ASTM D1015-99(2004)
(Test Method)Standard Test Method for Freezing Points of High-Purity Hydrocarbons
Standard Test Method for Freezing Points of High-Purity Hydrocarbons
SCOPE
1.1 This test method describes 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 Notes 2, 3, and 4. 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.
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An American National Standard
Designation:D1015–99 (Reapproved 2004)
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 (e) 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
1.2 The values stated in SI units are to be regarded as the of the purity of the material under test. A knowledge of the
standard. The values in parentheses are for information only. purity of these hydrocarbons is often needed to help control
1.3 This standard does not purport to address all of the their manufacture and to determine their suitability for use as
safety concerns, if any, associated with its use. It is the reagent chemicals or for conversion to other chemical inter-
responsibility of the user of this standard to establish appro- mediates or finished products.
priate safety and health practices and determine the applica-
5. Apparatus
bility of regulatory limitations prior to use. For specific hazard
,
statements, see 5.1, 6.1 and 6.2. 5.1 Freezing-Point Apparatus, as shown in Figs. 1-3
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 com-
holders for the parts, and the absorption tubes.The outer walls
pounds, see Test Method D1016.
of all Dewar flasks can be covered with adhesive tape to
2. Referenced Documents
minimize danger from glass in case of breakage. (Warning—
2.1 ASTM Standards: Whenusingliquidnitrogenasarefrigerant,provideameansto
D1016 Test Method for Purity of Hydrocarbons from prevent condensation of oxygen in the space between the
Freezing Points freezing tube and the metal sheath and subsequent sealing of
D1265 Practice for Sampling Liquefied Petroleum (LP) the space by ice forming on the asbestos collar. Provide the
Gases (Manual Method) metal sheath with suitable openings in the sides and bottom.
D4057 Practice for Manual Sampling of Petroleum and Failure to do this may result in breakage of the freezing tube
Petroleum Products whentheliquefiedoxygenevaporateswithinthesealedspace.)
3. Summary of Test Method
3.1 The precise experimental measurement of the freezing
point is made from interpretation of time-temperature freezing
or melting curves.
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 on Physical and Chemical Methods.
Current edition approved May 1, 2004. Published May 2004. Originally
approved in 1949. Last previous edition approved in 1999 as D1015–99.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
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
the ASTM website. The sole source of supply of the apparatus known to the committee at this time
For details not given here, see Glasgow, A. R., Jr., Rossini, F. D., and Streiff, is Reliance Glass Works, Inc., Bensenville, IL.
A. J., “Determination of the Purity of Hydrocarbons by Measurement of Freezing If you are aware of alternative suppliers, please provide this information to
Points,” Journal of Research, JNBAA, National Institute of Standards and Tech- ASTM International Headquarters. Your comments will receive careful consider-
nology, Vol 35, No. 6, 1945, p. 355. ation at a meeting of the responsible technical committee , which you may attend.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D1015–99 (2004)
A—Bracket for motor, with rubber pad. Q—Asbestos 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—Asbestos 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,X8—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.
M8—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.
P8—Stopcock (high vacuum) to drying tube. i—Flow meter, for rates of 10 to 20 mL/min.
P9—Stopcock (high vacuum) to vacuum line.
FIG. 1 Assembly of the Freezing-Point Apparatus
D1015–99 (2004)
5.4 Null Point Indicator, may be either a galvanometer or a
microvolt ammeter.
5.4.1 Galvanometer, having a sensitivity of 0.1 mV/m at 1
m for highest precision or a sensitivity of 0.5 mV/m at 1 m for
routine precision.
,
5.4.2 Microvolt Ammeter.
5.5 Lamp and Scale, any suitable type.
5.6 Stopwatch or Clock, preferably having graduations in
minutes and hundredths of minutes.
,
5.7 High-Vacuum Oil Pump, capable of evacuating the
jacket of the freezing tube to a pressure of 0.133 Pa in 10 min
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-
1 cause of its safety.
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.
6.2.1 Use liquid nitrogen refrigerant only with adequate
C—Slanted connection to jacket of freezing tube.
ventilation. If liquid air is used as a refrigerant, it is imperative
D—Internal walls of jacket of freezing tube, silvered.
that any glass vessel containing hydrocarbon or other combus-
E—Spherical joint, 18/7.
tible compound and immersed in liquid air be protected with a
FIG. 2 Details of the Freezing Tube
suitable metal shield. The mixing of a hydrocarbon or other
combustible compound with liquid air due to the breaking of a
5.2 Resistance Bridge, Mueller type, reading from 0.0001 glass container would almost certainly result in a violent
to 50 V, in steps of 0.001 V. explosion. If liquid nitrogen is used as a refrigerant, no
5.3 Platinum Resistance Thermometer, precision grade, hydrocarbonsampleshouldeverbepermittedtocoolbelowthe
witharesistancenear25.5 Vat0°C,calibratedbytheNational condensation temperature of oxygen (−183°C at 1 atm). This
Institute of Standards andTechnology for the range from −190 would not be likely to occur in normal operation, but might
to 500°C.
occur if the apparatus were left unattended for some time.
,
6.3 Silica Gel, for use in silica gel funnel. If the gel has
been exposed to the atmosphere because of punctured or
loosely sealed containers, before use, dry the gel in a shallow
Apparatus described in 5.2, 5.3, 5.4, and 5.5 was manufactured by the Leeds
andNorthrupCo.,Philadelphia,PA,underthefollowingcatalognumbers:resistance
vessel at 150 to 205°C for 3 h, then transfer while hot to an
bridge, No. 8069 B; platinum resistance thermometer, No. 8163 B; galvanometer,
air-tight container.
highest precision, No. 2284 D; galvanometer, routine precision, No. 2430 A; lamp
andscale,No.2100.Thegalvanometer,routineprecision,No.2430-A,andthelamp
and scale, No. 2100, are still available from Leeds and Northrup. The platinum
resistance thermometer, No. 8163-B, is no longer available from Leeds and
Northrup, but is available with the same part number from Yellows Springs The sole source of supply of the apparatus known to the committee at this time
Instrument Co., Yellow Springs, OH. The resistance bridge No. 8069-B, and the is Keithley Instruments, Inc., 28775 Aurora Rd., Cleveland, OH.
galvanometer,highestprecision,No.2284-D,arenolongeravailable;however,they The sole source of supply of the apparatus known to the committee at this time
may be obtainable from instrument exchanges or used equipment suppliers. If other is Boekel Industries, Inc. Philadelphia, PA.
available instrumentation is substituted for the original, the precision statement of The sole source of supply of the apparatus known to the committee at this time
Section 13 will not apply. is Davison Chemical Co., Baltimore, MD.
D1015–99 (2004)
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.
J8—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 di-
ameter 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
D1015–99 (2004)
7.1.2 Open Containers—Refer to Practice D4057 for in-
structions on introducing samples into open-type containers
from bulk storage.
8. Calibration of Thermometric System and Conversion
of Resistance Readings to Temperature
8.1 Calibration of Resistance Bridge—The Mueller-type
resistance bridge should have its calibration checked at appro-
priate intervals by measurement of a suitable external certified
resistance, with intercomparison of the resistances of the
bridge.
8.2 CalibrationofResistanceThermometer—Theplatinum-
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-
1 1
A—Bakelite rod; 3.2 mm ( ⁄8 in.) in diameter, 317.5 mm (12 ⁄2 in.) in length.
perature Scale, for use in the range from −190 to 500°C,
B—German-silver tube, sealed to nichrome wire on one end and “sweated” on
namely, R , C, d, and b. If the thermometer has been properly
bakelite rod on other. 0
C—Nichrome wire, 1.191 mm ( ⁄64 in.) in diameter, with a helical coil on one constructed and annealed, the certified constants C, d, and b
end.
willnotchangesignificantlywithtime,butthevalueofR may
1 1
D—Stirrer, nichrome wire 1.6 to 3.2 mm ( ⁄16 to ⁄8 in.) in diameter, coiled on one
change slightly.
end.
E—Pyrex test tube.
NOTE 2—International Practical Temperature Scale (IPTS)—In 1968,
F—Metal shield; for precautions in use of liquid nitrogen and liquid air see R in
a new IPTS was adopted, replacing the previous scale in use since 1948.
legend to Fig. 1 and 5.1 and 6.2.
G—Cork stopper, with holes as shown. The1948IPTSwasbasedontheboilingpointofoxygen,thesulfurpoint,
H—Dewar flask, 1 pint size.
ice point, and steam point. The 1968 IPTS is based on the triple point of
I—Asbestos paddings.
water, tin point, zinc point, and boiling point of oxygen. The differences
J—Pyrex glass tube closed on one side.
in the two temperature scales T –T vary.Above 100°C the differences
68 48
K—Metal shield; for precautions in use of liquid nitrogen and liquid air see R in
are plus; below 100°C they may be either plus or minus.
legend to Fig. 1 and 5.1 and 6.2.
If the measured freezing point is to be used for the determination of
FIG. 4 Apparatus for Inducing Crystallization
purity according to Test Method D1016, the measured freezing point t,
f
and the freezing point of the pure material tf , should be on the same
o
temperature scale. The values of tf given in Test Method D1016 are on
o
the 1968 IPTS. Therefore, values of t determined using thermometers
f
calibrated on the 1948 scale should be converted to their 19
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