Determination of Vapor Pressure of Crude Oil: VPCR (Expansion Method)
Determination of Vapor Pressure of Crude Oil: VPCR (Expansion Method)
Determination of Vapor Pressure of Crude Oil: VPCR (Expansion Method)
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of volatile components.
Subcommittee D02.08 on Volatility.
Current edition approved April 1, 2016. Published April 2016. Originally
3.2.3 Reid vapor pressure equivalent (RVPE), n—a value
approved in 1999. Last previous edition approved in 2015 as D6377 – 15. DOI: calculated by a defined correlation equation (see Eq X1.1) from
10.1520/D6377-16. VPCR4 at 37.8 °C that is expected to be equivalent to the vapor
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or pressure value obtained by Test Method D323.
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 3.2.3.1 Discussion—As noted in 14.3 and Appendix X1,
the ASTM website. subsection X1.2, since Eq X1.1 for estimating RVPE is not
11). Unless otherwise indicated, it is intended that all reagents with Practice D3700. Sampling in accordance with Practice
conform to the specifications of the Committee on Analytical D4057 shall only be used for dead crude oil and if Practice
Reagents of the American Chemical Society where such D3700 is impractical.
specifications are available.3 Other grades may be used, pro-
NOTE 5—Sampling in accordance with Practice D4177 may also be
vided it is first ascertained that the reagent is of sufficient purity used instead of Practice D4057.
to permit its use without lessening the accuracy of the
determination. 8.1.2 For sampling in accordance with Practice D3700, a
7.1.1 The chemicals in 7.2.1, 7.2.2, and 7.2.3 are suggested floating piston cylinder with a minimum sample volume of
for verification of instrument performance (see Section 11), 200 mL shall be used if the overall volume of the test specimen
based on the air saturated reference fuels analyzed in the Test required for the vapor pressure determination, including the
Method D5191 2003 interlaboratory study (ILS)4 (see Table 1). rinsing procedure is not larger than 20 mL. Larger floating
Ptot used in Test Method D5191 is equivalent to VPCR4 used in piston cylinders can be used. The minimum piston back-
this test method). Such reference fuels are not to be used for pressure shall be higher than the sample vapor pressure at the
instrument calibration. Table 1 identifies the accepted reference introduction temperature of the measuring chamber plus
value (ARV) and uncertainty limits, as well as the acceptable 100 kPa for the shifting of the piston. The maximum back-
testing range for each of the reference fuels listed. pressure shall not exceed the maximum measurement pressure
7.1.2 The chemicals in 7.3.1 and 7.3.2 are suggested for use of the apparatus pressure transducer. Compressed air, or any
as rinsing solvents capable of cleaning the measuring chamber, other, non-flammable compressed gas, can be used as the
the valves and the inlet and outlet tubes. back-pressuring agent. The floating piston cylinder shall have
provisions for mechanical stirring of the sample and a second
7.2 Verification Fluids: valve at the inlet for rinsing.
7.2.1 2,2-Dimethylbutane, (Warning—2,2-dimethylbutane 8.1.3 Do not unnecessarily expose the samples to tempera-
is flammable and a health hazard.) tures exceeding 30 °C during sampling and storage. For
7.2.2 2,3-Dimethylbutane, (Warning—2,3-dimethylbutane prolonged storage, store the samples in an appropriate room or
is flammable and a health hazard.) refrigerator.
7.2.3 Pentane, (Warning—Pentane is flammable and a 8.1.4 Perform the vapor pressure determination on the first
health hazard.) test specimen withdrawn from the cylinder after the rinsing
7.3 Solvents: step in 9.3. Do not use the remaining sample in the floating
7.3.1 Toluene, (Warning—Toluene is flammable and a piston cylinder for more than three repeat vapor pressure
health hazard.) determinations.
7.3.2 Acetone, (Warning—Acetone is flammable and a 8.1.5 In the case of quality control checks with pure
health hazard.) compounds (see 11.1), smaller sample containers without
applied pressure can be used.
8. Sampling and Sample Introduction 8.2 Sampling Procedures:
8.1 General Requirements: 8.2.1 If the sample is contained in a pressurized source like
8.1.1 The extreme sensitivity of vapor pressure measure- a pipeline, use a floating piston cylinder and obtain the sample
ments to losses through evaporation and the resulting changes directly from the source under pressure. Rinse the cylinder by
in composition requires the utmost precaution and the most opening the rinsing valve until the crude oil emerges at the
meticulous care in the drawing and handling of samples. second inlet. Close the rinsing valve and let the piston move
Sampling of live crude oil shall be performed in accordance slowly until at least 200 mL of sample has entered the cylinder.
Close the inlet valve and apply the back pressure immediately.
Check the filling of the cylinder to be at least 200 mL.
3
Reagent Chemicals, American Chemical Society Specifications , American
NOTE 6—The current precision statements were derived from the 2005
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
ILS using samples in 250 mL floating piston cylinders (see 14.3).
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia 8.2.2 If the sample is taken from a non-pressurized source
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
like a storage tank, oil tanker, drum or other container, obtain
MD.
4
Supporting data have been filed at ASTM International Headquarters and may a sample and test specimen in accordance with Practice D4057.
be obtained by requesting Research Report RR:D02-1619. Use either a 250 mL or 1 L sized container filled between 70 %
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container, transfer the sample into the measuring chamber 10.2 Temperature Sensor—Verify the calibration of the
using a transfer tube or a syringe. platinum resistance thermometer used to monitor the measur-
ing chamber temperature at least every six months against a
9. Preparation of Apparatus
thermometer which is traceable to National Institute of Stan-
9.1 Prepare the instrument for operation in accordance with dards and Technology (NIST) or to national authorities in the
the manufacturer’s instructions. country the equipment is used.
9.2 Rinse the measuring chamber, if necessary with a
solvent. Toluene has a low vapor pressure and can be used 11. Quality Control Checks
successfully. Rinsing is performed by drawing the solvent into 11.1 Use a verification fluid (see 7.2) of known volatility as
the chamber by the piston and expelling the solvent into the an independent check against the instrument calibration each
waste container. day the instrument is in use. For pure compounds, multiple test
9.3 To avoid contamination of the test specimen with the specimens may be taken from the same container over time.
previous sample or the solvent, rinse the measuring chamber a Air saturate the verification fluid at temperatures between 0 °C
minimum of three times with the sample to be tested. Fill the to 1 °C as described in Test Method D5191 (see 8.4). Transfer
measuring chamber with sample to at least half the total the verification fluid into the measuring chamber using a
volume of the chamber for each rinse. This rinsing procedure transfer tube or a syringe. The temperature of the verification
shall always be carried out immediately before the measuring fluid shall be at 0 °C to 3 °C during the sample introduction,
procedure (see Section 12). and the measuring procedure shall be in accordance with
Section 12 with a V/L ratio of 4:1 and a measuring temperature
10. Calibration of 37.8 °C.
10.1 Pressure Transducer: 11.2 Table 1 provides the accepted reference value (ARV)
10.1.1 Perform a calibration check of the transducer as [Ptot] and uncertainty limits (at least 95 % confidence interval)
indicated from the quality control checks (see Section 11). The of reference fluids tested in the 2003 D5191 ILS.4 As stated in
calibration of the transducer is checked using two reference 7.1.1, the “Ptot” reference used in Test Method D5191 (and
points, zero pressure (<0.1 kPa) and the ambient barometric Table 1 of this test method) is equivalent to VPCR4 (37.8 °C)
pressure. in this test method. This information, combined with the
NOTE 8—Calibration frequency of the pressure transducer may vary tolerance value recommended by instrument manufacturers,
with instrument type and frequency of use. A calibration check of the was used to establish the acceptable testing range for the
pressure transducer at least once every six months is recommended. reference fuels to verify instrument performance.
10.1.2 Connect a McLeod gage or a calibrated electronic 11.3 Values obtained within the acceptable testing range
vacuum measuring device to the vacuum source in line with the intervals in Table 1 indicate that the instrument is performing
measuring chamber (see Note 7). Apply vacuum to the mea- at the level deemed acceptable by this standard. If values
suring chamber (see Note 9). When the vacuum measuring outside the acceptable testing range intervals are obtained,
device registers a pressure less than 0.1 kPa, adjust the verify the quality of the pure compound(s) and re-check the
transducer control to zero or to the actual reading on the calibration of the instrument (see Section 10). (Warning—The
vacuum measuring device as dictated by the instrument design use of single component verification materials such as those
or manufacturer’s instructions. listed in Table 1 will only prove the calibration of the
NOTE 9—Refer to Annex A6.3 of Test Method D2892 for further details equipment. It will not check the accuracy of the entire test
ture. test results obtained by the same operator with the same
12.1.2 For samples contained in a non-pressurized apparatus under constant operating conditions on identical test
container, set the sample introduction temperature of the material would, in the long run, in the normal and correct
measuring chamber to 20 °C. operation of the test method, exceed the values calculated as
12.1.3 For samples with a pour point higher than 15 °C, set per the following equations only in one case in twenty:
the sample introduction temperature of the measuring chamber 14.1.1.1 For samples in pressurized Floating Piston Cylin-
at least 5 °C above the pour point temperature of the sample ders:
but no higher than the measuring temperature. V/L 5 4 and Tm 5 37.8°C:repeatability 5 2.48 kPa ~ 37.8°C ! (2)
12.1.4 For measurements with V/L ratios < 1, the sample
may not be exposed to the atmosphere and shall be contained V/L 5 0.02 and Tm 5 37.8°C:repeatability 5 5.61 kPa ~ 37.8°C ! (3)
in a floating piston cylinder. The sample introduction tempera- 14.1.1.2 For samples in nonpressurized sample containers:
ture of the measuring chamber shall be equal to the measuring
V/L 5 4 and Tm 5 37.8°C:repeatability 5 2.29 kPa ~ 37.8°C ! (4)
temperature to avoid any influence due to sample expansion.
12.2 Set the V/L to the desired value X:1 (for test results 14.1.2 Reproducibility—The difference between two single
related to Test Method D323, set the V/L to 4:1). and independent results obtained by different operators work-
ing in different laboratories on identical material would, in the
12.3 If the sample is contained in a pressurized floating long run, in the normal and correct operation of the test
piston cylinder, mix it vigorously with the mechanical stirrer, method, exceed the following values in only one case in
otherwise shake the container with the non-pressurized sample, twenty:
to ensure a homogenous sample. 14.1.2.1 For samples in pressurized Floating Piston Cylin-
12.4 Follow the manufacturer’s instructions for introducing ders:
the test specimen into the measuring chamber. The volume of V/L 5 4 and Tm 5 37.8°C:reproducibility 5 4.26 kPa ~ 37.8°C ! (5)
the specimen shall be such that after the expansion to the final
V/L 5 0.02 and Tm 5 37.8°C:reproducibility 5 20.3 kPa ~ 37.8°C !
volume the programmed V/L is achieved.
(6)
12.5 After closing the inlet valve, expand the volume of the
measuring chamber to the final volume. 14.1.2.2 For samples in nonpressurized sample containers:
12.6 Switch-on the shaker, and leave it on during the entire V/L 5 4 and Tm 5 37.8°C:reproducibility 5 5.26 kPa ~ 37.8°C ! (7)
measuring procedure. 14.2 Bias—Since there is no accepted reference material
12.7 Adjust the temperature control to the measuring tem- suitable for determining the bias for the procedures in this test
perature (for results related to Test Method D323, adjust to a method, a bias cannot be determined.
temperature of 37.8 °C). The measuring temperature shall not 14.3 Relative Bias to Test Method D323—A statistically
be lower than at least 10 °C above the pour point temperature significant relative bias was observed for crude oil in a limited
of the sample. interlaboratory test program the 2005 ILS6 between
5
MNL 7, Manual on Presentation of Data Control Chart Analysis, “Section 3:
Control Charts for Individuals,” 6th edition, ASTM International, W. Conshohocken, 6
Supporting data have been filed at ASTM International Headquarters and may
PA. be obtained by requesting Research Report RR:D02-1643.
APPENDIXES
(Nonmandatory Information)
X1.1 The degree of expected agreement between in Eq X1.1 is not universally valid for all crude oils and it is
VPCR4 (37.8 °C) results by this test method for samples in recommended to report the VPCR4 (37.8 °C) result for all
either pressurized floating piston cylinders and nonpressurized crude oils. If Eq X1.1 is used to estimate RVPE, confirm its
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1 L containers, and RVP results by Test Method D323 using validity for the crude oil samples under test by analyzing
nonpressurized 1 L containers has been assessed in accordance samples by both Test Methods D323 and D6377. In any case,
with Practice D6708. Sample specific biases were observed. Eq X1.1 only applies to dead crude oil samples (see 3.2.1 and
The reproducibility of Test Method D323 for the 2005 ILS 3.2.1.1) with VPCR4 (37.8 °C) results between 34 kPa and
crude oil sample set was R=9 kPa.6 Due to the low number of 117 kPa (see 14.4), since live crude oil samples (see 3.2.2 and
the crude oil samples in the ILS, a direct comparison between 3.2.2.1) if tested by Test Method D323 in non-pressurized
the results of this test method and Test Method D323 is containers (for example, sample bottles or cans) will result in
suggestive. significant loss of vapors during the air saturation procedure in
Test Method D323 prior to analysis.
X1.2 As stated in 14.3, a statistically significant relative bias
was observed for crude oil in a limited 2005 interlaboratory test RVPE 5 A 3 VPCR4 ~ 37.8°C ! (X1.1)
program involving VPCR4 (37.8 °C) results obtained by this
where:
test method and results obtained using Test Method D323. For
the six crude oil samples evaluated in the limited interlabora- A = 0.834 (for samples in pressurized floating piston
tory test program, RVP results determined by Test Method cylinders), and
A = 0.915 (for samples in nonpressurized 1-L sample
D323, based on VPCR4 (37.8 °C) results obtained by this test
containers)
method, can be predicted by Eq X1.1. However, the correlation
X2.1 For several purposes, for example, transport and X2.1.2 Increase the measuring temperature in steps to the
storage, it may be useful to measure the vapor pressure highest temperature of interest but not higher than 100 °C.
behavior of crude oil versus temperature. To obtain such Each step is measured according with 12.7 and 12.8.
information proceed as follows. X2.1.3 The result is either recorded as a series of values, or
X2.1.1 Follow the instructions outlined in 12.1 – 12.8. The plotted as log (VPCRX) versus 1/T, where T is the absolute
initial measuring temperature is programmed to the lowest measuring temperature in °K (°C + 273.2).
temperature of interest but not lower than the temperature NOTE X2.1—No precision data have been developed for temperatures
stated in 12.7. different from 37.8 °C.
Subcommittee D02.08 has identified the location of selected changes to this standard since the last issue
(D6377 – 15) that may impact the use of this standard. (Approved April 1, 2016.)
(1) Revised 1.2, 8.3.1, 8.3.3, 11.1, 3.2.3.1, and 14.4. (2) Updated 12.1.
Subcommittee D02.08 has identified the location of selected changes to this standard since the last issue
(D6377 – 14) that may impact the use of this standard. (Approved Oct. 1, 2015.)
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