D 6378 - 22
D 6378 - 22
for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D6378 − 22
1
D6378 − 22
D4306 Practice for Aviation Fuel Sample Containers for 5. Significance and Use
Tests Affected by Trace Contamination 5.1 Vapor pressure is a very important physical property of
D4953 Test Method for Vapor Pressure of Gasoline and volatile liquids for shipping and storage.
Gasoline-Oxygenate Blends (Dry Method)
D5191 Test Method for Vapor Pressure of Petroleum Prod- 5.2 The vapor pressure of gasoline and gasoline-oxygenate
ucts and Liquid Fuels (Mini Method) blends is regulated by various government agencies.
D5842 Practice for Sampling and Handling of Fuels for 5.3 Specifications for volatile petroleum products generally
Volatility Measurement include vapor pressure limits to ensure products of suitable
D5854 Practice for Mixing and Handling of Liquid Samples volatility performance.
of Petroleum and Petroleum Products
D6299 Practice for Applying Statistical Quality Assurance 5.4 In this test method, an air saturation procedure prior to
and Control Charting Techniques to Evaluate Analytical the measurement is not required, thus eliminating losses of
Measurement System Performance high volatile compounds during this step. This test method is
D6300 Practice for Determination of Precision and Bias faster and minimizes potential errors from improper air satu-
Data for Use in Test Methods for Petroleum Products, ration. This test method permits VPX determinations in the
Liquid Fuels, and Lubricants field.
D6708 Practice for Statistical Assessment and Improvement 5.5 This test method can be applied in online applications in
of Expected Agreement Between Two Test Methods that which an air saturation procedure prior to the measurement
Purport to Measure the Same Property of a Material cannot be performed.
3. Terminology 6. Apparatus
3.1 Definitions of Terms Specific to This Standard: 6.1 The apparatus suitable for this test method employs a
3.1.1 dry vapor pressure equivalent (DVPE), n—a value small volume, cylindrically shaped measuring chamber with
calculated by a correlation equation from the total pressure associated equipment to control the chamber temperature
(Test Method D5191), which is equivalent to the value ob- within the range from 0 °C to 100 °C. The measuring chamber
tained on the sample by Test Method D4953, Procedure A. shall contain a movable piston with a maximum dead volume
3.1.2 partial pressure from dissolved air (PPA), n—the of less than 1 % of the total volume at the lowest position to
pressure exerted in vacuum from dissolved air that escapes allow sample introduction into the measuring chamber and
from the liquid phase into the vapor phase. expansion to the desired vapor-liquid ratio. A static pressure
3.1.3 Reid vapor pressure equivalent (RVPE), n—a value transducer shall be incorporated in the piston. The measuring
calculated by a correlation equation from the TPX, which is chamber shall contain an inlet/outlet valve combination for
equivalent to the value obtained on the sample by Test Method sample introduction and expulsion. The piston and the valve
D323. combination shall be at the same temperature as the measuring
chamber to avoid any condensation or excessive evaporation.
3.1.4 total pressure (TPX), n—the pressure exerted in
6.1.1 The measuring chamber shall be designed to contain
vacuum by air- and gas-containing petroleum products, com-
between 5 mL and 15 mL of liquid and vapor and be capable of
ponents and feedstocks, and other liquids, in the absence of
maintaining a vapor-liquid ratio of 4:1 to 1:1. The accuracy of
undissolved water at a vapor-liquid ratio of X:1.
the adjusted vapor-liquid ratio shall be within 0.05.
3.1.5 vapor pressure (VPX), n—the total pressure minus the
PPA in the liquid at a vapor-liquid ratio of X:1. NOTE 5—The measuring chamber employed by the instruments used in
generating the precision and bias statements were constructed of nickel
VPX 5 TPX 2 PPA (1) plated aluminum and stainless steel with a total volume of 5 mL.
Measuring chambers exceeding a 5 mL capacity can be used, but the
4. Summary of Test Method precision and bias statements (see Section 16) are not known to apply.
4.1 Employing a measuring chamber with a built-in piston, 6.1.2 The pressure transducer shall have a minimum opera-
a sample of known volume is drawn into the temperature tional range from 0 kPa to 200 kPa (0 psi to 29 psi) with a
controlled chamber at 20 °C or higher. After sealing the minimum resolution of 0.1 kPa (0.01 psi) and a minimum
chamber, the temperature of the chamber is increased to a accuracy of 60.2 kPa (60.03 psi). The pressure measurement
specified value simultaneously with the first expansion. Two system shall include associated electronics and readout devices
further expansions are performed to a final volume of (X + 1) to display the resulting pressure reading.
times that of the test specimen. After each expansion, the TPX 6.1.3 Electronic temperature control shall be used to main-
is determined. The PPA and the solubility of air in the specimen tain the measuring chamber at the prescribed temperature
are calculated from the three resulting pressures. The (VPX) is within 60.1 °C for the duration of the vapor pressure measure-
calculated by subtracting the PPA in the liquid from TPX. ment.
NOTE 4—For liquids containing very low levels of high vapor pressure 6.1.4 A platinum resistance thermometer shall be used for
contaminants, which behave like a gas, this test method of determination measuring the temperature of the measuring chamber. The
of the PPA and gases may lead to wrong results since the partial pressure
of the contaminants will be included in the PPA. This effect is shown when minimum temperature range of the measuring device shall be
the value of the PPA and gases exceeds the average maximum limit of from 0 °C to 100 °C with a resolution of 0.1 °C and an
7 kPa (1 psi). accuracy of 60.1 °C.
2
D6378 − 22
TABLE 1 Accepted Reference Value (ARV) and Acceptable Testing Range for Reference Fluids (Note 17)
Recommended Instrument Acceptable Testing Range for
ARV [VP4 (37.8 °C)] ± Uncertainty,
Reference Fluid Manufacturer Tolerance, Reference Fuel [VP4 (37.8 °C)],
(kPa)
(kPa) (kPa)
Pentane 107.9 ± 0.2 ±1.0 107.9 ± 1.2 (106.7 to 109.1)
2,2 Dimethylbutane 68.8 ± 0.2 ±1.0 68.8 ± 1.2 (67.6 to 70.0)
2,3 Dimethylbutane 51.7 ± 0.2 ±1.0 51.7 ± 1.2 (50.5 to 52.9)
Recommended Instrument Acceptable Testing Range for
ARV [VP4 (37.8 °C)] ± Uncertainty,
Reference Fluid Manufacturer Tolerance, Reference Fuel [VP4 (37.8 °C)],
(psi)
(psi) (psi)
Pentane 15.65 ± 0.03 ±0.14 15.65 ± 0.17 (15.48 to 15.82)
2,2 Dimethylbutane 9.98 ± 0.03 ±0.14 9.98 ± 0.17 (9.81 to 10.15)
2,3 Dimethylbutane 7.50 ± 0.03 ±0.14 7.50 ± 0.17 (7.33 to 7.67)
6.1.5 The vapor pressure apparatus shall have provisions for NOTE 7—Verification fluids reported by 12 of the D6378 data set
rinsing the measuring chamber with a solvent of low vapor participants in the 2003 ILS (see 16.1) included the following (with
number of data sets identified in parentheses): 2,2-dimethylbutane (11),
pressure or with the next sample to be tested. and 2,3-dimethylbutane (1).
6.2 Vacuum Pump for Calibration, capable of reducing the
7.2 Cyclopentane, (Warning—Cyclopentane is flammable
pressure in the measuring chamber to less than 0.01 kPa
and a health hazard).
(0.001 psi) absolute.
6.3 McLeod Vacuum Gauge or Calibrated Electronic 7.3 2,2-Dimethylbutane, (Warning—2,2-dimethylbutane is
Vacuum Measuring Device for Calibration, to cover at least the flammable and a health hazard).
range from 0.01 kPa to 0.67 kPa (0.1 mm to 5 mm Hg). The 7.4 2,3-Dimethylbutane, (Warning—2,3-dimethylbutane is
calibration of the electronic vacuum measuring device shall be flammable and a health hazard).
regularly verified in accordance with Annex A6.3 on Vacuum
Sensors in Test Method D2892. 7.5 Methanol, (Warning—Methanol is flammable and a
health hazard).
6.4 Pressure Measuring Device for Calibration, capable of
measuring local station pressure with an accuracy and a 7.6 2-Methylpentane, (Warning—2-methylpentane is flam-
resolution of 0.1 kPa (1 mm Hg), or better, at the same mable and a health hazard).
elevation relative to sea level as the apparatus in the laboratory. 7.7 Pentane, (Warning—Pentane is flammable and a health
NOTE 6—This test method does not give full details of instruments hazard).
suitable for carrying out this test. Details on the installation, operation, and
maintenance of each instrument may be found in the manufacturer’s 7.8 Toluene, (Warning—Toluene is flammable and a health
manual. hazard).
7. Reagents and Materials 7.9 Cyclopentane, 98.0 minimum purity (Warning—
Cyclopentane is flammable and a health hazard).
7.1 Purity of Reagents—Use chemicals of at least 99 %
purity for verification of instrument performance (see Section
8. Sampling and Sample Introduction
11). Unless otherwise indicated, it is intended that all reagents
conform to the specifications of the Committee of Analytical 8.1 General Requirements:
Reagents of the American Chemical Society6 where such 8.1.1 The extreme sensitivity of vapor pressure measure-
specifications are available. Lower purities can be used, ments to losses through evaporation and the resulting changes
provided it is first ascertained that the reagent is of sufficient in composition is such as to require the utmost precaution and
purity to permit its use without lessening the accuracy of the the most meticulous care in the drawing and handling of
determination. samples.
7.1.1 The chemicals in 7.3, 7.4, and 7.7 are suggested for 8.1.2 Obtain a sample and test specimen in accordance with
verification of instrument performance (see Section 11), based Practice D4057, D4177, D4306, D5842, or D5854 when
on the reference fuels analyzed in the 2003 interlaboratory appropriate, except do not use the Sampling by Water Dis-
study (ILS) (see 16.1, Table 1, and Note 17). Such reference placement section for fuels containing oxygenates.
fuels are not to be used for instrument calibration. Table 1
identifies the accepted reference value (ARV) and uncertainty 8.1.2.1 For gasolines and gasoline-oxygenate blends, use
limits, as well as the acceptable testing range for each of the either a 250 mL or 1 L (1 qt) sized container filled between
reference fuels listed. 70 % and 80 % with sample. Samples in containers of other
sizes, as prescribed in 8.1.2, may be used with the same ullage
requirements, but precision can be affected.
6
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
Standard-Grade Reference Materials, American Chemical Society, Washington, NOTE 8—Relative bias information when testing gasoline and gasoline-
DC. For suggestions on the testing of reagents not listed by the American Chemical oxygenate blends using 250 mL or 1 L containers is given in Section 16.
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma- 8.1.2.2 For aviation turbine fuel, use a 100 mL size con-
copeial Convention, Inc. (USPC), Rockville, MD. tainer filled to a minimum of 80 % with sample. However,
3
D6378 − 22
samples in containers of other sizes as prescribed in 8.1.2 may dissolved gas relative to ambient barometric pressure. Hydro-
be used, with the same ullage requirement, but the precision carbon loss increases as saturation gas pressure increases.
can be affected. Sealed sample systems are recommended for gas saturations
8.1.3 Perform the VPX determination, including the rinsing greater than about 2 bar gas pressure (about 2 atmospheres or
(see 9.3), on the first test specimen withdrawn from a sample 30 psia).
container. Do not use the remaining sample in the container for 8.2.5 For bottle samples, insert the sample introduction tube
a second VPX determination. If a second determination is as close to the sample bottle bottom as practical.
necessary, obtain a new sample. This condition does not apply 8.2.6 Pressurized samples from a sealed sample system,
when the sample is aviation turbine fuel. pressurized floating pressure cylinders or equivalent may be
used within the pressure and temperature limits specified by the
NOTE 9—For gasoline and gasoline-oxygenate blends, the effect of
taking more than one test specimen from the same sample container was manufacturer for the instrument being used. Excessive ex-
evaluated as part of the 2003 ILS (see 16.1). A precision effect was tremes of pressure and temperature may result in precision
observed between the first and second replicates taken from the containers different than that measured under the conditions of ambient
evaluated. The current precision statements were derived using the first pressure and temperature used to prepare the precision state-
test specimen withdrawn from 250 mL and 1 L containers.
NOTE 10—For aviation turbine fuels the effect of taking more than one
ment. The temperature and pressure of the sample system
test specimen from the same sample container was evaluated as part of the should be controlled so that only a single phase liquid is in the
2007 ILS (see 16.1). No precision effect was observed between the first sealed sample system during sample introduction.
and second replicates taken from the 100 mL containers evaluated. 8.2.6.1 Excessive cooling of samples that contain alcohols
8.1.4 Protect samples from excessive temperatures prior to could result in phase separation (see 8.4), extraction of alcohol,
testing. This can be accomplished by storage in an appropriate and a lower vapor pressure value being determined, unless the
ice bath or refrigerator. sample remains well mixed during sample introduction (that is,
8.1.5 Do not test samples stored in leaky containers. Discard introduction of a test specimen is representative of the com-
and obtain a new sample if leaks are detected. position once heated to test temperature). This can be pre-
vented by not cooling samples containing alcohols, prior to the
8.2 Sampling Handling—This test method does not require
vapor pressure determination.
pre-chilling of the sample and air saturation at ambient
8.2.6.2 Excessive cooling of samples may result in forma-
barometric pressure in order to limit the variability in the
tion of ice or hydrates that may impair proper operation of the
dissolved gas content of the sample prior to measurement. This
sample system.
test method measures the total sample vapor pressure at three
8.2.6.3 Excessive heating of samples may result in vapor
V/L ratios (triple expansion) in order to estimate the partial
formation, resulting in a higher or lower measured vapor
pressure of dissolved gas and hydrocarbon partial pressure
pressure, depending if vapor or remaining liquid phase is
using ideal gas calculations. This has been shown to be
introduced, respectively.
acceptable up to at least 5 bar (about 5 atmospheres) of gas
saturation. 8.3 Verification of Sample Container Filling—If the sample
8.2.1 Samples may be introduced to the instrument over a is contained in a transparent container, verify that the container
wide variation of temperatures and pressures, provided the test is 70 % to 80 % full by suitable means, such as by using a
specimen remains as a single phase (that is, no separated liquid marked ruler or by comparing it to a like container that has the
or gaseous phase). Experiments with temperatures between 70 % and 80 % levels clearly marked. If the container is not
–10 °C to +50 °C and ambient pressures up to 300 kPa have transparent, unseal it and, using a suitable gauge, confirm that
been found suitable with certain gasoline samples.7 the sample volume equals 70 % to 80 % of the container
8.2.2 For gasoline and gasoline-oxygenate blends, the pre- capacity (see Note 11). When the sample is aviation turbine
cision statement is based on sample introduction at ambient fuel, verify that the container is at least 80 % full prior to
temperature and pressure from either 250 mL or 1 L containers. removal of the first specimen.
For aviation turbine fuels, the precision is based on sample NOTE 11—For non-transparent containers, one way to confirm that the
introduction at ambient temperature and pressure from 100 mL sample volume equals 70 % to 80 % of the container capacity is to use a
containers. Precision may be affected with sample introduction dipstick that has been pre-marked to indicate the 70 % and 80 % container
capacities. The dipstick should be of such material that it shows wetting
under different conditions, but such information has not been
after being immersed and withdrawn from the sample. To confirm the
determined. sample volume, insert the dipstick into the sample container so that it
8.2.3 Sample pre-chilling or air saturation, or both, are not touches the bottom of the container at a perpendicular angle before
required, but sample chilling, air saturation, or degassing, or a removing the dipstick.
combination thereof, is acceptable, as it will have no significant 8.3.1 Discard the sample if the container is filled to less than
effect on the result. This allows vapor pressure and distillation 70 %, by volume, of the container capacity.
tests to be conducted on the same sample. 8.3.2 If the container is more than 80 % by volume full,
8.2.4 Degassing and some hydrocarbon loss occurs during pour out enough sample to bring the container contents within
the air saturation step when the sample is supersaturated with the 70 % to 80 % by volume range. Do not return any sample
to the container once it has been withdrawn.
8.3.3 Reseal the container, if opened.
7
Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D02-1609. Contact ASTM Customer 8.4 Verification of Single Phase Sample—After drawing the
Service at service@astm.org. test specimens and transferring them into the instrument for
4
D6378 − 22
TABLE 2 Accepted Reference Value (ARV) and Acceptable Test Range for Reference Fluids from the 2020 ILSA, B
analysis, check the remaining sample for phase separation. If with instrument type and frequency of use. A calibration check of the
the sample is contained in a transparent container, this obser- pressure transducer at least once every six months is recommended.
vation can be made prior to sample transfer. If the sample is 10.1.2 Connect a McLeod gauge or a calibrated electronic
contained in a non-transparent container, shake the sample vacuum measuring device to the vacuum source in line with the
thoroughly and immediately pour a portion of the remaining measuring chamber (see Note 13). Apply vacuum to the
sample into a glass container and observe for evidence of phase measuring chamber. When the vacuum measuring device
separation. A hazy appearance is to be carefully distinguished registers a pressure less than 0.1 kPa (0.8 mm Hg), adjust the
from separation into distinct phases. If the sample separates transducer control to zero or to the actual reading on the
into two distinct phases with a discernible common boundary, vacuum measuring device as dictated by the instrument design
then discard the test and the sample. If the sample has a hazy or manufacturer’s instructions.
appearance, but does not have two distinct phases, then phase
separation has not occurred. The test is valid, but the precision NOTE 13—Refer to Annex A6.3 on Vacuum Sensors in Test Method
D2892 for further details concerning the calibration of electronic vacuum
and bias in Section 16 may not apply (see 15.2). This measuring devices and proper maintenance of McLeod gauges.
verification procedure does not apply when the sample is
aviation turbine fuel. 10.1.3 Open the measuring chamber of the apparatus to
atmospheric pressure and observe the corresponding pressure
9. Preparation of Apparatus value of the transducer. Ensure that the apparatus is set to
9.1 Prepare the instrument for operation in accordance with display the TPX and not a calculated or corrected value.
the manufacturer’s instructions. Compare this pressure value with the pressure obtained from a
mercury barometer, or equivalent, as the pressure reference
9.2 Rinse the measuring chamber, if necessary, with a standard. The pressure measuring device shall measure the
solvent. Acetone has a sufficiently low vapor pressure and can local station pressure at the same elevation as the apparatus in
be used successfully. Rinsing is performed by drawing the the laboratory at the time of pressure comparison.
solvent into the chamber by the piston and expelling the
solvent into the waste container. NOTE 14—Many aneroid barometers, such as those used at weather
stations and airports, are precorrected to give sea level readings. These
9.3 To avoid contamination of the test specimen with the shall not be used for calibration of the apparatus.
previous sample or the solvent, rinse the measuring chamber a
minimum of three times with the sample to be tested. Fill the 10.1.4 Repeat 10.1.2 and 10.1.3 until the zero and baromet-
measuring chamber with sample to at least half the total ric pressures read correctly without further adjustments.
volume of the chamber for each rinse. This rinsing procedure 10.2 Temperature Sensor—Verify the calibration of the
shall always be carried out immediately before the measuring platinum resistance thermometer used to monitor the measur-
procedure (see 13.4). ing chamber temperature at least every six months against a
9.4 If a syringe is used for introduction of the test specimen, nationally traceable thermometer, such as one that is traceable
ensure the syringe is at the same temperature conditions as the to National Institute of Standards and Technology (NIST) or to
sample. Avoid water contamination of the syringe reservoir by national authorities in the country in which the equipment is
suitably sealing the syringe during the cooling process. used.
5
D6378 − 22
(ARV) and uncertainty limits (at least 95 % confidence inter- 13.2 Set the vapor-liquid ratio to the desired value X:1 (for
val) of reference fluids tested in the 2003 ILS (see 16.1) and test results related to Test Method D5191, set the vapor-liquid
2020 ILS,8 which is based on the vapor pressure ratio to 4:1).
(VP4 (37.8 °C)) value measured. This information, combined 13.3 Connect an aliquot of sample either in a syringe,
with the tolerance value recommended by instrument pressurized sample container, or tubing immersed in the
manufacturers, was used to establish the acceptable testing sample to the inlet of the apparatus. Make provisions to avoid
range for the reference fuels to verify instrument performance. loss of high volatiles in the sample. The overall volume of the
NOTE 15—In the 2003 ILS (see 16.1), a study was conducted to
determine the effect that the percent capacity of material in the 250 mL
sample shall exceed the volume of three rinsing cycles plus the
reference fluid containers had on precision and bias through replicate final test volume. Follow the manufacturer’s instructions for
testing from the same bottle. The data indicated that there was no introducing the test specimen into the measuring chamber.
statistically observable effect on precision and bias for 3 of the 4 reference
fluids. For materials with DVPE values >100 kPa, such as pentane, the 13.4 Perform the three rinsing cycles (see 9.3) immediately
precision appears to worsen with diminishing liquid volume in the bottle. after connecting the sample.
It is recommended that if pentane is used, that the % capacity in the
container be ≥50 %.
13.5 Introduce the test specimen into the measuring cham-
NOTE 16—In the 2007 ILS (see 16.1) using aviation turbine fuel, 2,2 ber by a stroke of the piston. The volume of the specimen shall
dimethylbutane was tested producing results comparable to the 2003 ILS be such that after the expansion to the final volume the
(see 16.1). A mean of 68.6 kPa with a standard deviation of 0.3 kPa was programmed vapor-liquid ratio is achieved.
determined. In the 2007 ILS (see 16.1) with aviation turbine fuels,
99.95 % toluene was tested with a mean of 7.7 kPa and standard deviation 13.6 Close the inlet valve, and make the first expansion by
of 0.2 kPa. a stroke of the piston.
11.2 Values obtained within the acceptable testing range 13.7 Allow the temperature of the measuring chamber to
intervals in Table 1 and/or Table 2 indicate that the instrument increase to within 0.1 °C of the desired test temperature.
is performing at the level deemed acceptable by this standard. Monitor the TPX at least once per second for at least 1 min.
If values outside the acceptable testing range intervals are When all readings taken within 20 s agree within 0.3 kPa,
obtained, verify the quality of the pure compound(s) and record this resulting total pressure as TPX,1.
re-check the calibration of the instrument (see Section 10).
NOTE 17—A reference fluid consisting of a 44.0/56.0 (m/m) blend of
13.8 Make the second expansion, and monitor the TPX at
pentane/toluene was included in the 2003 ILS (see 16.1), but results least once per second for at least 1 min. When all readings
indicated that the data was not normally distributed. taken within 20 s agree within 0.3 kPa, record this resulting
11.3 When testing reference fluids, especially pentane, carry total pressure as TPX,2.
out one repeat test if the initial result is outside the allowed 13.9 Repeat 13.8 for the third expansion, and record the
tolerance. If the test result still remains outside the allowed resulting total pressures as TPX,3.
tolerance, refer to the manufacturer’s instructions as extra 13.10 Check for Sample Separation—After introducing the
flushing could be required. Azeotropic effects between pentane test specimen into the instrument for analysis, check the
and samples with ethanol content can cause carryover effects remaining sample for sample separation (see 8.4). This condi-
and increase the measured pentane result. tion does not apply when the sample is aviation turbine fuel.
12. Quality Control Checks
14. Calculation
12.1 After having verified that the instrument is performing
properly, use a quality control (QC) sample that is representa- 14.1 Calculate the partial pressure of the air, PPAt, at the test
tive of the fuel(s) routinely tested by the laboratory to confirm temperature t, using the following equation:
that the instrument is in statistical control following the ~ TPX,1 2 TPX,3 !~ TPX,2 2 TPX,3 !
guidelines given in Practice D6299. PPAt 5 (2)
V3 2 V1
V2 2 V1
~ TPX,1 2 TPX,2 ! 2 ~ TPX,1 2 TPX,3 !
12.2 Record the VP4 (37.8 °C) value and compare this to the
decision criteria for statistical control. If the result is found to where:
be outside the decision criteria for statistical control, initiate an
TPX, 1 = total pressure after first expansion,
investigation for root causes.
TPX,2 = total pressure after second expansion,
12.3 Store the QC sample in an environment suitable for TPX,3 = total pressure after third and final expansion,
long term storage without sample degradation. See Appendix V1 = volume after the first expansion,
X3 for guidelines and suggestions for preparing, storing, and V2 = volume after the second expansion, and
isolating QC samples for use in the test. V3 = final volume after the third expansion.
13. Procedure 14.2 Calculate the vapor pressure VPX,t at test temperature t,
using the following equation:
13.1 Set the sample introduction temperature of the measur-
ing chamber between 20 °C and 37.8 °C. VPX,t 5 TPX,3 2 PPAt (3)
where:
8
Supporting data have been filed at ASTM International Headquarters and may PPAt = partial pressure of the air at temperature t.
be obtained by requesting Research Report RR:D02-2035. Contact ASTM Customer
Service at service@astm.org. 14.3 See Appendix X1 for the derivation of the equations.
6
D6378 − 22
15. Report TABLE 3 Repeatability (Gasoline and Gasoline-oxygenate
Blends)
15.1 Report the results to the nearest 0.1 kPa (0.01 psi),
Container Size Repeatability (r)
along with the volume container size (250 mL or 1 L for
250 mL 0.52 kPa (0.08 psi)
gasoline and gasoline-oxygenate blends; for aviation turbine
fuel, 100 mL) in which the result was obtained, and specify the 1L
0.015 s X1B d
test temperature and vapor-liquid ratio.
where:
VPX ~ Tm°C ! 5 ##.# kPa or ##.## psi (4)
X = VP4 (37.8 °C) kPa (psi), and
Pair~ Tm°C ! 5 ##.# kPa or ##.## psi (5) B = 9 kPa (1.31 psi).
where:
X = vapor-liquid ratio,
Pair = partial pressure of the dissolved air, and identical test material withdrawn from 100 mL containers
Tm = measuring temperature. within short intervals of time would exceed the values in Table
15.2 If a haze was observed in 8.4, state on the report 4 with an approximate probability of 5 % (one case in 20 in the
document that the test sample was hazy. Examples of accept- long run) in the normal and correct operation of the test
able reporting statements are a result of xx.xH or the statement method.
“Sample Hazy - Yes.” 16.1.6 Reproducibility (Gasoline and Gasoline-Oxygenate
Blends)—The difference between two single and independent
16. Precision and Bias results obtained by different operators applying the same test
16.1 Precision—The precision of this test method was method in different laboratories using different apparatus on
developed in three separate ILS; for gasoline and gasoline- identical test material withdrawn from 250 mL or 1 L contain-
oxygenate blends in 2003 for 1 L containers and in 2016 for ers would exceed the following value associated with 250 mL
250 mL containers; for aviation turbine fuel in 2007 for containers or the value calculated for 1 L containers as per the
100 mL containers. equation in Table 5 with an approximate probability of 5 %
16.1.1 2016 ILS3 with 250 mL Containers—The precision (one case in 20 in the long run) in the normal and correct
data are based on 13 laboratories, instruments from 4 different operation of the test method.
manufacturers, 16 types of hydrocarbons with ethanol blends 16.1.7 Reproducibility (Aviation Turbine Fuel)—The differ-
up to 85 % (volume fraction), and other hydrocarbon- ence between two single and independent results obtained by
oxygenate blends at a test temperature of 37.8 °C and a V/L different operators applying the same test method in different
ratio of 4:1 in the nominal VP4 (37.8 °C) range of 16.0 kPa laboratories using different apparatus on identical test material
to 97.6 kPa (2.3 psi to 14.2 psi). withdrawn from 100 mL containers would exceed the values in
16.1.2 2003 ILS2 with 1 L Containers—The precision are Table 6 with an approximate probability of 5 % (one case in 20
based on 12 laboratories, 2 types of instruments, and 20 types in the long run) in the normal and correct operation of the test
of hydrocarbon and hydrocarbon-oxygenate blends at a test method.
temperature of 37.8 °C and a V/L ratio of 4:1, in the nominal 16.1.8 See Table 7 for a summary of the precision values on
VP4 range of 17.0 kPa to 106.0 kPa (2.5 psi to 15.4 psi). gasoline and gasoline-oxygenate blends values determined in
16.1.3 2007 ILS4 with 100 mL Containers—The precision kPa (psi) from Tables 3 and 5.
of this test method for aviation turbine fuels are based on 7 16.2 Bias—Since there is no accepted reference material
laboratories, 2 types of instruments, and 11 samples of aviation suitable for determining the bias for the procedure in this test
turbine fuel (Jet A, A1, C, JP4, TS-1), and toluene at test method, bias has not been determined.
temperatures of 25.0 °C, 37.8 °C, 50.0 °C, and 37.8 °C and a 16.3 Relative Bias to Test Method D5191—The degree of
V/L ratio of 4:1, in the nominal VP4 range of 0.1 kPa to expected agreement between VP4 (37.8 °C) results by this test
107.5 kPa (0.0 psi to 15.6 psi). method and DVPE results by Test Method D5191 for gasoline
16.1.4 Repeatability (Gasoline and Gasoline-Oxygenate and gasoline-oxygenate blends has been assessed in accor-
Blends)—The difference between two independent results ob- dance with Practice D6708. The degree of agreement can be
tained by the same operator in a given laboratory applying the further improved using bias correction schemes considered in
same test method with the same apparatus under constant Practice D6708. Sample specific biases were observed, but
operating conditions on identical test material withdrawn from they can be included in the calculation of between-method
250 mL or 1 L containers within short intervals of time would reproducibility as a random effect.
exceed the following value associated with 250 mL containers 16.3.1 Predicted DVPE3 with 250 mL containers:
or the value calculated for 1 L containers as per the equation in
Table 3 with an approximate probability of 5 % (one case in 20 Predicted DVPE250 mL container 5 VP4 ~ 37.8 °C ! 250 mL container
in the long run) in the normal and correct operation of the test 2 Relative Bias (6)
method. where:
16.1.5 Repeatability (Aviation Turbine Fuel)—The differ-
VP4 (37.8 °C)250 mL container = result determined by this
ence between two independent results obtained by the same
method using a 250 mL
operator in a given laboratory applying the same test method
container, and
with the same apparatus under constant operating conditions on
7
D6378 − 22
TABLE 4 Repeatability (Aviation Turbine Fuel) between two such single and independent results. For method
Temperature, °C
Repeatability
Effective Range (kPa)
X results, this will be Predicted DVPE results (Eq 6 and Eq 7)
(kPa) and for method Y results, this will be Test Method D5191
25 0.6 0.1–11.0 DVPE results.
37.8 0.06(Y + 4) 0.3–17.0
50 0.035(Y + 15) 0.5–26.0 16.4.2 Based on the 2016 ILS3 and 2003 ILS,2 an evaluation
100 1.70 5.4–107.5 of between-method reproducibility between a single predicted
where: DVPE result from this method versus a single Test Method
Y = VP4 kPa
D5191 DVPE result, for the sample types and property ranges
studied, is expected to exceed the following between-method
TABLE 5 Reproducibility (Gasoline and Gasoline-oxygenate reproducibility (RXY), as defined in Practice D6708, about 5 %
Blends) of the time:
Container Size Reproducibility (R)
250 mL 1.51 kPa (0.22 psi) TABLE 9 Between-Method Reproducibility
Container Size RXY
1L 250 mL 2.29 kPa (0.33 psi)
0.0273 s X1B d
1L œ0.57R X 10.53R Y kPa or (psi)
2 2
where:
X = VP4 (37.8 °C) kPa (psi), and (See Table 8 for nominal values.)
B = 9 kPa (1.31 psi).
where:
X = predicted DVPE = VP4_bias-corrected,
Y = DVPE,
TABLE 6 Reproducibility (Aviation Turbine Fuel) RX = Test Method D6378 reproducibility, and
RY = Test Method D5191 reproducibility.
Reproducibility
Temperature, °C Effective Range (kPa)
(R) kPa
25 1.0 0.1–11.0
37.8 0.11(Y + 4) 0.3–17.0 16.4.3 As a consequence of sample-specific biases, RXY is
50 0.065(Y + 15) 0.5–26.0
100 2.2 5.4–107.5
larger than the individual reproducibility for DVPE and VP4.
where: Users intending to use VP4 bias-corrected as a predictor of
Y = VP4 kPa DVPE are advised to assess the required degree of prediction
agreement relative to the estimated RXY to determine the
fitness-for-use of the prediction.
Relative Bias = 0.81 kPa (0.12 psi). 16.5 Relative Bias (250 mL Containers Versus 1 L
2
16.3.2 Predicted DVPE with 1 L containers: Containers)—The degree of expected agreement between VP4
(37.8 °C) results obtained by this test method using 250 mL
Predicted DVPE1 L container 5 VP4 ~ 37.8 ° C! 1 L container 2 Relative Bias
containers versus 1 L containers has been assessed in accor-
(7) dance with Practice D6708. The degree of agreement between
where: the two container sizes can be improved using a bias correction
VP4 (37.8 °C)1 L container = result determined by this method formula as shown in Eq 8 (kPa) or Eq 9 (psi). No sample
using a 1 L container, and specific biases were observed in the Practice D6708 analysis.
Relative Bias = 1.005 kPa (0.15 psi). Predicted VP 4 ~ 37.8 °C ! 1 L container ~ kPa! 5
16.4 Between-method Reproducibility (RXY)—Between Pre- VP 4 ~ 37.8 °C ! 250 mL container ~ kPa! 10.137 (8)
dicted DVPE values determined by Eq 6 and Eq 7, and Test Predicted VP 4 ~ 37.8 °C ! 1 L container ~ psi! 5
Method D5191. VP 4 ~ 37.8 °C ! 250 mL container ~ psi! 10.02 (9)
16.4.1 As defined in Practice D6708, between-method re- NOTE 18—The precision and bias statements may not be applicable to
producibility is a quantitative expression of the random error gasolines observed to be hazy in 8.4.
associated with the difference between two results obtained by
different operators using different apparatus and applying the 17. Keywords
two methods X and Y, respectively, each obtaining a single 17.1 aviation turbine fuel; dry vapor pressure; gasoline;
result on an identical test sample, when the methods have been gasoline and gasoline-oxygenate blends; hydrocarbon-
assessed and an appropriate bias-correction has been applied. It oxygenate blends; mini method; petroleum products; vapor
is defined as the 95 % confidence limit for the difference pressure; variable volume method
8
D6378 − 22
TABLE 7 Repeatability and Reproducibility Values for Nominal VP4 (37.8 °C) Values Determined by the Method
250 mL Containers 1 L Containers 250 mL Containers 1 L Containers
VP4 (37.8 °C) r R r R VP4 (37.8 °C) r R r R
(kPa) (kPa) (kPa) (kPa) (kPa) (psi) (psi) (psi) (psi) (psi)
20 0.52 1.51 0.44 0.79 2.50 0.08 0.22 0.06 0.10
25 0.52 1.51 0.51 0.93 3.00 0.08 0.22 0.06 0.12
30 0.52 1.51 0.59 1.06 3.50 0.08 0.22 0.07 0.13
35 0.52 1.51 0.66 1.20 4.00 0.08 0.22 0.08 0.14
40 0.52 1.51 0.74 1.34 4.50 0.08 0.22 0.09 0.16
45 0.52 1.51 0.81 1.47 5.00 0.08 0.22 0.09 0.17
50 0.52 1.51 0.89 1.61 5.50 0.08 0.22 0.10 0.19
55 0.52 1.51 0.96 1.75 6.00 0.08 0.22 0.11 0.20
60 0.52 1.51 1.04 1.88 6.50 0.08 0.22 0.12 0.21
65 0.52 1.51 1.11 2.02 7.00 0.08 0.22 0.12 0.23
70 0.52 1.51 1.19 2.16 7.50 0.08 0.22 0.13 0.24
75 0.52 1.51 1.26 2.29 8.00 0.08 0.22 0.14 0.25
80 0.52 1.51 1.34 2.43 8.50 0.08 0.22 0.15 0.27
85 0.52 1.51 1.41 2.57 9.00 0.08 0.22 0.15 0.28
90 0.52 1.51 1.49 2.70 9.50 0.08 0.22 0.16 0.30
95 0.52 1.51 1.56 2.84 10.00 0.08 0.22 0.17 0.31
100 0.52 1.51 1.64 2.98 10.50 0.08 0.22 0.18 0.32
105 0.52 1.51 1.71 3.11 11.00 0.08 0.22 0.18 0.34
11.50 0.08 0.22 0.19 0.35
12.00 0.08 0.22 0.20 0.36
12.50 0.08 0.22 0.21 0.38
13.00 0.08 0.22 0.21 0.39
13.50 0.08 0.22 0.22 0.40
14.00 0.08 0.22 0.23 0.42
14.50 0.08 0.22 0.24 0.43
15.00 0.08 0.22 0.24 0.45
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D6378 − 22
APPENDIXES
(Nonmandatory Information)
X1.1.2.2 The free volume VA for the air in the sample can be where:
defined as follows: TPX,1 = total pressure after first expansion,
V A 5 ~ k/100! V L (X1.4) TPX,2 = total pressure after second expansion,
TPX,3 = total pressure after third and final expansion,
where: V1 = vapor volume after the first expansion,
k = solubility of air in the sample in %, and V2 = vapor volume after the second expansion, and
VL = sample volume. V3 = final vapor volume after the third expansion.
X1.1.2.3 Applying the gas law equation for the three differ-
X1.1.2.6 The air corrected vapor pressure is calculated by:
ent volumes and using the term VA for the free air volume, the
following relationship can be defined: VPX 5 TPX,3 2 PPAX,3 (X1.9)
X2.1 The vapor pressure VPX can be determined at a t = previous test temperature during the gas determina-
temperature t1 that is different from the test temperature t tion procedure, in °C.
according to the following procedure:
X2.1.4 Calculate the air corrected vapor pressure VPX,t1 at
X2.1.1 After determination of TPX,3 at temperature t, regu-
temperature t1, using the following equation:
late the temperature of the measuring chamber to the tempera-
ture t1 ± 0.1 °C. VPX,t1 5 TPX,t1 2 PPAt1 (X2.2)
X2.1.2 Monitor the TPX at least once per second for at least where:
1 min. When all readings taken within 20 s agree within TPX,t1 = total pressure at temperature t1, and
0.3 kPa, record this resulting total pressure as TPX,t1. PPAt1 = partial pressure of the air at temperature t1.
X2.1.3 The partial pressure of the air at the temperature t1, X2.1.5 The result of calculations from equations Eq X2.1
PPAt1, can be determined using the following equation derived and Eq X2.2 shall be considered as approximate as the effects
from the gas laws as follows: of temperature on the solubility of air in the fluid under test
PPAt1 5 PPAt ~ 273.21t 1 ! / ~ 273.21t ! (X2.1) have not been included. The differences between test results
where: calculated by equations Eq X2.1 and Eq X2.2, and those from
PPAt = partial pressure of the air at test temperature t, the VPx(t) procedure (see Section 13) where the vapor pressure
t1 = current temperature of the measuring chamber, in °C, test is carried out at the required temperature, have not been
and determined.
10
D6378 − 22
X3. GUIDELINES AND SUGGESTIONS FOR PREPARING, STORING, AND ISOLATING QC SAMPLES
FOR USE IN THIS TEST
X3.1 A suggested approach for preparing samples for qual- but are required to keep retain samples of samples they initially
ity control (QC) purpose using a volatile liquid petroleum test for a specific amount of time before discarding. The
product such as gasoline, is to obtain a homogeneous bulk suggestion is to test the retain sample that is about to be
supply (for example, ≥20 L) of the material in a suitably sized discarded (that is, the retain sample has reached its required
and sealed container filled to 70 % to 80 % capacity that is retention period) and plot the differences between the results
representative of the sample types that are to be measured for from the original certification analysis and the retain results
the intended period of time (for example, select a summer (calculated by Measurementinitial – Measurementfinal) using in-
grade gasoline or winter grade gasoline depending on the vapor dividual (I-chart), moving range (MR), and optional exponen-
pressure season). Since analysis by D6378 does not require tially weighted moving average (EWMA) control charts as
pre-chilling of the sample to 0 °C to 1 °C as required in D5191, indicated in Practice D6299. Separate control charts should be
this bulk supply may be kept at ambient conditions or in a maintained for product grades that are significantly different in
refrigerated location, such as in a “cold room.” Portions of the
vapor pressures (for example, winter grade gasoline versus
bulk supply may be transferred into smaller 250 mL or 1 L
summer grade gasoline).
containers filled to 70 % to 80 % capacity and stored until
needed for analysis or transferred from the bulk supply X3.2.1 The mean of the I-chart of differences is expected to
container just prior to analysis. be zero; an out-of-control signal (individual chart or EWMA)
represents a potential signal for either a shift in the test method
X3.2 An alternative approach is to test retained samples
as practiced by the site or a change in the retain sample relative
prior to disposal as a technique to estimate site precision by
to the original. Both root causes are of high operational
comparing results obtained on the initial sample analysis with
the results obtained on retained samples containing the same significance to the site. This approach has the additional benefit
material. This approach may be advantageous for laboratories of continuously monitoring the integrity of the retain system in
that may not have access to bulk supplies of a given sample, addition to evaluating the site’s test method precision.
SUMMARY OF CHANGES
Subcommittee D02.08 has identified the location of selected changes to this standard since the last issue
(D6378 – 20) that may impact the use of this standard. (Approved July 1, 2022.)
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11