Astm D4052-11
Astm D4052-11
Astm D4052-11
1. Scope*
1.1 This test method covers the determination of the density,
relative density, and API Gravity of petroleum distillates and
viscous oils that can be handled in a normal fashion as liquids
at the temperature of test, utilizing either manual or automated
sample injection equipment. Its application is restricted to
liquids with total vapor pressures (see Test Method D5191)
typically below 100 kPa and viscosities (see Test Method D445
or D7042) typically below about 15 000 mm2/s at the temperature of test. The total vapor pressure limitation however can be
extended to >100 kPa provided that it is first ascertained that no
bubbles form in the U-shaped, oscillating tube, which can
affect the density determination. Some examples of products
that may be tested by this procedure include: gasoline and
gasoline-oxygenate blends, diesel, jet, basestocks, waxes, and
lubricating oils.
1.1.1 Waxes and highly viscous samples were not included
in the 1999 interlaboratory study (ILS) sample set that was
used to determine the current precision statements of the
method, since all samples evaluated at the time were analyzed
at a test temperature of 15C. Wax and highly viscous samples
require a temperature cell operated at elevated temperatures
necessary to ensure a liquid test specimen is introduced for
analysis. Consult instrument manufacturer instructions for
appropriate guidance and precautions when attempting to
analyze wax or highly viscous samples. Refer to the Precision
and Bias section of the method and Note 8 for more detailed
information about the 1999 ILS that was conducted.
1.2 In cases of dispute, the referee method is the one where
samples are introduced manually as in 6.3 or 6.4, as appropriate for sample type.
1.3 This test method should not be applied to samples so
dark in color that the absence of air bubbles in the sample cell
cannot be established with certainty. For the determination of
density in crude oil samples use Test Method D5002.
1
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.04.0D on Physical and Chemical Methods.
Current edition approved Oct. 15, 2011. Published December 2011. Originally
approved in 1981. Last previous edition approved in 2009 as D405209. DOI:
10.1520/D4052-11.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Standards volume information, refer to the standards Document Summary page on
the ASTM website.
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3. Terminology
3.1 Definitions:
3.1.1 density, nmass per unit volume at a specified
temperature.
3.1.2 relative density, nthe ratio of the density of a
material at a stated temperature to the density of water at a
stated temperature.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 adjustment, vthe operation of bringing the instrument to a state of performance suitable for its use, by setting or
adjusting the density meter constants.
3.2.1.1 DiscussionOn some digital density analyzer instruments, an adjustment may be made rather than calibrating
the instrument. The adjustment procedure uses air and redistilled, freshly boiled water (WarningHandling water at
boiling or near boiling temperature can present a safety hazard.
Wear appropriate personal protective equipment.) as standards
to establish the linearity of measurements over a range of
operating temperatures.
3.2.2 calibration, vset of operations that establishes the
relationship between the reference density of standards and the
corresponding density reading of the instrument.
4. Summary of Test Method
4.1 A small volume (approximately 1 to 2 mL) of liquid
sample is introduced into an oscillating sample tube and the
change in oscillating frequency caused by the change in the
mass of the tube is used in conjunction with calibration data to
determine the density, relative density, or API Gravity of the
sample. Both manual and automated injection techniques are
described.
5. Significance and Use
5.1 Density is a fundamental physical property that can be
used in conjunction with other properties to characterize both
the light and heavy fractions of petroleum and petroleum
products.
5.2 Determination of the density or relative density of
petroleum and its products is necessary for the conversion of
measured volumes to volumes at the standard temperature of
15C.
6. Apparatus
6.1 Digital Density AnalyzerA digital analyzer consisting
of a U-shaped, oscillating sample tube and a system for
electronic excitation, frequency counting, and display. The
analyzer shall accommodate the accurate measurement of the
sample temperature during measurement or shall control the
sample temperature as described in 6.2. The instrument shall be
capable of meeting the precision requirements described in this
test method.
6.2 Circulating Constant-Temperature Bath, (optional), capable of maintaining the temperature of the circulating liquid
constant to 60.05C in the desired range. Temperature control
can be maintained as part of the density analyzer instrument
package.
6.3 Syringes, for use primarily in manual injections, at least
2 mL in volume with a tip or an adapter tip that will fit the
opening of the oscillating tube.
3
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
MD.
4
Suitable solvent naphthas are marketed under various designations such as
Petroleum Ether, Ligroine, or Precipitation Naphtha.
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D4052 11
7.6 Dry Air, for drying the oscillator tube.
8. Sampling, Test Specimens, and Test Units
8.1 Sampling is defined as all the steps required to obtain an
aliquot of the contents of any pipe, tank, or other system, and
to place the sample into the laboratory test container. The
laboratory test container and sample volume shall be of
sufficient capacity to mix the sample and obtain a homogeneous sample for analysis.
8.2 Laboratory SampleUse only representative samples
obtained as specified in Practices D4057 or D4177 for this test
method.
8.3 Test SpecimenA portion or volume of sample obtained
from the laboratory sample and delivered to the density
analyzer sample tube. The test specimen is obtained as follows:
8.3.1 Mix the sample if required to homogenize taking care
to avoid the introduction of air bubbles. The mixing may be
accomplished as described in Practice D4177 or Test Method
D4377. Mixing at room temperature in an open container can
result in the loss of volatile material from certain sample types
(for example, gasoline samples), so mixing in closed, pressurized containers or at least 10C below ambient temperature is
required for such sample types where loss of volatile material
is a potential concern. For some sample types, such as viscous
lube oils that are prone to having entrained air or gas bubbles
present in the sample, the use of an ultrasonic bath (see 6.7)
without the heater turned on (if so equipped), has been found
effective in dissipating bubbles typically within 10 min.
NOTE 2When mixing samples with volatile components, consider the
sample properties in relation to both ambient temperature and pressure.
9. Preparation of Apparatus
9.1 Set up the density analyzer (including the constant
temperature bath and related attachments, if necessary) following the manufacturers instructions. Adjust the bath or internal
temperature control so that the desired test temperature is
established and maintained in the sample compartment of the
analyzer. Calibrate the instrument at the same temperature at
which the density or relative density of the sample is to be
measured or perform an adjustment (see 3.2.1Discussion) in
preparation of analyzing samples. (WarningPrecise setting
(1)
where:
T = temperature, K, and
P = barometric pressure, torr.
10.2.5 Determine the density of water at the temperature of
test by reference to Table 1.
10.2.6 Using the observed T-values and the reference values
for water and air, calculate the values of the Constants A and B
using the following equations:
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D4052 11
TABLE 1 Density of WaterA
Temperature,
C
Density,
g/mL
Temperature,
C
Density,
g/mL
Temperature,
C
Density,
g/mL
0.0
3.0
4.0
5.0
10.0
15.0
15.56
16.0
17.0
18.0
19.0
20.0
0.999840
0.999964
0.999972
0.999964
0.999699
0.999099
0.999012
0.998943
0.998774
0.998595
0.998404
0.998203
21.0
22.0
23.0
24.0
25.0
26.0
27.0
28.0
29.0
30.0
35.0
37.78
0.997991
0.997769
0.997537
0.997295
0.997043
0.996782
0.996511
0.996231
0.995943
0.995645
0.994029
0.993042
40.0
45.0
50.0
55.0
60.0
65.0
70.0
75.0
80.0
85.0
90.0
100
0.992212
0.990208
0.988030
0.985688
0.983191
0.980546
0.977759
0.974837
0.971785
0.968606
0.965305
0.958345
A
Densities conforming to the International Temperature Scale 1990 (ITS 90)
were extracted from Appendix G, Standard Methods for Analysis of Petroleum and
Related Products 1991, Institute of Petroleum, London.
A5
[Tw2
Ta2#/[dw
da #
B 5 Ta2 ~A 3 da!
(2)
(3)
(4)
(5)
where:
Tw = observed period of oscillation for cell containing
water,
Ta = observed period of oscillation for cell containing air,
dw = density of water at test temperature, and
da = density of air at test temperature.
11. Quality Control Checks
11.1 Confirm the instrument is in statistical control at least
once a week when it is in use, by analyzing a quality control
(QC) sample that is representative of samples typically analyzed. Analysis of a single QC sample can be sufficient.
Analysis of QC sample results can be carried out using control
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D4052 11
chart techniques.5 If the QC sample result determined causes
the lab to be in an out-of-control situation, such as exceeding
the labs control limits, instrument recalibration or adjustment
is required. An ample supply of QC sample material should be
available for the intended period of use, and must be homogeneous and stable under the anticipated storage conditions. Prior
to monitoring the measurement process, the user of the method
needs to determine the average and control limits of the QC
sample. The QC sample precision should be checked against
the method precision to ensure data quality.
11.2 Although not mandatory, it is recommended that periodic analyses of certified density standards (i.e., traceable to
national standards) that are separate from those that may be
used in calibrating the instrument, be used to confirm testing
accuracy.
12. Procedure
12.1 Manual Injection:
12.1.1 Introduce a small amount (about 1 to 2 mL) of
sample into the clean, dry sample tube of the instrument using
a suitable syringe or alternative, as described in 6.4.
12.1.2 The sample can also be introduced by siphoning.
Plug the external TFE-fluorocarbon capillary tube into the
entry port of the sample tube. Immerse the other end of the
capillary in the sample and apply suction to the other port using
a syringe or vacuum line until the sample tube is properly filled
(see Note 1).
12.1.3 Ensure that the sample tube is properly filled and that
no gas bubbles are present. The sample must be homogeneous
and free of even the smallest gas bubbles. Check the integrity
of the filled sample by using optical or physical methods to
verify absence of gas bubbles. If gas bubbles are detected,
empty and refill the sample tube, and recheck for gas bubbles.
NOTE 6If the sample is too dark in color to determine the absence of
bubbles with certainty, the density cannot be measured within the stated
precision limits of Section 15.
5
ASTM MNL 7, Manual on Presentation of Data Control Chart Analysis,
Section 3: Control Charts for Individuals, 6th ed., ASTM International, W.
Conshohocken, PA.
6
Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D02-1734.
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TABLE 2 Density (g/mL) and Relative Density (Repeatability)
Range
Sample Types
0.710.78
0.800.88
(6)
(7)
where:
Tw = observed period of oscillation for cell containing
water,
Ts = observed period of oscillation for cell containing
sample,
dw = density of water at test temperature,
K1 = instrument constant for density,
K2 = instrument constant for relative density, and
T = temperature of test, C.
13.3 If it is necessary to convert a result obtained using the
density meter to API Gravity, or a density or relative density at
another temperature, Guide D1250 can be used only if the glass
expansion factor has been excluded.
NOTE 7Some digital density analyzers are equipped to automatically
calculate and report sample results in API gravity units (see Test Method
D287 or D1298), based on the density or relative density results, or a
combination thereof, determined by this test method and using the
appropriate conversion equation derived from Guide D1250 (which
Testing Condition
Repeatability
Single Determination
(Manual injection)
Average of 2 Determinations
(Manual or automated injections)
Single Determination
(Manual or automated injection)
Average of 2 Determinations
(Manual or automated injections)
0.00045
0.00031
0.00016
0.00011
excludes the glass expansion factor), for the specific sample type being
analyzed.
14. Report
14.1 In reporting density, state the test temperature and the
units (for example: density at 20C = 0.8765 g/mL or 876.5 kg/
m3).
14.2 In reporting relative density, state both the test temperature and the reference temperature, but no units (for
example: relative density, 20/20C = 0.xxxx).
14.3 Report the final result for density or relative density to
four significant figures.
14.4 If reporting sample results in API gravity units (see
Note 7), report the final results to the nearest 0.1 API.
14.5 In some cases, it may be necessary to report if results
were based on a single determination or an average of two
determinations, as well as if results were determined by manual
injection or automated injection to meet specific requirements,
such as data recipients wanting to know such information in
order to understand how to interpret results relative to the
published method precision values. In such cases, it is permissible to report this information along with the test results.
15. Precision and Bias 6
15.1 The precision of the method as obtained by statistical
examination of interlaboratory test results at a test temperature
of 15C is as follows for the following sample types and
ranges:
15.1.1 RepeatabilityThe difference between successive
test results obtained by the same operator with the same
apparatus under constant operating conditions on identical test
material, would in the long run, in the normal and correct
operation of the test method, exceed the following value only
in one case in twenty:
15.1.1.1 Density (g/mL) and Relative DensitySee Table 2.
15.1.1.2 API GravitySee Table 3.
15.1.2 ReproducibilityThe difference between two single
and independent results, obtained by different operators working in different laboratories on identical test material, would in
the long run, in the normal and correct operation of the test
method, exceed the following values only in one case in
twenty:
15.1.2.1 Density (g/mL) and Relative DensitySee Table 4.
15.1.2.2 API GravitySee Table 5.
NOTE 8The ASTM Interlaboratory Study (ILS) conducted in Fall
19996 involved 11 labs and 23 samples. The samples included 5 motor
gasolines, 1 motor gasoline + ethanol, 4 reformulated gasolines (RFG), 2
lube oils, 1 basestock oil, 4 Jet-A fuels, 1 JP8 fuel, and 5 diesel fuels. The
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TABLE 3 API Gravity (Repeatability)
Range
5166
2945
Sample Types
Gasoline and RFG
Testing Condition
Repeatability
Single Determination
(Manual injection)
Average of 2 Determinations
(Manual or automated injections)
Single Determination
(Manual or automated injection)
Average of 2 Determinations
(Manual or automated injections)
0.090
0.063
0.032
0.022
0.800.88
Sample Types
Gasoline and RFG
Testing Condition
Reproducibility
Single Determination
(Manual injection)
Average of 2 Determinations
(Manual or automated injections)
Single Determination
(Manual or automated injection)
Average of 2 Determinations
(Manual or automated injections)
0.001900.0344 (D0.75)
0.001950.0315 (D0.75)
0.00052
0.00050
2945
Sample Types
Gasoline and RFG
Testing Condition
Reproducibility
Single Determination
(Manual injection)
Average of 2 Determinations
(Manual or automated injections)
Single Determination
(Manual or automated injection)
Average of 2 Determinations
(Manual or automated injections)
15.2 BiasAfter suggestions of its existence from literature,7 a study has been performed which has confirmed the
presence of a bias between known density values for reference
materials and from values determined according to this test
method on the same reference materials. The matrix for this
bias study comprised 15 participants, each analyzing four
reference oils with certified density values, established by the
Netherlands Meet Instituut (NMI), by pyknometry, covering
densities in the range of 747 to 927 kg/m3 at 20C, with
viscosities between 1 and 5000 mPa.s (also at 20C). This
study is documented in ASTM Research Report RR:D021387.8 Method users should, therefore, be aware that results
obtained by this test method can be biased by as much as 0.6
kg/m3 (0.0006 g/mL).
NOTE 10Newer instrumentation exists which purports to correct
density results due to the influence of viscosity. However, the responsible
ASTM Technical Committee has not yet performed a new interlaboratory
study to confirm the elimination of the bias described in ASTM Research
Report RR:D02-1387.8
7
Fitzgerald, H. and D., An Assessment of Laboratory Density Meters,
Petroleum Review, November 1992, pp. 544549.
8
Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D02-1387.
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16. Keywords
16.1 API Gravity; density; digital density analyzer; petroleum distillates; petroleum products; relative density
SUMMARY OF CHANGES
Subcommittee D02.04 has identified the location of selected changes to this standard since the last issue
(D405209) that may impact the use of this standard.
(1) Revised 8.3.1, 8.3.2, 12.1.3, and 12.1.4.
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