ASTM D1015-05(2015)
(Test Method)Standard Test Method for Freezing Points of High-Purity Hydrocarbons (Withdrawn 2019)
Standard Test Method for Freezing Points of High-Purity Hydrocarbons (Withdrawn 2019)
SIGNIFICANCE AND USE
4.1 The freezing point measured by this test method, when used in conjunction with the physical constants for the hydrocarbons listed in Test Method D1016, allows the determination of the purity of the material under test. A knowledge of the purity of these hydrocarbons is often needed to help control their manufacture and to determine their suitability for use as reagent chemicals or for conversion to other chemical intermediates or finished products.
SCOPE
1.1 This test method covers a procedure for the precise measurement of the freezing points of high-purity hydrocarbons.
1.2 The values stated in SI units are to be regarded as the standard. The values in parentheses are for information only.
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific hazard statements, see 5.1, 6.1 and 6.2.
Note 1: For the calculation of the molal purity of essentially pure compounds from measured freezing points and for procedures to be used for the sampling and determination of purity of certain specific compounds, see Test Method D1016.
WITHDRAWN RATIONALE
This test method covers a procedure for the precise measurement of the freezing points of high-purity hydrocarbons.
Formerly under the jurisdiction of Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants, this test method was withdrawn in December 2019 for the following reasons: (1) D1015 was developed, along with D1016, in the 1940s for the purpose of determination of purity of hydrocarbons using freezing point measurements. This method of testing hydrocarbon purity has been replaced by more precise instrument techniques such as gas chromatography in the industry. (2) The precision statements (repeatability and reproducibility) do not conform to current ASTM requirements and the precision of the method was not obtained in accordance with RR: D02-1007 or ASTM D6300. This standard, together with its companion method D1015, are being withdrawn with no replacement because it is no longer relevant as it is not used by the industry.
General Information
Relations
Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D1015 − 05 (Reapproved 2015)
Standard Test Method for
Freezing Points of High-Purity Hydrocarbons
This standard is issued under the fixed designation D1015; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope 4. Significance and Use
1.1 This test method covers a procedure for the precise 4.1 The freezing point measured by this test method, when
measurement of the freezing points of high-purity hydrocar- used in conjunction with the physical constants for the hydro-
bons. carbonslistedinTestMethodD1016,allowsthedetermination
of the purity of the material under test. A knowledge of the
1.2 The values stated in SI units are to be regarded as the
purity of these hydrocarbons is often needed to help control
standard. The values in parentheses are for information only.
their manufacture and to determine their suitability for use as
1.3 This standard does not purport to address all of the
reagent chemicals or for conversion to other chemical inter-
safety concerns, if any, associated with its use. It is the
mediates or finished products.
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
5. Apparatus
bility of regulatory limitations prior to use. For specific hazard 4,5
5.1 Freezing-Point Apparatus, as shown in Figs. 1-3
statements, see 5.1, 6.1 and 6.2.
comprising a freezing tube, a metal sheath for the freezing
NOTE 1—For the calculation of the molal purity of essentially pure tube, a Dewar flask for the cooling bath, a Dewar flask for the
compounds from measured freezing points and for procedures to be used
warming bath, a stirring mechanism, suitable clamps and
for the sampling and determination of purity of certain specific
holders for the parts, and the absorption tubes.The outer walls
compounds, see Test Method D1016.
of all Dewar flasks can be covered with adhesive tape to
minimize danger from glass in case of breakage. (Warning—
2. Referenced Documents
Whenusingliquidnitrogenasarefrigerant,provideameansto
2.1 ASTM Standards:
prevent condensation of oxygen in the space between the
D1016Test Method for Purity of Hydrocarbons from Freez-
freezing tube and the metal sheath and subsequent sealing of
ing Points
the space by ice forming on the ceramic (or glass) fiber collar.
D1265Practice for Sampling Liquefied Petroleum (LP)
Provide the metal sheath with suitable openings in the sides
Gases, Manual Method
and bottom. Failure to do this may result in breakage of the
D4057Practice for Manual Sampling of Petroleum and
freezing tube when the liquefied oxygen evaporates within the
Petroleum Products
sealed space.)
5.2 Resistance Bridge, Mueller type, reading from
3. Summary of Test Method
0.0001Ω to 50Ω, in steps of 0.001Ω.
3.1 The precise experimental measurement of the freezing
point is made from interpretation of time-temperature freezing
The sole source of supply of the apparatus known to the committee at this time
or melting curves.
is Reliance Glass Works, Inc., Bensenville, IL.
If you are aware of alternative suppliers, please provide this information to
ASTM International Headquarters. Your comments will receive careful consider-
1 1
This test method is under the jurisdiction of ASTM Committee D02 on
ation at a meeting of the responsible technical committee, which you may attend.
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of Apparatus described in 5.2, 5.3, 5.4, and 5.5 was manufactured by the Leeds
Subcommittee D02.04.0D on Physical and Chemical Methods. andNorthrupCo.,Philadelphia,PA,underthefollowingcatalognumbers:resistance
CurrenteditionapprovedJune1,2015.PublishedJuly2015.Originallyapproved bridge, No. 8069 B; platinum resistance thermometer, No. 8163 B; galvanometer,
in 1949. Last previous edition approved in 2010 as D1015–05 (2010). DOI: highest precision, No. 2284 D; galvanometer, routine precision, No. 2430 A; lamp
10.1520/D1015-05R15. andscale,No.2100.Thegalvanometer,routineprecision,No.2430-A,andthelamp
For referenced ASTM standards, visit the ASTM website, www.astm.org, or and scale, No. 2100, are still available from Leeds and Northrup. The platinum
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM resistance thermometer, No. 8163-B, is no longer available from Leeds and
Standards volume information, refer to the standard’s Document Summary page on Northrup, but is available with the same part number from Yellows Springs
the ASTM website. Instrument Co., Yellow Springs, OH. The resistance bridge No. 8069-B, and the
For details not given here, see Glasgow, A. R., Jr., Rossini, F. D., and Streiff, galvanometer,highestprecision,No.2284-D,arenolongeravailable;however,they
A. J., “Determination of the Purity of Hydrocarbons by Measurement of Freezing may be obtainable from instrument exchanges or used equipment suppliers. If other
Points,” Journal of Research, JNBAA, National Institute of Standards and available instrumentation is substituted for the original, the precision statement of
Technology, Vol 35, No. 6, 1945, p. 355. Section 13 will not apply.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D1015 − 05 (2015)
A—Bracket for motor, with rubber pad. Q—Ceramic (or glass) fiber collar.
1 1
B—Motor, with reduction gears, to give 120 r/min. R—Brass cylinder, 317.5 mm (12 ⁄2 in.) in length and 54 mm (2 ⁄8 in.) in inside diameter,
with bakelite collar; when liquid nitrogen is used, the metal shield must be provided with
suitable openings in sides and bottom (see 5.1). If liquid air is used, the metal shield should
be constructed so as to keep hydrocarbon from contact with liquid air (see 6.2).
C—Coupling. (See Fig. 3). S—Dewar flask, for cooling or warming bath; approximate inside diameter, 101 mm (4 in.);
approximate inside depth, 330 mm (13 in.).
D—Wheel. (See Fig. 3). T—Ceramic (or glass) fiber pad at bottom of cylinder R.
E—Steel rod. (See Fig. 3). U—Wood block support.
F—Bearing. (See Fig. 3). V—Table top.
G—Support for bearing. (See Fig. 3). W—Wall.
H—Support for freezing tube. X, X'—Spherical joint, 18/7.
I—Adjustable clamp holder. Y—Standard metal (copper or brass) to glass taper connections soldered.
J—Clamp for freezing tube. Z—Connection to vacuum pump.
K—Stirrer. (See Fig. 3). a—Anhydrous calcium sulfate, with indicator.
L—Thermometer. b—Anhydrous magnesium perchlorate, granular.
M—Tube for inlet of dry air, with 12/5 spherical joint. d—Separating layer of glass wool.
M'—12/5 spherical joint connection to rotameter. e—Ascarite.
N—Cork stopper, with holes as shown, plus a small hole f—Anhydrous calcium sulfate.
for the “seed” wire.
O—Freezing tube, with silvered jacket. (See Fig. 2) g—To air.
P—Stopcock on freezing tube. h—To source of compressed air.
P'—Stopcock (high vacuum) to drying tube. i—Flow meter, for rates of 10 mL ⁄ min to 20 mL ⁄ min.
P9—Stopcock (high vacuum) to vacuum line.
FIG. 1 Assembly of the Freezing-Point Apparatus
D1015 − 05 (2015)
5,8
5.7 High-Vacuum Oil Pump, capable of evacuating the
jacket of the freezing tube to a pressure of 0.133Pa in 10min
or less.
5.8 Seeding Apparatus, as shown in Fig. 4, for inducing
crystallization.
5.9 Silica Gel Funnel, as shown in Fig. 5, for filtering
compoundsthroughsilicageltoremovewater.Tobeusedonly
when specified in Test Method D1016.
6. Materials
6.1 Carbon Dioxide Refrigerant—Solid carbon dioxide in a
suitable liquid. (Warning—Extremely cold (−78.5°C). Liber-
ates heavy gas which can cause suffocation. Contact with skin
causes burns or freezing, or both. Vapors can react violently
with hot magnesium or aluminum alloys.) Acetone is recom-
mended. (Warning—Extremely flammable. Harmful if in-
haled. High concentrations can cause unconsciousness or
death. Contact can cause skin irritation and dermatitis. Use
refrigerant bath only with adequate ventilation.)
6.2 Liquid Nitrogen or Liquid Air—(Warning—Extremely
cold. Liberates gas which can cause suffocation. Contact with
skin causes burns or freezing, or both. Vapors can react
violently with hot magnesium or aluminum alloys.) For use as
a refrigerant. If obtainable, liquid nitrogen is preferable be-
cause of its safety.
6.2.1 Use liquid nitrogen refrigerant only with adequate
ventilation. If liquid air is used as a refrigerant, it is imperative
that any glass vessel containing hydrocarbon or other combus-
tible compound and immersed in liquid air be protected with a
suitable metal shield. The mixing of a hydrocarbon or other
combustible compound with liquid air due to the breaking of a
glass container would almost certainly result in a violent
A—High-vacuum stopcock, hollow plug, oblique 3 ⁄2-mm bore.
B—Inside opening of freezing tube, which must have no bulge at this point. explosion. If liquid nitrogen is used as a refrigerant, no
C—Slanted connection to jacket of freezing tube.
hydrocarbonsampleshouldeverbepermittedtocoolbelowthe
D—Internal walls of jacket of freezing tube, silvered.
condensation temperature of oxygen (−183°C at 1atm). This
E—Spherical joint, 18/7.
would not be likely to occur in normal operation, but might
FIG. 2 Details of the Freezing Tube
occur if the apparatus were left unattended for some time.
5,9
6.3 Silica Gel, for use in silica gel funnel. If the gel has
been exposed to the atmosphere because of punctured or
5.3 Platinum Resistance Thermometer , precision grade,
loosely sealed containers, before use, dry the gel in a shallow
with a resistance near 25.5Ω at 0°C, calibrated by the
vesselat150°Cto205°Cfor3h,thentransferwhilehottoan
National Institute of Standards and Technology for the range
air-tight container.
from −190°C to 500°C.
5.4 Null Point Indicator, may be either a galvanometer or a 7. Sampling
microvolt ammeter.
7.1 Sampling from Bulk Storage:
5.4.1 Galvanometer, having a sensitivity of 0.1mV⁄m at
7.1.1 Cylinder—Refer to Practice D1265 for instructions on
1m for highest precision or a sensitivity of 0.5mV⁄m at 1 m
introducing samples into a cylinder from bulk storage.
for routine precision.
5,7 7.1.2 Open Containers—Refer to Practice D4057 for in-
5.4.2 Microvolt Ammeter.
structions on introducing samples into open-type containers
5.5 Lamp and Scale, any suitable type.
from bulk storage.
5.6 Stopwatch or Clock, preferably having graduations in
minutes and hundredths of minutes.
The sole source of supply of the apparatus known to the committee at this time
is Boekel Industries, Inc. Philadelphia, PA.
7 9
The sole source of supply of the apparatus known to the committee at this time The sole source of supply of the apparatus known to the committee at this time
is Keithley Instruments, Inc., 28775 Aurora Rd., Cleveland, OH. is Davison Chemical Co., Baltimore, MD.
D1015 − 05 (2015)
A—Stainless steel rod, round.
B—German-silver tube.
C—Pins.
D—Holes, 3.2 mm ( ⁄8 in.) in diameter.
1 3
E—Brass wheel, with three holes; tapped for machine screws, spaced 12.7 mm ( ⁄2 in.), 19.05 mm ( ⁄4 in.), and 25.4 mm (1 in.) from center;
normal position is 19.05 mm ( ⁄4 in.) from center.
F—Steel rod.
G—Set screws.
H—Brass coupling.
I—Steel shaft.
J—Steel rod, round.
J'—Steel rod, square.
K—Connecting pin.
L—Brass sleeve bearing.
M—Steel pipe, 12.7 mm ( ⁄2 in.) nominal size.
N—Brass coupling.
O—Brass tee.
P—Aluminum.
1 9
Q—Double helical stirrer, made by winding 1.6 mm ( ⁄16 in.) diameter nichrome wire downwards on a cylinder 14.3 mm ( ⁄16 in.) in outside diam-
eter to form the inner helix, and then upwards over a cylinder 20.7 mm ( ⁄16 in.) in outside diameter to form the outer helix, with the two ends
silver soldered together.
R—Place where shaft of the double helical stirrer is joined to the stirrer shaft.
Metric Equivalents
mm 0.794 11.91 4.763 24 74.612 77.8 9.53 22.23 28.6 60.33 117.5 6.4 57.15 108 63.5 114.3 215.98
1 15 3 15 15 7 3 7 1 3 5 1 1 1 1 1 1
in. ⁄32 ⁄32 ⁄16 ⁄16 2 ⁄16 3 ⁄16 ⁄8 ⁄8 1 ⁄8 2 ⁄8 4 ⁄8 ⁄4 2 ⁄4 4 ⁄4 2 ⁄2 4 ⁄2 8 ⁄2
FIG. 3 Details of the Stirring Assembly and Supports
D1015 − 05 (2015)
priate intervals by measurement of a suitable external certified
resistance, with intercomparison of the resistances of the
bridge.
8.2 Calibration of Resistance Thermometer—The platinum-
resistance thermometer is provided with four calibration con-
stants certified by the National Institute of Standards and
Technology for use in converting the resistance of the ther-
mometer into temperature according to the International Tem-
perature Scale, for use in the range from −190°C to 500°C,
namely, R , C, δ, and β. If the thermometer has been properly
constructed and annealed, the certified constants C, δ, and β
willnotchangesignificantlywithtime,butthevalueofR may
change slightly.
NOTE2—InternationalPracticalTemperatureScale(IPTS)—In1968,a
new IPTS was adopted, replacing the previous scale in use since 1948.
The1948IPTSwasbasedontheboilingpointofoxygen,thesulfurpoint,
1 1
A—Bakelite rod; 3.2 mm ( ⁄8 in.) in diameter, 317.5 mm (12 ⁄2 in.) in length.
ice point, and steam point. The 1968 IPTS is based on the triple point of
B—German-silver tube, sealed to nichrome wire on one end and “sweated” on
water, tin point, zinc point, and boiling point of oxygen. The differences
bakelite rod on other.
in the two temperature scales T –T vary.Above 100°C the differences
68 48
C—Nichrome wire, 1.191 mm ( ⁄64 in.) in diameter, with a helical coil on one
are plus; below 100°C they may be either plus or minus.
end.
If the measured freezing point is to be used for the determination of
1 1
D—Stirrer, nichrome wire 1.6 mm to 3.2 mm ( ⁄16 in. to ⁄8 in.) in diameter, coiled
purity according to Test Method D1016, the measured freezing point t,
f
on one end.
and the freezing point of the pure material tf , should be on the same
E—Pyrex test tube. o
temperature scale. The values of tf given in Test Method D1016 are on
F—Metal shield; for precautions in use of liquid nitrogen and liquid air see R in
o
legend to Fig. 1 and 5.1 and 6.2. the 1968 IPTS. Therefore, values of t determined using thermometers
f
G—Cork stopper, with holes as shown.
calibrated on the 1948 scale should be converted to their 1968 IPTS
H—Dewar flask, 1 pint size.
equivalent. This conversion can be made by applying the appropriate
I—Ceramic (or glass) fiber paddings.
correction from Table 1.
J—Pyrex glass tube closed on one side.
K—Metal shield; for
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.