling
and lower standard components: point temperature against its corresponding accumulated percent slice
BPx 5 m u · ~ RTx 2 RT1 ! 1BP1 (7) area. Draw a smooth curve connecting the points.

mu = (BPu − BP1) / (RTu − RT1),
BPx = boiling point extrapolated, 12.1 Precision—The precision of this test method as deter-
RTx = retention time to be extrapolated, mined by the statistical examination of the Interlaboratory
RT1 = retention time of the lower bound component in the Study (ILS) is as follows:
calibration table, 12.1.1 Repeatability—The difference between successive
BP1 = boiling point of the lower bound component in the test results obtained by the same operator with the same
calibration table,
RTu = retention time of the upper bound component in the
calibration table, and material would, in the long run, in the normal and correct
BPu = boiling point of the upper bound component in the operation of the test method, exceed the following values by
calibration table. only one case in twenty (see Table 4).
10.9.2.6 If the interpolation time is larger than the last
retention time in the calibration table, then extrapolate using
5
the last two standard components in the table: Supporting data have been filed at ASTM International Headquarters and may
BPx 5 m n · ~ RTx 2 RTn21 ! 1BPn21 (8) Service at service@astm.org.
TABLE 4 Repeatability (r) and Reproducibility (R)

X = Temperature Obtained in (°C)A
(°C) Temperature
% m/m r (°C) R (°C) Range
RR Samples
0.5 (IBP) 2.2844 9.3886 142 to 419
5 1.4949E03 * X ^ (-1.1741) 4.6038E03 * X ^ (-1.1741) 201 to 458
10 1.6442 4.2859 232 to 465
20 8.753E-03 * (588.151 - X) 2.152E-02 * (588.151 - X) 272 to 487
30 6.157E-03 * (637.8967 - X) 1.835E-02 * (637.8967 - X) 303 to 497
40 1.114E-02 * (568.737 - X) 2.956E-02 * ( 568.737- X) 329 to 505
50 1.2821 3.3963 354 to 512
60 1.2853 2.8556 382 to 519
70 1.0698 * (528.001 - X) ^ 0.0664 2.367 * (528.001 - X) ^ 0.0664 414 to 526
80 1.5749 3.0534 435 to 536
90 2.4209 *(560.6001 - X) ^ -0.1658 4.9104* (560.6001 - X) ^ -0.1658 449 to 557
95 1.8112 5.0888 462 to 563
99.5 (FBP) 7.259E-04 * X ^ 1.4248 2.517E-03 * X ^ 1.4248 508 to 612
A
Round boiling point to the nearest 0.5 °C.
11
D7213 − 15 (2019)
12.1.2 Reproducibility—The difference between two single 12.2.1 A rigorous, theoretical definition of the boiling range
and independent results obtained by different operators work- distribution of petroleum fractions is not possible due to the
ing in different laboratories on identical test material would, in complexity of the mixture as well as the unquantifiable
the long run, exceed the following values only one case in interactions among the components (for example, azeotropic
twenty (see Table 4). behavior). Any other means used to define the distribution
12.1.3 Example calculations on the precision is shown in would require the use of a physical process, such as conven-
Table 5. tional physical distillation or gas chromatographic character-
NOTE 6—This precision estimate is based on the analysis of 10 samples ization. This would therefore result in a method-dependent
by 10 laboratories. definition and would not constitute a true value from which
12.2 Bias—Because the boiling point distribution can be bias can be calculated.
defined only in terms of a test method, no bias for these
procedures in Test Method D7213 for determining the boiling 13. Keywords
range distribution of light and middle petroleum fractions by 13.1 boiling range distribution; distillation; gas chromatog-
gas chromatography have been determined. raphy; petroleum; simulated distillation
12
D7213 − 15 (2019)
TABLE 5 Example of Precision at Selected Temperatures
% m/m T (°C) r (°C) R (°C)
0.5 (IBP) 280.5 2.3 9.4
5 329.5 1.7 5.1
10 348.5 1.6 4.3
20 379.5 1.8 4.5
30 400 1.5 4.4
40 435.5 1.5 3.9
50 433 1.3 3.4
60 450.5 1.3 2.9
70 470 1.4 3.1
80 485.5 1.6 3.0
90 503 1.2 2.5
95 512.5 1.8 5.0
99.5 (FBP) 560 6.0 20.7
APPENDIXES
X1. BOILING POINTS OF NONPARAFFINIC HYDROCARBONS
X1.1 There is an apparent discrepancy in the boiling point atmospheric boiling points are plotted against the observed
of multiple ring-type compounds. When the retention time of retention times. If columns contained different percentages of
these compounds are compared to n-paraffins of equivalent stationary phase or different temperature programming rates
atmospheric boiling point, these ring compounds appear to be are used, the slope and curvature on the n-paraffin curve (solid
eluted early from methyl silicone columns. A plot showing 36 line) would change, but the relative relationships would remain
compounds other than n-paraffins plotted along the calibration essentially the same. Deviations of simulated distillation boil-
curve for n-paraffins alone is shown in Fig. X1.1. The ing points, as estimated from the curve, from actual boiling
numbered dots are identified in Table X1.1. In this figure the points for a few compounds are shown in Table X1.2. The
deviations obtained by plotting boiling points at 10 mm Hg
rather than 76 mm Hg are tabulated also. It is apparent that the
deviation is much less at 10 mm Hg pressure. This indicates
that the distillation data produced by gas chromatography
closely approximates those obtained in reduced pressure dis-
tillations. Since the vapor-pressure-temperature curves for
multiple-ring type compounds do not have the same slope or
curvature as those of n-paraffins, an apparent discrepancy
would exist when n-paraffin boiling points at atmospheric
pressure are used.
X1.2 However, this discrepancy does not introduce any
significant error when comparing with laboratory distillation
because the pressure shall be reduced in such procedures when
overhead temperature reach approximately 260 °C (500 °F) to
prevent cracking of the sample. Thus, distillation data are
FIG. X1.1 Boiling Point—Retention Time Relationships for Sev- subject to the same deviations experienced in simulated distil-
eral High-Boiling Multiple-Ring Type Compounds (see Table X1.1) lation by gas chromatography.
13
D7213 − 15 (2019)
TABLE X1.1 Compound Identification—Number Dots (see Fig. X1.1)
Boiling Point, Boiling Point,
Number Compound Number Compound
°C (°F) °C (°F)
2 80 (176) benzene 27 227 (441) di-n-amylsulfide
3 84 (183) thiophene 28 234 (453) tri-isopropylbenzene
5 111 (231) toluene 30 241 (466) 2-methlynaphthalene
6 116 (240) pyridine 31 295 (473) 1-methlynaphthalene
8 136 (277) 2,5-dimethlythiophene
9 139 (282) p-xylene 34 254 (894) indole
10 143 (289) di-n-propylsulfide 35 279 (534) acenaphthene
12 152 (306) cumene
13 159 (319) 1-hexahydroindan 38 298 (568) n-decylbenzene
14 171 (339) 1-decene 39 314 (598) 1-octadecene
15 173 (344) sec-butylbenzene
17 178 (352) 2,3-dihydroindene 41 339 (642) phenanthrene
18 183 (361) n-butylbenzene 42 342 (647) anthracene
19 186 (366) trans-decalin
20 194 (382) cis-decalin 44 346 (655) acridine
21 195 (383) di-n-propyldisulfide 45 395 (743) pyrene
23 231 (416) 1-dodecene 47 404 (496) triphenylene
25 218 (424) naphthalene 49 438 (820) naphthacene
26 221 (430) 2,3-benzothiophene 50 447 (837) chrysene
TABLE X1.2 Deviations of Simulated Distillation Boiling Points from Actual Boiling Points
Deviations from Deviations from
Boiling Point,
Compound Actual Boiling Point, Actual Boiling Point,
°C (°F) (760 mm)
°C (°F) (760 mm) °C (°F) (10 mm)
benzene 80 (176) +3 (+6) -2 (-4)
thiophene 84 (183) +4 (+7) +1 (+2)
toluene 111 (231) +2 (+3) -1 (-2)
p-xylene 139 (282) 0 (0) +2 (+4)
1-dodecene 213 (416) 0 (0) 0 (0)
naththalene 218 (424) -11 (-20) -4 (-8)
2,3-benzothiophene 221 (430) -13 (-23) 0 (0)
dibenzothiophene 332 (630) -32 (-58) -6 (-10)
phenanthrene 339 (642) -35 (-63) -9 (-16)
athracene 342 (647) -36 (-64) -8 (-15)
pyrene 395 (743) -48 (-87) -16 (-29)
A
chrysene 447 (837) -60 (-108)
A
No data at 10 mm for chrysene.
X2. ALTERNATIVE CARRIER GASES TO HELIUM
NOTE X2.1—This appendix contains instrument conditions and results D7213 NITROGEN
obtained using nitrogen or hydrogen as an alternate carrier gas. At this Column: 5 m 0.5 3 mm-0.8 µ PDMS
time, because the test method precision and bias performance information Carrier: N2 20 mL/min
using the alternate carrier gases and conditions listed in this appendix have Oven: 40 °C to 390 °C at 10 °C ⁄min
hold -10 min
not been studied in accordance with the proper ASTM ILS process, this
FID: 400 °C
appendix is included only for information purposes. Results obtained Air: 450 mL/min H2: 45 mL/min
under the conditions described in this appendix are not considered to be Mup: N2: 15 mL/min
valid D2887 results, and shall not be represented as such. (Warning—Use SAMPLE: 0.1 µL 10 % to 20 % IN CS2
caution when hydrogen is used as the carrier gas. The use of a hydrogen D7213 HYDROGEN
sensor in the GC oven is strongly recommended in order to shut off the Column: 5 m 0.53 mm 0.8 µ PDMS
hydrogen source in case of a high concentration buildup of hydrogen Carrier: H2 20 mL/min
which exceeds the explosive limit.) Oven: 40 °C to 390 °C at 10 °C ⁄min
hold-5 min
FID: 400 °C
X2.1 This section lists the conditions for using alternative Air: 450 mL/min H2: 25 mL/min
carrier gases to helium. The data below shows the conditions: Mup: N2: 25 mL/min
SAMPLE : 0.1 µL 10 % to 20 % IN CS2
X2.2 Typical chromatogram obtained with hydrogen carrier

for the calibration is shown in Fig. X2.1. Fig. X2.2 is the
chromatogram of the reference gas oil #1–batch 2 utilizing H2
as carrier.
14
D7213 − 15 (2019)
FIG. X2.1 Typical Chromatogram Obtained with Hydrogen Carrier for Calibration
FIG. X2.2 Chromatogram of Reference Gas Oil #1–Batch 2 Utilizing H2 as Carrier
15
D7213 − 15 (2019)
TABLE X2.1 ASTM D2887 Reference Gas Oil #1 Batch 2 Boiling Point Distribution Values Obtained with H2 (left) and with N2 (right) Car-
rier Gases
% Off BP(°C) QC(°C) (-) Limit % Off BP(°C) QC(°C) (-) Limit
IBP 110.9 106.1 4.8 7 IBP 112.4 106.1 6.3 7
5 174.2 172.8 1.4 4.1 5 174.7 172.8 1.9 4.1
10 196.7 195.6 1.2 4.4 10 197.7 195.6 2.2 4.4
15 216.8 215.6 1.3 4.7 15 217.8 215.6 2.2 4.7
20 234.4 233.3 1 5 20 235.4 233.3 2.1 5
25 251.2 25 252.7
30 267.5 266.7 0.8 4.8 30 268.9 266.7 2.3 4.8
35 283.4 35 284.9
40 298.1 297.8 0.3 4.3 40 299.3 297.8 1.5 4.3
45 310.2 45 311.1
50 320.8 321.1 –0.3 4.3 50 321.8 321.1 0.7 4.3
55 331.4 55 332.2
60 341.1 341.7 –0.6 4.3 60 342 341.7 0.3 4.3
65 349.9 350 –0.1 4.3 65 350.6 350 0.6 4.3
70 358.1 358.3 –0.3 4.3 70 358.8 358.3 0.5 4.3
75 367.5 367.8 –0.3 4.3 75 368.1 367.8 0.4 4.3
80 377.4 377.8 –0.4 4.3 80 378.1 377.8 0.3 4.3
85 389.9 390 –0.1 4.3 85 390.6 390 0.6 4.3
90 406.3 406.1 0.2 4.3 90 407 406.1 0.9 4.3
95 430.9 431.1 –0.2 5 95 431.9 431.1 0.8 5
FBP 498 496.1 1.9 11.8 FBP 499.7 496.1 3.6 11.8
16

Evaluating Lubricity of Diesel Fuels by the High-Frequency
Reciprocating Rig (HFRR) by Visual Observation1

1.1 This test method covers the evaluation of the lubricity of 2.1 ASTM Standards:2
diesel fuels using a high-frequency reciprocating rig (HFRR). D975 Specification for Diesel Fuel Oils
1.2 This test method is applicable to middle distillate fuels, Petroleum Products
such as Grades No. 1-D S15, S500, and S5000, and Grades No. D4177 Practice for Automatic Sampling of Petroleum and
2-D S15, S500, and S5000 diesel fuels, in accordance with Petroleum Products
Specification D975; and other similar petroleum-based fuels D4306 Practice for Aviation Fuel Sample Containers for
which can be used in diesel engines. This test method also is Tests Affected by Trace Contamination
applicable to biodiesel blends. B5 was included in the round D6078 Test Method for Evaluating Lubricity of Diesel Fuels
robin program that determined the precision statement. by the Scuffing Load Ball-on-Cylinder Lubricity Evalua-
NOTE 1—It is not known that this test method will predict the
tor (SLBOCLE)
performance of all additive/fuel combinations. Additional work is under- E18 Test Methods for Rockwell Hardness of Metallic Ma-
way to establish this correlation and future revisions of this test method terials
may be necessary once this work is complete. E92 Test Methods for Vickers Hardness and Knoop Hard-
1.3 The values stated in SI units are to be regarded as ness of Metallic Materials
standard. No other units of measurement are included in this 2.2 SAE Standard:3
standard. SAE-AMS 6440 Steel, Bars, Forgings, and Tubing, 1.45 Cr
(0.93-1.05C) (SAE 52100), for Bearing Applications
safety concerns, if any, associated with its use. It is the 2.3 ISO Standard:4
responsibility of the user of this standard to establish appro- ISO 3290 Roller Bearings, Balls – Dimensions and toler-
priate safety, health, and environmental practices and deter- ances
Specific warning statements are given in Section 7. 3. Terminology
1.5 This international standard was developed in accor- 3.1 Definitions:
dance with internationally recognized principles on standard- 3.1.1 boundary lubrication, n—a condition in which the
ization established in the Decision on Principles for the friction and wear between two surfaces in relative motion are
Development of International Standards, Guides and Recom- determined by the properties of the surfaces and the properties
mendations issued by the World Trade Organization Technical of the contacting fluid, other than bulk viscosity.
Barriers to Trade (TBT) Committee. 3.1.1.1 Discussion—Metal to metal contact occurs and the
chemistry of the system is involved. Physically adsorbed or
1
2
Subcommittee D02.E0 on Burner, Diesel, Non-Aviation Gas Turbine, and Marine contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Fuels. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved Aug. 1, 2018. Published September 2018. Originally the ASTM website.
3
published in 2011. Last previous edition approved in 2016 as D7688 – 11 (2016). Available from SAE International (SAE), 400 Commonwealth Dr., Warrendale,
DOI: 10.1520/D7688-18. PA 15096-0001, http://www.sae.org.
4
This test method was developed by ISO/TC22/SC7/WG6 and is a part of ISO Available from American National Standards Institute (ANSI), 25 W. 43rd St.,
12156. 4th Floor, New York, NY 10036, http://www.ansi.org.

1
D7688 − 18
chemically reacted soft films (usually very thin) support
contact loads. As a result, some wear is inevitable.
3.1.2 lubricity, n—a qualitative term describing the ability
of a fluid to affect friction between, and wear to, surfaces in
relative motion under load.
3.1.2.1 Discussion—In this test method, the lubricity of a
fluid is evaluated by the wear scar, in microns, produced on an
oscillating ball from contact with a stationary disk immersed in
the fluid operating under defined and controlled conditions.
3.2 Abbreviations:
3.2.1 HFRR—high frequency reciprocating rig
3.2.2 WSD—wear scar diameter FIG. 1 Schematic Diagram of HFRR (not including instrumenta-
tion)
4.1 A 2-mL test specimen of fuel is placed in the test
reservoir of an HFRR. scribed test conditions. Correlation of HFRR test results with
4.2 A vibrator arm holding a nonrotating steel ball and field performance of diesel fuel injection systems has not yet
loaded with a 200 g mass is lowered until it contacts a test disk been determined.
completely submerged in the fuel. When the fuel temperature 5.6 This test method is designed to evaluate boundary
has stabilized, the ball is caused to rub against the disk with a lubrication properties. While viscosity effects on lubricity in
1 mm stroke at a frequency of 50 Hz for 75 min. this test method are not totally eliminated, they are minimized.
4.3 The test fuel temperature is maintained at 60 °C and the
ambient relative humidity is maintained between 30 % and 6. Apparatus
85 %. 6.1 High-Frequency Reciprocating Rig (HFRR),6,7—(see
4.4 At the conclusion of the test, the upper specimen holder Fig. 1) capable of rubbing a steel ball loaded with a 200 g mass
is removed from the vibrator arm and cleaned. The dimensions against a stationary steel disk completely submerged in a test
of the major and minor axes of the wear scar are measured fuel. The apparatus uses a 1 mm stroke length at a frequency of
under 100× magnification and recorded. 50 Hz for 75 min. Complete operating conditions are listed in
Table 1.
5. Significance and Use 6.2 Test Reservoir, capable of holding a test disk in a rigid
5.1 Diesel fuel injection equipment has some reliance on manner beneath the test fuel. The temperature of this reservoir,
lubricating properties of the diesel fuel. Shortened life of and consequently the test fuel contained in it, is maintained by
engine components, such as diesel fuel injection pumps and means of a closely attached electrically controlled heater pad.
injectors, has sometimes been ascribed to lack of lubricity in a 6.3 Control Unit6,7for controlling stroke length, frequency,
diesel fuel. test reservoir temperature, friction force, electrical contact
5.2 The trend of HFRR test results to diesel injection system potential, and test duration, with an electronic data acquisition
pump component distress due to wear has been demonstrated and control system.
in pump rig tests for some fuel/hardware combinations where 6.4 Microscope, capable of 100× magnification in gradua-
boundary lubrication is believed to be a factor in the operation tions of 0.1 mm and incremented in divisions of 0.01 mm.
of the component.5 6.4.1 Glass Slide Micrometer7,8with a scale ruled in
5.3 The wear scar generated in the HFRR test is sensitive to 0.01 mm divisions.
contamination of the fluids and test materials, the temperature 6.5 Cleaning Bath, ultrasonic seamless stainless steel tank
of the test fuel, and the ambient relative humidity. Lubricity with adequate capacity and a cleaning power of 40 W or
evaluations are also sensitive to trace contaminants acquired greater.
during test fuel sampling and storage.
6.6 Desiccator, capable of storing test disks, balls, and
5.4 The HFRR and Scuffing Load Ball on Cylinder Lubric- hardware.
ity Evaluator (SLBOCLE, Test Method D6078) are two meth-
ods for evaluating diesel fuel lubricity. No absolute correlation
has been developed between the two test methods. 6
5.5 The HFRR may be used to evaluate the relative effec- is PCS Instruments, 78 Stanley Gardens, London W3 7SZ, England.
7
If you are aware of alternative suppliers, please provide this information to
tiveness of diesel fuels for preventing wear under the pre- ASTM International Headquarters. Your comments will receive careful consider-
ation at a meeting of the responsible technical committee,1 which you may attend.
8
5
Nikanjam, M., Crosby, T., Henderson, P., Gray, C., Meyer, K, and Davenport, is Catalog No. 31-16-99 from Bausch & Lomb World Headquarters, One Bausch &
N., “ISO Diesel Fuel Lubricity Round Robin Program,” SAE, Paper No. 952372, Lomb Place, Rochester, NY 14604-2701. A certificate of traceability from the
SAE Fuels and Lubricants Meeting, Oct. 16-19, 1995, Toronto, Canada. National Institute of Standards and Technology is available.
2
D7688 − 18
TABLE 1 Test Conditions demonstrating that test balls and test disks meet the requirements listed in
Fluid volume 2 mL ± 0.20 mL 7.8 and 7.9.
Stroke length 1 mm ± 0.02 mm 7.10 Wiper, wiping tissue, light-duty, lint-free, hydrocarbon-
Frequency 50 Hz ± 1 Hz
Fluid temperature 60 °C ± 2°C free, disposable.
Relative humidity between 30 % and 85 %
Applied load 200 g ± 1 g 8. Sampling and Sample Containers
Test duration 75 min ± 0.1 min
Bath surface area 6 cm2 ± 1 cm2 8.1 Unless otherwise specified, samples shall be taken by
the procedure described in Practice D4057 or Practice D4177.
8.2 Because of the sensitivity of lubricity measurements to
7. Reagents and Materials trace materials, sample containers shall be only fully epoxy-
7.1 Acetone, reagent grade (Warning—Extremely flam- lined metal, amber borosilicate glass, or polytetrafluorethylene
mable. Vapors may cause flash fire). (PTFE), cleaned and rinsed thoroughly at least three times with
7.2 Compressed Air, containing less than 0.1 ppmv hydro- the product to be sampled before use, as specified under
carbons and 50 ppmv water. (Warning—Compressed gas Containers for Lubricity Testing in Practice D4306.
under high pressure. Use with extreme caution in the presence 8.3 New sample containers are preferred, but if not
of combustible material.) available, the Containers for Lubricity Testing section of
7.3 Gloves, appropriate for the reagents used. Practice D4306 gives guidance on suitable cleaning procedures
for each type of container.
7.4 Reference Fluids:
7.4.1 Fluid A9—High lubricity reference (Warning— 9. Preparation of Apparatus
Flammable). Store in clean, borosilicate glass with an alumi-
9.1 Test Disks, (as received):
num foil-lined insert cap or a fully epoxy-lined metal container.
9.1.1 Place disks in a clean beaker. Transfer a sufficient
Store in dark area.
volume of heptane or 50/50 isooctane/2-propanol into the
7.4.2 Fluid B9—Low lubricity reference (Warning—
beaker to completely cover the test disks.
Flammable. Vapor harmful). Store in clean, borosilicate glass
9.1.2 Place beaker in ultrasonic cleaner and turn on for
with an aluminum foil-lined insert cap or a fully epoxy-lined
7 min.
metal container. Store in a dark area.
9.1.3 Handle all clean test pieces with clean forceps. Re-
7.5 Heptane, reagent grade. (Warning—Extremely flam- move the test disks and repeat the above cleaning procedure
mable. Vapors may cause flash fire.) from 9.1.1 with acetone for 2 min.
7.6 Isooctane, reagent grade. (Warning—Extremely flam- 9.1.4 Dry and store in desiccator.
mable. Vapors may cause flash fire.) NOTE 3—Drying operations can be accomplished using compressed air
7.7 2-propanol, reagent grade. (Warning—Extremely flam- jet at 140 kPa to 210 kPa pressure.
mable. Vapors may cause flash fire.) 9.2 Test Balls, (as received)—The test balls are to be cleaned
7.8 Test Ball, (Grade 28 per ISO 3290) of SAE-AMS 6440 following the same procedure, 9.1.1 to 9.1.4, as for the test
steel, with a diameter of 6.00 mm, having a Rockwell hardness disks.
“C” scale (HRC) number of 58-66, in accordance with Test 9.3 Hardware—All hardware and utensils that come into
Methods E18. contact with the test disks, test balls, or test fuel, shall be
7.8.1 Test balls are an extremely important part of the cleaned by washing thoroughly with heptane or 50/50
process and can significantly affect results. An equivalency isooctane/2-propanol, rinsed with acetone, and dried.
evaluation was conducted on test balls and test disks and can be
found in ASTM Research Report RR: RR:D02-1890.10 10. Test Apparatus Inspection and Verification
7.9 Test Disk, 10 mm disk of SAE-AMS 6440 steel ma- 10.1 Recommended Calibration Intervals:
chined from annealed rod, having a Vickers hardness “HV 30,” 10.1.1 Stroke Length—Every three months.
in accordance with Specification E92, a scale number of 10.1.2 Temperature Probes—Every twelve months.
190-210, turned, lapped, and polished to a surface finish of less 10.2 Test Apparatus—Verify test apparatus performance and
than 0.02 µm Ra. accuracy at least every 20 tests by testing each reference fluid
7.9.1 Test disks are an extremely important part of the in accordance with this section. Perform one test with each
process and can significantly affect results. An equivalency reference fluid. If the WSD for either fluid is outside the
evaluation was conducted on test balls and test disks and can be specified limits provided with each fluid by the ASTM Test
found in ASTM Research Report RR: RR:D02-1890.10 Monitoring Center, verify that the test is performed correctly,
NOTE 2—Users are encouraged to request a certificate of conformance and repeat both reference tests. If necessary, calibrate the
HFRR by following the steps in the instrument manual, and
9
Reference Fluids A and B are available from ASTM Test Monitoring Center, then test each of the high and low reference fluids.
6555 Penn Ave., Pittsburgh, PA 15026–4489.
10
Supporting data have been filed at ASTM International Headquarters and may 11. Procedure
Service at service@astm.org. 11.1 Table 1 summarizes the test conditions.
3
D7688 − 18
11.2 Strict adherence to cleanliness requirements and to the 13. Calculation
specified cleaning procedures is required. During handling and 13.1 Calculate the wear scar diameter as follows:
installation procedures, protect cleaned test parts (disks, balls,
reservoir, screws, heater block, and push rod) from contami- WSD 5 @ ~ M1N ! /2 # · @ 1000#
nation by using clean forceps and wearing appropriate gloves. where:
11.3 Using forceps, place the test disk into the test reservoir, WSD = wear scar diameter, µm,
shiny side up. Secure the test disk to the test reservoir and the M = major axis, mm, and
test reservoir to the test apparatus. Ensure the unit’s tempera- N = minor axis, mm.
ture probe is properly placed in the reservoir. Ensure the 14. Report
relative humidity in the test laboratory is between 30 % and
85 %. (Warning—relative humidity is an important parameter. 14.1 Report the following information:
Performing the test outside of the relative humidity limits will 14.1.1 Major axis and minor axis to the nearest 0.01 mm,
affect the lubricity result.) and wear scar diameter to the nearest 10 µm.
14.1.2 Description of the test fuel and date sample taken.
11.4 Using forceps, place the test ball into the upper 14.1.3 Record the batch number of the test specimens.
specimen holder and attach the holder to the end of the vibrator 14.1.4 Date of testing.
arm. Ensure the holder is horizontal before fully securing the 14.1.5 Report the test method number, D7688.
unit.
15. Precision and Bias11,12
11.5 Using a pipette, place 2 mL 6 0.2 mL of the test fuel
into the test reservoir. 15.1 Precision—The precision was developed using fuels
representing a range of lubricity levels as well as a practical
11.6 Set the test parameters according to Table 1.
mix of common types of fuels, such as Grade No. 1-D, Grade
11.7 Lower the vibrator arm and suspend a 200 g weight No. 2-D, additized, and a biodiesel blend. The precision data
from the arm. Start the test. were developed in a 2008 cooperative testing program involv-
11.8 At the completion of the test, lift up the vibrator arm. ing ten testing laboratories from the United States, Canada, and
Remove the upper specimen holder. South Africa. There were six distinct fluids and each laboratory
received four samples of each fuel to conduct replicate testing
11.9 Rinse the test ball (still in the holder) in cleaning both with the microscope and the digital camera. The fluids
solvents and wipe and dry thoroughly with a tissue. were blind coded so that replicate samples were not known to
11.10 Remove the test reservoir and properly dispose of the the operator. A randomized test sequence was provided and
fuel. each laboratory was requested to use the same operator and
11.11 Place the test ball holder under the microscope and equipment for all 24 samples.
measure the wear scar diameter in accordance with Section 12. 15.1.1 The difference between two test results obtained by
the same operator with the same apparatus under constant
12. Measurement of the Wear Scar operating conditions on identical test material would, in the
long run, in the normal and correct operation of the test
12.1 Turn on the microscope light and position the test ball method, exceed the following value in only one case in twenty:
under microscope at 100× magnification. Repeatability = 70 µm
12.2 Focus the microscope and adjust the stage such that the 15.1.2 The difference between two single and independent
wear scar is centered within the field of view. results obtained by different operators working in different
laboratories on identical test material would, in the long run, in
12.3 Align the wear scar to a divisional point of reference
the normal and correct operation of the test method, exceed the
on the numerical scale with the mechanical stage controls.
following value in only one case in twenty:
Measure the major axis to the nearest 0.01 mm. Record the
Reproducibility = 90 µm
readings on the data sheet.
15.2 Bias—The procedure in this test method has no bias
12.4 Align the wear scar to a divisional point of reference
because lubricity is not a fundamental and measurable fluid
on the numerical scale with the mechanical stage controls.
property and thus is evaluated in terms of this test method.
Measure the minor axis to the nearest 0.01 mm. Record the
readings on the data sheet. 16. Keywords
12.5 Record the condition of the wear area if different from 16.1 boundary lubrication; diesel fuel; friction; HFRR; lu-
the reference standard test, that is, debris color, unusual bricity; wear
particles or wear pattern, visible galling, and so forth, and
presence of particles in the test reservoir. 11
Nikanjam, M., Rutherford, J., “Improving the Precision of the HFRR Lubricity
Test,” SAE Paper No. 2006-01-3363.
NOTE 4—Refer to Annex A1 for guidance to determine the boundaries 12
of the wear scar. be obtained by requesting Research Report RR:D02-1718.
4
D7688 − 18
ANNEX
A1. MEASUREMENT OF HFRR WEAR SCARS
INTRODUCTION
Annex A of ISO 12156-1:2006 (E) Measurement of HFRR wear scars, used by permission from
ISO/CS.
A1.1 The appearance of the wear scar on the ball can vary A1.2 In some cases, for example when low-lubricity refer-
with fuel type, particularly when lubricity additives are present. ence fluids are tested, the boundary between the scar and the
In general, the wear scar appears to be a series of scratches in discolored (but unworn) area of the ball is distinct, and it is
the direction of motion of the ball, somewhat larger in the x easy to measure the scar size. In other cases, the central
direction than in the y direction. scratched part of the scar is surrounded by a less distinct worn
area, and there is no sharp boundary between the worn and
unworn areas of the ball. In these cases, it can be more difficult
to see or measure the true scar shape; as shown in Fig. A1.1,
the overall wear scar comprises the distinct and the less distinct
areas.
A1.3 Photographic examples of various wear scar shapes
are shown in Fig. A1.2, together with an assessment of the
overall scar boundary.
5
D7688 − 18
FIG. A1.1 Example of a Wear Scar with an Indistinct Boundary
6
D7688 − 18
FIG. A1.2 Examples of Wear Scars
7
D7688 − 18
FIG. A1.2 Examples of Wear Scars (continued)
SUMMARY OF CHANGES
Subcommittee D02.E0 has identified the location of selected changes to this standard since the last issue
(D7688 – 11 (2016)) that may impact the use of this standard. (Approved Aug. 1, 2018.)
(1) Revised subsections 7.8 and 7.9, adding new subsections (2) Added new Note 2.
7.8.1 and 7.9.1.
8
D7688 − 18
9

Determination of Organic Chloride Content in Crude Oil by
Distillation Followed by Detection Using Combustion Ion
Chromatography1
1. Scope priate safety, health, and environmental practices and deter-

1.1 This test method covers the determination of organic mine the applicability of regulatory limitations prior to use.
chloride (above 1 µg/g organically-bound chlorine) in crude 1.7 This international standard was developed in accor-
oils, using distillation and combustion ion chromatography. dance with internationally recognized principles on standard-
1.2 This test method involves the distillation of crude oil Development of International Standards, Guides and Recom-
test specimens to obtain a naphtha fraction prior to chloride mendations issued by the World Trade Organization Technical
determination. The chloride content of the naphtha fraction of Barriers to Trade (TBT) Committee.
the whole crude oil can thereby be obtained. See Section 5
regarding potential interferences. 2. Referenced Documents
1.3 The test procedure covers the determination of organic 2.1 ASTM Standards:2
chloride in the washed naphtha fraction of crude oil by D86 Test Method for Distillation of Petroleum Products and
combustion ion chromatography. Other halides can be deter- Liquid Fuels at Atmospheric Pressure
mined but are not included in the precision statement of the test D1193 Specification for Reagent Water
method. D1298 Test Method for Density, Relative Density, or API
1.4 The values stated in SI units are to be regarded as Gravity of Crude Petroleum and Liquid Petroleum Prod-
standard. The preferred concentration units are micrograms of ucts by Hydrometer Method
chloride per gram of sample. D4052 Test Method for Density, Relative Density, and API
1.4.1 Exception—The values given in parentheses are for Gravity of Liquids by Digital Density Meter
information only. D4057 Practice for Manual Sampling of Petroleum and
Petroleum Products
1.5 Warning—Mercury has been designated by many regu-
D4177 Practice for Automatic Sampling of Petroleum and
latory agencies as a hazardous material that can cause central
Petroleum Products
nervous system, kidney and liver damage. Mercury, or its
D4929 Test Method for Determination of Organic Chloride
vapor, may be hazardous to health and corrosive to materials.
Content in Crude Oil
Caution should be taken when handling mercury and mercury
D6299 Practice for Applying Statistical Quality Assurance
containing products. See the applicable product Material
and Control Charting Techniques to Evaluate Analytical
Safety Data Sheet (MSDS) for details and EPA’s website—
Measurement System Performance
http://www.epa.gov/mercury/faq.htm—for additional informa-
D6300 Practice for Determination of Precision and Bias
tion. Users should be aware that selling mercury and/or
Data for Use in Test Methods for Petroleum Products and
mercury containing products into your state or country may be
Lubricants
prohibited by law.
D6708 Practice for Statistical Assessment and Improvement
1.6 This standard does not purport to address all of the of Expected Agreement Between Two Test Methods that
safety concerns, if any, associated with its use. It is the Purport to Measure the Same Property of a Material
responsibility of the user of this standard to establish appro- E288 Specification for Laboratory Glass Volumetric Flasks
E969 Specification for Glass Volumetric (Transfer) Pipets
1
2
Subcommittee D02.03 on Elemental Analysis. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Current edition approved Oct. 1, 2017. Published November 2017. DOI: Standards volume information, refer to the standard’s Document Summary page on
1
D8150 − 17
3. Summary of Test Method 4.1.2.2 Since crude oil deposits worldwide exhibit different
3.1 Distillation—A crude oil distillation is performed to yields of naphtha, the working range of detection for this
obtain the naphtha cut at 204 °C (400 °F). The distillation method shall cover a broad range, possibly as high as 50 µg/g
method was adapted from Test Method D86 for the distillation in a naphtha fraction.
of petroleum products as well as Test Method D4929 for 4.1.3 Organic chloride present in the crude oil (for example,
determination of organic chloride content in crude oil. The methylene chloride, perchloroethylene, etc.) is usually distilled
naphtha cut is washed with caustic, repeatedly when necessary, into the naphtha fraction. Some compounds break down during
until all hydrogen sulfide is removed. The naphtha cut, free of fractionation and produce hydrochloric acid, which has a
hydrogen sulfide, is then washed with water, repeatedly when corrosive effect. Some compounds survive fractionation and
necessary, to remove inorganic halides (chlorides). are destroyed during hydro-treating (desulfurization of the
naphtha).
3.2 Detection Using Combustion Ion Chromatography—A
sample of known weight or volume is placed into a sample boat 4.2 Other halides can also be used for dewaxing crude oil; in
and introduced at a controlled rate into a high temperature such cases, any organic halides will have similar impact on the
combustion tube. There, the sample is combusted in an oxygen refining operations as the organic chlorides.
rich pyrohydrolytic environment. The gaseous by-products of 4.3 Organic chloride species are potentially damaging to
the combusted sample are trapped in an absorption medium refinery processes. Hydrochloric acid can be produced in
where the hydrogen halides (HX) formed during combustion hydro- treating or reforming reactors and the acid accumulates
disassociate into their respective ions, X- while the sulfur in condensing regions of the refinery. Unexpected concentra-
oxides (SOX) formed are further oxidized to SO42- in the tions of organic chlorides cannot be effectively neutralized and
presence of an oxidizing agent. An aliquot of known volume of damage can result. Organic chlorides are not known to be
the absorbing solution is then automatically injected into an ion naturally present in crude oils and usually result from cleaning
chromatograph (IC) by means of a sample injection valve. The operations at producing sites, pipelines, or tanks. It is important
halide and sulfate anions are separated on the anion separation for the oil industry to have common methods available for the
column of the IC. The conductivity of the eluent is reduced determination of organic chlorides in crude oil, particularly
with an anion suppression device prior to the ion chromato- when transfer of custody is involved.
graph’s conductivity detector, where the anions of interest are
measured. Quantification of the chlorine in the original com- 5. Interferences
busted sample is achieved by first calibrating the system with 5.1 Detection Using Combustion Ion Chromatography—
a series of standards containing known amounts of chlorine and Substances that co-elute with the anions of interest will
then analyzing unknown samples under the same conditions as interfere. A high concentration of one anion can interfere with
the standards. The combined system of pyrohydrolytic com- other constituents if their retention times are close enough to
bustion followed by ion chromatographic detection is referred affect the resolution of their peak.
to as Combustion Ion Chromatography (CIC).
6. Purity of Reagents
4. Significance and Use
6.1 Purity of Reagents—Reagent grade chemicals shall be
4.1 Organic chlorides do not occur naturally in crude oil. used in all tests. Unless otherwise indicated, it is intended that
When present, they result from contamination in some manner, all reagents shall conform to the specifications of the Commit-
such as disposal of chlorinated solvent used in many dewaxing tee on Analytical Reagents of the American Chemical Society,
pipeline or other equipment operations. where such specifications are available.3 Other grades can be
4.1.1 Uncontaminated crude oil will contain no detectable used, provided it is first ascertained that the reagent is of
organic chloride, and most refineries can handle very small sufficiently high purity to permit its use without lessening the
amounts without deleterious effects. accuracy of the determination.
4.1.1.1 Most trade contracts specify that no organic chloride
6.2 Purity of Water—Unless otherwise indicated, references
is present in the crude oil.
to water shall be understood to mean reagent water as defined
4.1.2 Several pipelines have set specification limits less than
by Type I of Specification D1193.
1 µg/g organic chlorides in the whole crude, and less than 5
µg/g in the light naphtha, based on the yield of naphtha being DISTILLATION AND CLEANUP PROCEDURE
20 % of the original sample.
4.1.2.1 To ensure less than 1 µg/g organic chloride in the 7. Apparatus
crude oil, the amount measured in the naphtha fraction shall be 7.1 Round-Bottom Boiling Flask, borosilicate, 1 L, single
less than 1/f (where f is the naphtha fraction calculated with Eq short neck with 24/40 outer ground-glass joint.
1). For example, a crude oil sample with 1 µg/g of organic
chloride but a 10 % yield of naphtha would create a naphtha
containing 10 µg/g organic chloride. Further, a crude contain- 3
Reagent Chemicals, American Chemical Society Specifications, American
ing 1 µg/g of organic chloride but a 40 % yield of naphtha Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
would create a naphtha containing 2.5 µg/g organic chloride.
Due to the difference in naphtha yields, the impact on refining and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
operations can be significantly different. MD.
2
D8150 − 17
7.2 Tee Adapter, borosilicate, 75° angle side-arm, 24/40 tainer. (Warning—Samples that are collected at temperatures
ground-glass joints. below room temperature can undergo expansion and rupture
7.3 Thermometer, ASTM thermometer 2C (–5 °C to 300 °C) the container. For such samples, do not fill the container to the
or 2F, (20 °F to 580 °F). top; leave sufficient air space above the sample to allow room
7.3.1 Other temperature measuring devices, such as thermo- for expansion.)
couples or resistance thermometers, can be used when the 9.2 If the test unit is not used immediately, then thoroughly
temperature reading obtained by these devices is determined to mix in its container prior to taking a test specimen. Some test
produce the same naphtha fraction that is obtained when units can require heating to ensure sample homogenization.
mercury-in-glass thermometers are used. (Warning—When heating is required, care should be taken so
7.4 Thermometer Adapter, borosilicate, 24/40 inner ground- that no organic chloride containing hydrocarbons are lost.)
glass joint.
10. Preparation of Distillation Apparatus
7.5 Liebig Condenser, borosilicate, 300 mm length, 24/40
ground-glass joints. 10.1 Clean all glassware by rinsing successively with tolu-
7.6 Vacuum Take-Off Adapter, borosilicate, 105° angle bend, ene and acetone. After completing the rinse, dry the glassware
24/40 ground-glass joints. using a stream of dry nitrogen gas. Obtain and record the
masses of the round-bottom flask and receiving cylinder.
7.7 Receiving Cylinder, borosilicate, 250 mL capacity, 24/40 Assemble the glass distillation apparatus using stopcock grease
outer ground-glass joint. to seal all joints and wire clamps to prevent loosening of the
7.8 Wire Clamps, for No. 24 ground-glass joints, stainless joints. Adjust the thermometer position within the adapter tee
steel. such that the lower end of the capillary is level with the highest
point on the bottom of the inner wall of the adapter tee section
7.9 Receiver Flask, for ice bath, 4 L.
that connects to the condenser.
7.10 Copper Tubing, for heat exchanger to cool condenser NOTE 1—A diagram illustrating the appropriate positioning of the
water, 6.4 mm outside diameter, 3 m length. thermometer can be found in Test Method D86.
7.11 Electric Heating Mantle, Glas-Col Series 0, 1 L size, 10.2 Form the copper tubing into a coil to fit inside the
140 W upper heating element, 380 W lower heating element, receiver flask, leaving room in the center of the flask for the
or equivalent. receiving cylinder. With the PVC tubing, connect one end of
7.12 Variable Transformer, 2, for temperature control of the copper coil to the water source, and connect the other end
upper and lower heating elements, 120 V, 10 amps. of the coil to the lower fitting of the Liebig condenser cooling
jacket. Connect the upper condenser fitting to the water drain.
8. Reagents and Materials Fill the receiver flask with an ice/water mixture, and turn on the
8.1 Acetone, chloride-free. (Warning—Extremely water. Maintain the temperature of the condenser below 10 °C.
flammable, can cause flash fires. Health hazard.)
11. Procedure
8.2 Caustic Solution, 1 M potassium hydroxide
(Warning—Can cause severe burns to skin.) prepared in 11.1 Add a 500 mL crude oil test specimen to a tared round
distilled/deionized water. bottom flask. Obtain and record the mass of the crude oil-filled
flask to the nearest 0.1 g. Connect the flask to the distillation
8.3 Deionized Water.
apparatus. Place the heating mantle around the flask, and
8.4 Filter Paper, Whatman No. 41 or equivalent. support the heating mantle/flask from the bottom. Connect the
8.5 Stopcock Grease.4 heating mantle to the variacs. Turn on the variacs and start the
distillation. During the distillation, adjust the variac settings to
8.6 Toluene, chloride-free. (Warning—Flammable. Health
give a distillation rate of approximately 5 mL ⁄min. Continue
hazard.)
the distillation until a thermometer reading of 204 °C (400 °F)
9. Sampling is attained. When the temperature reaches 204 °C (400 °F), end
the distillation by first disconnecting and removing the receiv-
9.1 Obtain a test unit in accordance with Practice D4057 or ing cylinder. After the receiving cylinder has been removed,
D4177. To preserve volatile components, which are in some turn off the variacs and remove the heating mantle from the
samples, do not uncover samples any longer than necessary. flask. Obtain and record the mass of the receiving cylinder and
Samples should be analyzed as soon as possible, after taking distillate.
from bulk supplies, to prevent loss of organic chloride or
contamination due to exposure or contact with sample con- NOTE 2—Appendix X2 describes a caution regarding crude oil sample
preparation using water washing prior to distillation. While this method
permits water washing of the distilled naphtha, as described in Section
4
The sole source of supply of the stop-cock grease known to the committee at 11.2, it does not include neat sample preparation by water washing of the
this time is Dow Corning silicone, available from Dow Corning Corporation, crude oil sample prior to testing. The information provided in Appendix
Corporate Center, PO Box 994, Midland, MI. If you are aware of alternative X2 should not be interpreted as support for this preparation practice.
suppliers, please provide this information to ASTM International Headquarters.
Your comments will receive careful consideration at a meeting of the responsible 11.1.1 The precision and bias statements were determined
technical committee,1 which you may attend. using mercury-in-glass thermometers only. Therefore, when
3
D8150 − 17
alternativee temperature measuring devices are used, the cut- system is swept by a humidified inert carrier gas and shall be
off temperature shall be that which will produce a naphtha cut capable of allowing the quantitative delivery of the material to
similar to what would be yielded when mercury-in-glass be analyzed into the oxidation zone at a controlled rate.
thermometers are used. Such alternative temperature measur-
13.4 Boat Inlet Cooler—Sample volatility requires an appa-
ing devices shall not be expected to exhibit the same tempera-
ratus capable of cooling the sample boat prior to sample
ture lag characteristics as mercury-in-glass thermometers.
injection into the boat.
11.2 Transfer the naphtha fraction from the receiving cylin-
der to a separatory funnel. Using the separatory funnel, wash 13.5 Gas Flow Control—The apparatus shall be equipped
the naphtha fraction three times with equal volumes of the with flow controllers capable of maintaining a constant flow of
caustic solution (1 M KOH). Follow the caustic wash with a oxygen and argon or helium carrier gas.
water wash, again washing three times with equal volumes. 13.5.1 Gas Regulators, two-stage, gas regulators capable of
The caustic wash removes hydrogen sulfide, while the water regulating the pressures to 40 psi to 60 psi shall be used for the
wash removes traces of inorganic chlorides either originally carrier and combustion gases. Follow instrument manufactur-
present in the crude or from impurities in the caustic solution. er’s recommendations for pressure regulation.
After the washings are complete, filter the naphtha fraction to 13.6 Furnace—An electric furnace which can maintain a
remove residual freestanding water. Store the naphtha fraction minimum temperature of 900 °C.
in a clean glass bottle. This naphtha fraction can now be
analyzed for organic chlorides by combustion ion chromatog- 13.7 Gas Absorption Unit, having an absorption tube with
raphy. sufficient capacity to hold a minimum of 5 mL which is
automatically filled with a known volume of absorption solu-
11.3 Measure the density of the crude oil specimen and the
tion by a built-in burette or other similar device. The gas
naphtha fraction by obtaining the mass of 10.0 mL (using a
absorption unit is interfaced to the IC and injects an aliquot of
10 mL volumetric flask) of each to the nearest 0.1 g.
the absorption solution into the IC after the sample is com-
NOTE 3—Alternatively, the density of the crude oil specimen and the
naphtha fraction can be determined using a digital density meter as busted and the by- products of combustion are absorbed. The
specified in Test Method D4052. gas absorption unit rinses the absorption tube and the transfer
lines from the combustion tube to the gas absorption unit with
12. Calculation
Type I reagent water ( 8.3) or other appropriate absorption
12.1 Calculate the naphtha fraction, f, using Eq 1 as follows: solution prior to sample combustion and after the absorption
Mn solution is injected into the IC to minimize cross contamina-
f5 (1) tion.
Mc
where: 13.8 Gas-Tight Sampling Syringe, of 10 µL, 25 µL, 50 µL,

f = mass fraction of naphtha collected, 100 µL, or 250 µL capacity and capable of accurately deliver-
Mn = mass of naphtha collected, and ing microliter quantities.
Mc = mass of crude oil specimen. 13.9 Pyrohydrolytic Combustion Tube, made of quartz and
12.2 Calculate the density of the naphtha fraction using Eq capable of withstanding temperatures up to 1100 °C. The
2 as follows: combustion tube shall be of ample volume and can include
quartz wool or other suitable medium to provide sufficient
m
Density, g/mL 5 (2) mixing and surface area to ensure complete combustion of the
v
sample.
where:
13.10 Humidifier Delivery System, capable of delivering
m = mass of sample specimen, g, and Type 1 reagent water (Section 8.3) to the combustion tube at a
v = volume of sample specimen, mL.
controlled rate sufficient to provide a pyrohydrolytic environ-
DETECTION USING COMBUSTION ION ment.
CHROMATOGRAPHY 13.11 Ion Chromatograph (IC), (see Note 5) an analytical
system with all required accessories including columns, sup-
13. Apparatus
pressor and detector.
13.1 Autosampler, capable of accurately delivering a known
volume of sample, typically in the range of 10 µL to 100 µL, NOTE 5—Many different companies manufacture automatic ion chro-
matographs. Consult the specific manufacturer instruction manuals for
into the sample boat. details regarding setup and operation.
NOTE 4—The sample syringe should be rinsed with clean solvent
followed by a rinse with the next sample when changing from one vial to 13.11.1 Injection System, capable of delivering 20 µL to
another. Follow the manufacturer’s recommendation to minimize carry- 500 µL with a precision better than 1 % or as recommended for
over.
this determination by the manufacturer. Larger volumes can be
13.2 Balance, analytical, with sensitivity to 0.0001 g. used as long as the performance criteria of the method are not
13.3 Boat Inlet System, The system provides a sampling degraded.
port for the introduction of liquid samples into the sample boat 13.11.2 Pumping System, capable of delivering mobile
and is connected to the inlet of the combustion tube. The phase flows between 0.2 mL ⁄min and 2.5 mL/min with a
4
D8150 − 17
precision better than 2 %, or as recommended for this deter- 13.14 Volumetric Pipets–Type Class A, in accordance with
mination by the manufacturer. Specification E969 at the volume required for preparation of
13.11.3 Continuous Eluent Generation (optional), to auto- standards, reagents, and solutions.
matically prepare and purify the eluent used in the ion
chromatography. Electrolytic eluent generation and auto-buret 14. Reagents and Materials
preparation of eluent by means of in-line dilution of a stock 14.1 Purity of Reagents—Reagent grade or higher purity
solution have been found satisfactory for this method. Other chemicals shall be used for the preparation of all samples,
continuous eluent generation devices can be used if the standards, eluent, and regenerator solutions. Unless otherwise
precision and accuracy of the method are not degraded. indicated, it is intended that all reagents shall conform to the
13.11.4 Anion Pre-concentration Column (optional), used specification of the Committee on Analytical Reagents of the
for anion pre-concentration and matrix elimination. Pre- con- American Chemical Society, where such specifications are
centration enables larger volumes of absorbing solu- available.3 Other grades can be used, provided that the reagent
tion (1 mL to 3 mL) to be analyzed without the associated is of sufficiently high purity to permit its use without lessening
water dip. Matrix elimination refers to the elimination of any the accuracy of the determination.
unreacted hydrogen peroxide in the absorbing solution prior to NOTE 6—Purity of reagents are of particular importance when perform-
injection onto the guard and anion separator columns and ing trace analysis (samples containing 1 mg/kg or less in analyte
concentration). A system reagent blank should provide a chromatographic
potentially interfere with the fluoride peak resolution.
area response no greater than 50 % (1⁄2) of the lowest calibration standard.
13.11.5 Guard Column, for protection of the analytical
column from strongly retained constituents. Improved separa- 14.2 Purity of Water—Unless otherwise indicated, refer-
tion is obtained with additional theoretical plates. ences to water shall be understood to mean Type 1 having
13.11.6 Anion Separator Column, capable of producing 18 MΩ cm resistance and conforming to Specification D1193.
satisfactory baseline separation of the anion peak of interest as 14.3 Quartz Wool—(fine grade) or other suitable absorbent
shown in Fig. 1. material can be used that is stable and capable of withstanding
13.11.7 Anion Suppressor Device, reduces the background temperatures inside the furnace.
conductivity of the eluent after separation by the anion NOTE 7—Materials meeting the requirements in 8.4 provide a more
separator column. Both chemical and continuous electrolytic uniform injection of the sample into the boat by wicking any remaining
drops of the sample from the tip of the syringe needle prior to introduction
suppressors have been found satisfactory for this method. of the sample into the furnace. Consult instrument manufacturer recom-
Other anion suppressor devices can be used as long as the mendations for further guidance.
precision and accuracy of the method are not degraded.
14.4 Argon or Helium, carrier gas minimum 99.99 % purity.
13.11.8 Conductivity Detector, temperature controlled to NOTE 8—Purification scrubbers to ensure the removal of containments
0.01 °C, capable of at least 0 µS ⁄cm to 15 000 µS ⁄cm on a such as moisture (molecular sieve) and hydrocarbon trap filters (activated
linear scale. charcoal or equivalent) are recommended.
13.11.9 Data Acquisition System, an integrator or computer 14.5 Oxygen, combustion gas minimum 99.75 % purity.
data handling system capable of integrating the peak areas of
the ion chromatograph. 14.6 Calibration Standards, certified calibration standards
from commercial sources or calibration standards prepared in
13.12 Quartz or Ceramic Sample Boats, of sufficient size to the laboratory containing the elements or anions at the concen-
hold 10 µL to 100 µL. The boat is filled with quartz wool or trations of interest.
other suitable material (8.4) to wick any remaining drops of the 14.6.1 1-Chloropentane, FW 106.59, 33.2% Cl.
sample from the tip of the syringe needle prior to introduction 14.6.2 Organic Chloride Standard, Chloropentane (FW
of the sample into the furnace. 106.59, 33.2% Cl) diluted in isooctane has been used success-
13.13 Volumetric Flasks–Type Class A, in accordance with fully for chloride calibration. Other sources of organic chloride
Specification E288 at the volume required for the preparation can be used as long as performance, precision, and accuracy
of standards, reagents, and solutions. are not degraded.
FIG. 1 Anion Peak of Interest (Chloride)
5
D8150 − 17
NOTE 9—Calibration standards can have a useful shelf life of about P = % purity of target standard compounds listed in 14.6.1,
three months if properly stored in a cool, dark place.
NOTE 10—A correction for chemical impurity can be used if deemed
and
necessary. K = 106 (correction factor to convert g/mL to µg/mL).
14.7 Eluent Solution—Follow the specific guidelines for the 14.11 Absorption Solution—Type I water conforming to
preparation and use of the eluent solution from the manufac- Specification D1193.
turer of the columns being used. Other concentrations can be 14.12 Working Standard Solution—Calculate the correct
used if precision and accuracy of the method is not degraded. concentrations obtained from the stock standard solution in
The solutions recommended by the column manufacturer can 14.10 and prepare a working standard by diluting the stock
be purchased from qualified vendors as long as the standard solution with solvent (14.9).
performance, precision, and accuracy are not degraded (see 14.12.1 Prepare a 50.0 µg/mL working standard by using a
Section 15 regarding Hazards). 5.0 mL Type Class A volumetric pipet (Specification E969) and
14.8 Suppressor Solutions: pipet 5.0 mL of the 1000 µg/mL stock standard solution(s)
14.8.1 Chemical Suppressor Regenerant Solution—Follow (14.10) into a 100 mL Type Class A volumetric flask (Speci-
the specific manufacturer guidelines for the preparation and use fication E288) and dilute to mark with solvent (14.9).
of the suppressor solution. The manufacturer recommended 14.13 Calibration Standards—Prepare calibration standards
solutions can be purchased from qualified vendors as long as by diluting the working standard solution (14.12) to create
the performance, precision, and accuracy are not degraded. 0.5 µg ⁄mL, 1.0 µg ⁄mL, 5.0 µg ⁄mL, 10 µg ⁄mL, and 25 µg ⁄mL
14.8.2 Electrolytic Suppressor Current Setting—Follow the calibration standards by pipetting 1.0 mL, 2.0 mL, 10.0 mL,
specific guidelines for the current setting from the vendor of 20.0 mL, and 50.0 mL of working standard solution with the
the suppressor being used based upon the flow rate and eluent appropriate Class A volumetric pipets into five separate 100
concentration being used for the analysis. mL Class A volumetric flasks and dilute to the mark with
solvent (14.9). The calibration standards used to calibrate the
14.9 Solvent—The solvent of choice should be capable of
system will include the solvent (14.9) as zero, the working
dissolving the standard or sample. The solvent should contain
standard for the 50 µg/mL and encompass the following
less than 0.05 mg/kg of the elements or anions of interest. The
approximate concentrations of calibration standards: 0.0 µg ⁄m,
blank value shall be determined for each new bottle of solvent.
0.5 µg ⁄m, 1.0 µg ⁄m, 5.0 µg ⁄m, 10 µg ⁄m, 25 µg ⁄m, and
Suggested solvents include, but are not limited to, iso-octane,
50 µg ⁄mL. The volume of working standard, in mL, needed to
xylene, toluene, and methanol.
prepare a calibration standard is determined using the formula
14.10 Stock Standard Solution(s) of approximately 1000 in Eq 4.
µg/mL—Prepare a stock standard solution by accurately weigh-
Conc cal 3 Vol cal
ing to within 10 % of the target weight for the target standard Vol work , mL 5 (4)
Conc work
compound listed in 14.6.1 into a 100 mL Type Class A
volumetric flask. Dilute to volume with the selected solvent where:
listed in 14.9. Calculate the actual concentration of the stock Volwork = volume of working standard needed to prepare
standard solution(s) for the element by using the formula in Eq the desired calibration standard, mL,
3 with the actual recorded weight of the target compound used Conccal = concentration of calibration standard desired,
for each element. This stock standard solution can be further µg/mL,
diluted to other desired concentrations. Other suitable Volcal = volume of calibration standard desired, mL, and
materials, weights and volumes can be substituted in preparing Concwork = concentration of working standard, µg/mL.
stock standard solution(s) as long as the performance of the 14.13.1 A summary outlining the preparation of the calibra-
method is not degraded. tion standards is shown in Table 1.
NOTE 11—Stock standard solutions from commercial sources can be 14.13.2 Final dilution volumes can be calculated using the
used if the accuracy, precision, and performance criteria of the method are formula in Eq 4.
not degraded.
NOTE 12—Alternative volumes and concentrations of working and
14.10.1 1-Chloropentane, (Chlorine), 0.3007 g target
weight.
TABLE 1 Calibration Standards—Preparation from Working
14.10.2 Calculate the actual concentration of the stock Standard Solution
standard solution(s) for chloride using Eq 3 with the actual
Calibration Working Standard Solution Final
recorded weight of the target compound. Standards Diluted
Conc Conc Volume Volume
A 3B 3P (µg/mL) (mL)A
Stock standard solution,µg/mL 5 3 106 (3) (µg/mL) (mL)B
V 3K
25 50.0 50 100
10 50.0 20 100
where: 5.0 50.0 10 100
A = mass of the target compound in grams, g, 1.0 50.0 2.0 100
B = % concentration of the elements in the respective target 0.5 50.0 1.0 100
A
compounds listed in 14.6.1, B
Use Class A volumetric pipets or equivalent meeting Specification E969.
V = final diluted volume, mL, Use Class A volumetric flasks or equivalent meeting Specification E288.
6
D8150 − 17
calibration standards can be prepared so long as the preparation meets the 16.3 Adjust gas flows and pyrolysis temperatures to the
concentration range needed to properly bracket the response of the operating conditions as recommended by the instrument manu-
samples and adhere to the scope of the method.
NOTE 13—Working standard solutions should be prepared on a regular
facturer.
basis depending upon the frequency of use and age. The working standard
solution can be retained, if refrigerated, for up to three months. Do not 17. Calibration
refrigerate working standard solution if prepared in benzene as the
benzene will freeze and cause erratic results. 17.1 Prior to the analysis of standards or samples, it is
NOTE 14—Alternatively, calibration standards can be prepared by necessary to run a series of system blanks (17.1.1) and solvent
gravimetric dilution provided the same solvents are used throughout. The blanks (17.1.2) to ensure cleanliness of the system. Follow the
solvent used for the stock standard solution, working standard and
manufacturer’s recommendation for this process.
calibration standards shall all be the same. In this case, the final
concentration unit for the calibration standards will remain µg/mL even 17.1.1 A system blank consists of a combustion ion chro-
though the dilutions were performed gravimetrically. matography (CIC) analysis with no solvent or sample injection
in which the same combustion, chromatography and time
15. Hazards protocols are used as for the sample analysis, but without the
15.1 Consult the current version of OSHA regulations, combustion of a sample or solvent blank. The system blank
supplier’s Safety Data Sheets (SDS), and local regulations for shall be equal to or less than 50 % (1⁄2) the area counts of the
all materials used in this test method. lowest calibration standard used for calibration.
15.2 High temperature and flammable hydrocarbons occur 17.1.2 A solvent blank consists of a combustion ion chro-
in the test method. Use materials that are rated for containing matography (CIC) analysis of the solvent used for preparation
these hydrocarbons in all sample containers and sample trans- of the calibration standards in which the same combustion,
fer apparatus. Exercise extra care when using flammable chromatography, and time protocols are used for the sample
materials near the oxidative furnace. analysis. The solvent blank area count shall be equal to or less
than 50 % (1⁄2) the area counts of the lowest calibration
15.3 Potassium hydroxide is a caustic alkali, which in an
standard used for calibration.
anhydrous or strong solution forms, is a hazardous material. In
contact with the skin, it produces burns that can be quite 17.1.3 The series of system blanks should be analyzed
serious unless promptly treated. Its action is insidious since it repeatedly until a stable baseline response is achieved.
produces no immediate stinging or burning sensation and Typically, 3 to 5 system blanks will be required following
damage to the skin can result before its presence is realized. start-up of the instrument. A stable background is considered
Eyes are particularly vulnerable to severe damage from alkalis. achieved when the analysis of a minimum of two consecutive
system blanks have area counts equal to or less than 15 %
15.4 Use safety goggles or face shields and rubber gloves relative difference for the anions of interest. If a stable baseline
when handling alkalis and avoid spillage on clothing. These response is not obtained, follow the manufacturer’s recommen-
materials rapidly attack wool and leather. dations to check for sources of contamination.
15.5 Use all appropriate safety precautions to clean up and
17.2 Prepare a series of calibration standards covering the
discard in accordance with all federal, state, and local health
range of samples to be analyzed by diluting the working
and environmental regulations.
standard (14.12) prepared from the stock standard solution
16. Preparation of Apparatus (14.10) to the desired final concentrations.
NOTE 15—Commercially available standards can be used as long as the
16.1 Set up the instrument in accordance with the manufac- accuracy and precision of the method is not degraded.
turer’s instructions. A typical diagram of a CIC system is
shown in Fig. 2. 17.3 Analyze the calibration standards covering the analyti-
cal range of the samples and determine the peak areas
16.2 Set instrument parameters in accordance with the corresponding to the chloride ion. The use of an automated
manufacturer’s instructions. sampling device is required to ensure accurate and repeatable
injection volumes and techniques.
17.4 An aliquot of absorbing solution following the com-
bustion of each standard is introduced into the IC for separation
and quantification. Retention times vary with operating condi-
tions. The standards, therefore, shall be analyzed by the IC in
the same manner as the sample solutions. Consult the manu-
facturer’s recommendations for analyte elution order.
17.5 After the standards have been analyzed, a calibration
curve is determined using a “best-fit” regression by plotting
concentration versus the integrated instrument response (peak
area) for chloride. Instrument response is calculated and
defined per the manufacturer’s recommendations. A typical
calibration includes a series of four or more standards contain-
FIG. 2 Combustion IC Diagram ing the elements of interest and bracketing the concentrations
7
D8150 − 17
that are in the samples. The calibration curve should have a 20.2 The organic chloride content of the original crude oil
correlation coefficient (r2) greater than 0.995. sample specimen is also expressed as µg/g. and shall reference
this test method.
18. Procedure
20.3 Should a modification be employed with a pre-water
18.1 Obtain a naphtha specimen using the procedure de- wash, as discussed in Appendix X2, make note on the report
scribed in Section 11. The concentrations in the naphtha with “D8150 Modified with Crude Pre-wash”.
specimen shall be less than the concentration of the highest
calibration standard and greater than the lowest calibration 21. Quality Assurance/Quality Control (QA/QC)
standard used in the calibration. If required, a dilution of the
sample can be performed. 21.1 Confirm the performance of the instrument and the test
procedure by analyzing a QC sample.
18.2 Analyze the samples using identical instrument condi- 21.1.1 When QA/QC protocols are already established in
tions as used for calibration. the testing facility, these can be used when they confirm the
18.3 Inspect the combustion tube and other flow path reliability of test result.
components to verify complete oxidation of the test specimen 21.1.2 When there is no QA/QC protocol established in the
after analysis. testing facility, Appendix X1 can be used as the QA/QC
18.4 If necessary, increase the residence time for the boat in system.
the furnace if coke or soot is observed on the boat after 21.2 Users of this test method are advised that in contractual
combustion. Decrease the boat drive introduction rate or hold agreements, one or more of the contracting parties can and can
times in the furnace, or both, if coke or soot is observed on the make Appendix X1 mandatory practice.
exit end of the combustion tube.
18.5 Clean any coke or soot as per the manufacturer’s 22. Precision and Bias5
instructions. After any cleaning or adjustment, assemble and 22.1 Precision—The precision of these test methods as
leak check the apparatus. Run a check standard to determine if determined by the statistical examination of the interlaboratory
the instrument needs to be recalibrated. test results is as follows:
19. Calculation results obtained by the same operator with the same apparatus
19.1 If the combustion ion chromatograph has a computer- under constant operating conditions on identical test materials
based data handling software, follow manufacturer procedures would, in the long run, in the normal and correct operation,
for calculation of chloride concentration in the naphtha fraction exceed the following values only in 5 % of the cases (one case
in units of µg/mL. in twenty).
19.2 For analyzers calibrated manually, calculate the con- 22.1.1.1 Values can be obtained for organically-bound chlo-
centration of chloride in the absorber solution, in units of rine for any given concentration above 1 µg ⁄g (in the original
µg/mL, using the peak area obtained from the sample and the crude oil specimen) using Eq 6 as follows:
calibration curve(s) generated in Section 17. Calculate the repeatability, r 5 0.2918~ X ! 0.6746 (6)
concentration of chloride in the naphtha fraction using the
where:
formula in Eq 5.
X = µg/g chloride.
C Abs 3 V Abs
Chloride, µg/g 5 3 1000 (5) 22.1.1.2 Calculated recovery values using the repeatability
V inj 3 D
definition for this method, described in Section 22.1.1.1, are
where: shown in Table 2.
CAbs = concentration of chloride in the absorption solution,
µg/mL,
VAbs = final volume of absorption solution, mL,
Vinj = volume of absorption solution analyzed (injected),
5
µL, Supporting data have been filed at ASTM International Headquarters and may
D = density of test specimen, mg/µL (equivalent to g/mL, Service at service@astm.org.
see 12.2), and
1000 = factor to convert mass of sample injected from
TABLE 2 Calculated Precision Values
milligrams to grams.
Cl, µg/g repeatability r, µg/g Reproducibility R, µg/g
19.3 The concentration of organic chloride in the original 1.0 0.29 0.76
crude oil sample specimen can be obtained by multiplying the 2.0 0.47 1.2
chloride concentration in the naphtha fraction (see 19.1 or 3.0 0.61 1.6
4.0 0.74 1.9
19.2) by the naphtha fraction, f (see 12.1). 5.0 0.86 2.3
6.0 0.98 2.5
20. Report 8.0 1.2 3.1
10 1.4 3.6
20.1 Report the organic chloride content of the naphtha 12 1.6 4.1
fraction in µg/g calculated in Section 19.
8
D8150 − 17
22.1.2 Reproducibility—The difference between two single 22.2 Bias—Since no generally accepted standard reference
and independent results obtained by different operators work- materials with known values of organic chlorides in crude oil
ing in different laboratories on identical material would, in the are available, bias of this test method cannot be determined.
long run, exceed the following values only in 5 % of the cases
(one case in twenty). 23. Keywords
22.1.2.1 Values can be obtained for organically-bound chlo-
23.1 analysis; anions; aromatics; chloride; chlorine; CIC;
rine for any given concentration above 1 µg ⁄g (in the original
crude oil specimen) using Eq 7 as follows: combustion; combustion ion chromatography; crude oil; hy-
drolysis; ion chromatography; organic chloride; organo-
Reproducibility, R 5 0.7599~ X ! 0.6746 (7) chlorine; organic halides ; oxidative pyrohydrolytic combus-
where: tion; pyrohydrolytic
X = µg/g chloride.
22.1.2.2 Calculated recovery values using the Reproducibil-
ity definition for this method, described in Section 22.1.2.1, are
shown in Table 2.
APPENDIXES
X1. GENERIC QUALITY CONTROL STATEMENT FOR D02 TEST METHODS
X1.1 Confirm the performance of the instrument and the test criticality of the quality being measured, the demonstrated
procedure by analyzing a QC sample. stability of the testing process, and customer requirements.
Generally, a QC sample should be analyzed on each day of
X1.2 Prior to monitoring the measurement process, the user
testing routine samples. The QC frequency should be increased
of the test method needs to determine the average value and
control limits of the QC sample (see Practice D6299 and when a large number of samples are routinely analyzed.
MNL76). However, when it is demonstrated that the testing is under
statistical control, the QC testing frequency can be reduced.
X1.3 Record the QC results and analyze by control charts or The QC sample precision should be periodically checked
other statistically equivalent techniques to ascertain the statis- against the ASTM test method precision to ensure data quality.
tical control status of the total testing process (see Practice
D6299 and MNL7). Any out-of-control data should trigger X1.5 It is recommended that, when possible, the type of QC
investigation for root cause(s). The results of this investigation sample that is regularly tested be representative of the samples
can, but not necessarily, result in instrument recalibration. routinely analyzed. An ample supply of QC sample material
X1.4 In the absence of explicit requirements given in the should be available for the intended period of use and shall be
test method, the frequency of QC testing is dependent on the homogeneous and stable under the anticipated storage condi-
tions.
6
MNL7, Manual of Presentation of Data Control Chart Analysis, 6th ed.,
Section 3: Control Chart for Individuals, ASTM International, W. Conshohocken, X1.6 See Practice D6299 and MNL7 for further guidance
PA. on QC and control charting techniques.
9
D8150 − 17
X2. CAUTION REGARDING CRUDE OIL SAMPLE PREPARATION USING WATER WASHING
X2.1 Under certain conditions, salt (inorganic chlorides salts prior to analysis can provide “false negative” results when
such as MgCl2 and CaCl2) contained within many crude oils considering refinery operations. The user of the method should
can undergo hydrolysis during the D86 distillation step used to consider how the data is to be used before choosing to
isolate the <204 °C fraction for analysis. The hydrolysis results implement a pre-distillation water wash. It is advised to
in the formation of hydrochloric acid (HCl), which can conduct the method as written, without pre-distillation wash.
subsequently react with available organic chloride precursors Then, if deemed necessary, conduct the evaluation with the
such as olefins, alcohols and esters that are present in the pre-distillation water wash in place, and report both results.
naphtha fraction, and form organic chlorides. These formed
organic chlorides remain in the naphtha fraction and are X2.3 In the event that a sample was prepared for testing by
reported in the final test result. As a result, some users have water washing the neat crude, the reported results shall include
adopted the practice of water washing neat crude samples prior the following statement indicating what sample preparation
to distillation, in order to remove what is often deemed a technique was employed. “D8150-Modified with Crude Pre-
potential interference. Wash.” When a pre-distillation water wash modification is
employed, the published precision may not apply.
X2.2 This crude oil sample preparation practice has the
potential to bias the final test results since the act of distillation X2.4 While this method permits water washing of the
simulates the conditions of an atmospheric crude distillation distilled naphtha, it does not include neat sample preparation
tower. Any organic chlorides that are present in the naphtha by water washing of the crude oil sample prior to testing, and
pose a risk to refinery operations therefore their presence or the information provided in this appendix should not be
absence in the test results are relevant. Removal of inorganic interpreted as support for this preparation practice.
10

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This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

Designation: 71 Section 1/97

Standard Test Method for

1. Scope* 1.5 WARNING—Mercury has been designated by many

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

FIG. 1 Temperature Probe Immersion in Constant Temperature Bath

A1. VISCOMETER TYPES AND CERTIFIED VISCOSITY REFERENCE STANDARDS

A1.1 Viscometer Types TABLE A1.1 Viscometer Types

A2. KINEMATIC VISCOSITY TEST THERMOMETERS

TABLE A2.1 General Specification for Thermometers

FIG. A2.1 Thermometer Designs

A3. TIMER ACCURACY

CEUARV 5 0.22 % ~ from the CVRS label or documentation!

X1. TROUBLESHOOTING GUIDE

(1) Revised subsection 6.4.2.

Standard Test Method for

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

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

FIG. 1 Illustrative Potentiometric Titration

X1. AN ALTERNATIVE METHOD FOR THE REMOVAL OF HYDROGEN SULFIDE

X2. GENERIC QUALITY CONTROL STATEMENT FOR D02 TEST METHODS

(1) Subsection 8.2.3 was revised.

Designation: D4052 − 18a

Standard Test Method for

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

3. Terminology 5. Significance and Use

TABLE 3 API Gravity (Repeatability)

TABLE 4 Density (g/mL) and Relative Density (Reproducibility)

TABLE 5 API Gravity (Reproducibility)

X1. ADJUSTMENT AND CALIBRATION PROCEDURE FOR NON-CALCULATING DENSITY METERS

X2.1 Noncalculating Density Analyzers—Using the ob- For relative density:

Designation: D4294 − 16´1

Standard Test Method for

1. Scope* 1.4 Volatile samples (such as high vapor pressure gasolines

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

million—mass ppm). Follow the manufacturer’s operating-

15. Quality Control 6

X1. ADDITIONAL DIESEL PRECISION STATEMENTS

X2. ADDITIONAL GASOLINE PRECISION STATEMENTS

X3. HANDLING OXYGENATED FUELS

(1) Updated subsections 16.1, 16.1.1, 16.1.2, 16.1.3, X1.1.1,

Standard Test Method for

1. Scope* 2. Referenced Documents

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

where: 15. Precision and Bias4

13. Report 16. Keywords

X1. QUALITY CONTROL (QC) MONITORING

(1) Updated the title.

Standard Test Method for

1. Scope* 3.2 Definitions of Terms Specific to This Standard:

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

A1. DETAILED DESCRIPTION OF APPARATUS

A1.2 Apparatus Exterior Interface—The exact layout may

FIG. A1.3 Apparatus Exterior

(1) Updated IP designation to 435/15. (2) Revised subsection 4.1.

Standard Test Method for

1. Scope* 2. Referenced Documents

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

A1. MEASUREMENT OF HFRR WEAR SCARS

FIG. A1.1 Example of a Wear Scar with an Indistinct Boundary

FIG. A1.2 Examples of Wear Scars

FIG. A1.2 Examples of Wear Scars (continued)

Standard Test Method for

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