This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

Designation: D1015 − 05 (Reapproved 2015)

Standard Test Method for

Freezing Points of High-Purity Hydrocarbons1
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. A number 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. carbons listed in Test Method D1016, allows the determination
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
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 5.1 Freezing-Point Apparatus,4,5 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
2. Referenced Documents minimize danger from glass in case of breakage. (Warning—
When using liquid nitrogen as a refrigerant, provide a means to
2.1 ASTM Standards:2 prevent condensation of oxygen in the space between the
D1016 Test 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.
D1265 Practice 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
D4057 Practice for Manual Sampling of Petroleum and freezing tube when the liquefied oxygen evaporates within the
Petroleum Products sealed space.)
3. Summary of Test Method 5.2 Resistance Bridge,6 Mueller type, reading from
0.0001 Ω to 50 Ω, in steps of 0.001 Ω.
3.1 The precise experimental measurement of the freezing
point is made from interpretation of time-temperature freezing
or melting curves.3
4
The sole source of supply of the apparatus known to the committee at this time
is Reliance Glass Works, Inc., Bensenville, IL.
5
If you are aware of alternative suppliers, please provide this information to
ASTM International Headquarters. Your comments will receive careful consider-
1
This test method is under the jurisdiction of ASTM Committee D02 on ation at a meeting of the responsible technical committee,1 which you may attend.
6
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. and Northrup Co., Philadelphia, PA, under the following catalog numbers: resistance
Current edition approved June 1, 2015. Published July 2015. Originally approved 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. and scale, No. 2100. The galvanometer, routine precision, No. 2430-A, and the lamp
2
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 [email protected]. 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
3
For details not given here, see Glasgow, A. R., Jr., Rossini, F. D., and Streiff, galvanometer, highest precision, No. 2284-D, are no longer available; 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.

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 D1015 − 05 (2015)

A—Bracket for motor, with rubber pad. Q—Ceramic (or glass) fiber collar.
B—Motor, with reduction gears, to give 120 r/min. R—Brass cylinder, 317.5 mm (121⁄2 in.) in length and 54 mm (21⁄8 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

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 D1015 − 05 (2015)
5.7 High-Vacuum Oil Pump,5,8 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
compounds through silica gel to remove water. To be used only
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
A—High-vacuum stopcock, hollow plug, oblique 31⁄2-mm bore. glass container would almost certainly result in a violent
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. hydrocarbon sample should ever be permitted to cool below the
D—Internal walls of jacket of freezing tube, silvered.
E—Spherical joint, 18/7. condensation temperature of oxygen (−183 °C at 1 atm). This
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.
6.3 Silica Gel, for use in silica gel funnel.5,9 If the gel has
been exposed to the atmosphere because of punctured or
5.3 Platinum Resistance Thermometer ,6 precision grade, loosely sealed containers, before use, dry the gel in a shallow
with a resistance near 25.5 Ω at 0 °C, calibrated by the vessel at 150 °C to 205 °C for 3 h, then transfer while hot to an
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,6 having a sensitivity of 0.1 mV ⁄m at
7.1.1 Cylinder—Refer to Practice D1265 for instructions on
1 m for highest precision or a sensitivity of 0.5 mV ⁄m at 1 m
introducing samples into a cylinder from bulk storage.
for routine precision.
5.4.2 Microvolt Ammeter.5,7 7.1.2 Open Containers—Refer to Practice D4057 for in-
structions on introducing samples into open-type containers
5.5 Lamp and Scale,6 any suitable type. from bulk storage.
5.6 Stopwatch or Clock, preferably having graduations in
minutes and hundredths of minutes.
8
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.

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 D1015 − 05 (2015)

A—Stainless steel rod, round.

B—German-silver tube.
C—Pins.
D—Holes, 3.2 mm (1⁄8 in.) in diameter.
E—Brass wheel, with three holes; tapped for machine screws, spaced 12.7 mm (1⁄2 in.), 19.05 mm (3⁄4 in.), and 25.4 mm (1 in.) from center;
normal position is 19.05 mm (3⁄4 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 (1⁄2 in.) nominal size.
N—Brass coupling.
O—Brass tee.
P—Aluminum.
Q—Double helical stirrer, made by winding 1.6 mm (1⁄16 in.) diameter nichrome wire downwards on a cylinder 14.3 mm (9⁄16 in.) in outside diam-
eter to form the inner helix, and then upwards over a cylinder 20.7 mm (13⁄16 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
in. 1⁄32 15⁄32 3⁄16 15⁄16 215⁄16 37⁄16 3⁄ 8 7⁄ 8 1 1 ⁄8 2 3⁄ 8 4 5⁄ 8 1⁄ 4 2 1⁄ 4 4 1 ⁄4 2 1 ⁄2 4 1⁄2 8 1⁄ 2

FIG. 3 Details of the Stirring Assembly and Supports

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 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, R0, C, δ, and β. If the thermometer has been properly
constructed and annealed, the certified constants C, δ, and β
will not change significantly with time, but the value of R0 may
change slightly.
NOTE 2—International Practical Temperature Scale (IPTS)—In 1968, a
new IPTS was adopted, replacing the previous scale in use since 1948.
The 1948 IPTS was based on the boiling point of oxygen, the sulfur point,
A—Bakelite rod; 3.2 mm (1⁄8 in.) in diameter, 317.5 mm (121⁄2 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 T68–T48 vary. Above 100 °C the differences
C—Nichrome wire, 1.191 mm (3⁄64 in.) in diameter, with a helical coil on one
are plus; below 100 °C they may be either plus or minus.
end.
D—Stirrer, nichrome wire 1.6 mm to 3.2 mm (1⁄16 in. to 1⁄8 in.) in diameter, coiled
If the measured freezing point is to be used for the determination of
on one end. purity according to Test Method D1016, the measured freezing point tf,
E—Pyrex test tube. and the freezing point of the pure material tfo, should be on the same
F—Metal shield; for precautions in use of liquid nitrogen and liquid air see R in temperature scale. The values of tfo given in Test Method D1016 are on
legend to Fig. 1 and 5.1 and 6.2. the 1968 IPTS. Therefore, values of tf determined using thermometers
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 precautions in use of liquid nitrogen and liquid air see R in 8.3 Checking of the Ice Point—Frequent measurements (at
legend to Fig. 1 and 5.1 and 6.2. least once every month) should be made of the resistance of the
FIG. 4 Apparatus for Inducing Crystallization given platinum thermometer at the ice point, 0 °C, as measured
on the given resistance bridge.10 This value should differ only
slightly from the certified value of R0. If the difference
becomes appreciable (approaching 0.001 Ω), the calibration of
the bridge should be checked. If the bridge has not changed, the
change has occurred in the thermometer, and a recalibration of
it is recommended.
8.4 Conversion of Resistance Readings to Temperature—
When determinations are made on a number of substances
having freezing points at different temperatures, time will be
saved by making up a table giving values of the resistance, R,
for each unit degree of temperature in the given range. Values
of resistance for unit degrees, for the ranges from −190 °C to
+50 °C and +50 °C to 290 °C, with differences between suc-
cessive unit degrees tabulated for linear interpolation (which is
permissible), may be easily placed on a single 300 mm by
400 mm (14 in. by 16 in.) sheet for each range. Calculate
values for the resistance, R, from unit values of temperature, t,
by means of one of the following equations:
For temperatures below 0°C:
R 5 R 0 $ 11Ct@ ~ 110.01 δ ! 2 1024 δt 2 1023 β ~ t 2 100! t 2 # % (1)
A—Filter funnel, with extension as shown, pyrex glass.
B—Adsorbent, silica gel, 28 to 200 mesh.
C—Glass wool.
For temperatures above 0°C:
R 5 R 0 $ 11Ct@ ~ 110.01 δ ! 2 1024 δt # % (2)
FIG. 5 Silica Gel Funnel

8. Calibration of Thermometric System and Conversion 10

The ice point may be measured according to the procedure described by J.
of Resistance Readings to Temperature Busse, “Temperature, Its Measurement and Control in Science and Industry,”
Section VIII, Reinhold Publishing Corp., 1941, p. 241. See also “Notes to
8.1 Calibration of Resistance Bridge—The Mueller-type Supplement Resistance Thermometer Certificates.” National Institute of Standards
resistance bridge should have its calibration checked at appro- and Technology, 1949.

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 D1015 − 05 (2015)
TABLE 1 Approximate Differences (T68-T48) in Kelvins, Between the Values of Temperature Given by the IPTS of 1968 and the IPTS of
1948
T68 C 0 −10 −20 −30 −40 −50 −60 −70 −80 −90 −100
−100 0.022 0.013 0.003 −0.006 −0.013 −0.013 −0.005 0.007 0.012 ... ...
−0 0.000 0.006 0.012 0.018 0.024 0.029 0.032 0.034 0.033 0.029 0.022
T68 C 0 10 20 30 40 50 60 70 80 90 100
0 0.000 −0.004 −0.007 −0.009 −0.010 −0.010 −0.010 −0.008 −0.006 −0.003 0.000
100 0.000 0.004 0.007 0.012 0.016 0.020 0.025 0.029 0.034 0.038 0.043
200 0.043 0.047 0.051 0.054 0.058 0.061 0.064 0.067 0.069 0.071 0.073
300 0.073 0.074 0.075 0.076 0.077 0.077 0.077 0.077 0.077 0.076 0.076
400 0.076 0.075 0.075 0.075 0.074 0.074 0.074 0.075 0.076 0.077 0.079
500 0.079 0.082 0.085 0.089 0.094 0.100 0.108 0.116 0.126 0.137 0.150
600 0.150 0.165 0.182 0.200 0.23 0.25 0.28 0.31 0.34 0.36 0.39
700 0.39 0.42 0.45 0.47 0.50 0.53 0.56 0.58 0.61 0.64 0.67
800 0.67 0.70 0.72 0.75 0.78 0.81 0.84 0.87 0.89 0.92 0.95
900 0.95 0.98 1.01 1.04 1.07 1.10 1.12 1.15 1.18 1.21 1.24
1000 1.24 1.27 1.30 1.33 1.36 1.39 1.42 1.44 ... ... ...

where: tapered male outlet of the reservoir trap (E in Fig. 1 of Test

t = given temperature, °C, on the International Tempera- Method D1016) if the material is normally gaseous. When
ture Scale (see Note 2), specified in Test Method D1016, filter the sample directly into
R = resistance of the thermometer in ohms at the tempera- a freezing tube (O in Fig. 1) through silica gel to remove water.
ture t, A detailed drawing of a funnel used for this purpose is shown
R0 = resistance of the thermometer in ohms at 0 °C, and in Fig. 5. Each time a freezing or melting curve is determined
C, δ, and β = constants certified for the given platinum after the sample is melted, it is necessary to remove the sample
thermometer by the National Institute of Standards and Tech- from the freezing tube and refilter it through silica gel into a
nology. dry freezing tube to remove water. When the sample is volatile
or normally gaseous at room temperature, cool the freezing
9. General Procedure for Determining a Freezing Curve tube before introduction of the sample in order to minimize
9.1 Assemble the apparatus, with no refrigerant and no loss by evaporation. Continue the flow of air (freed of carbon
sample yet in place, but with a stream of air, freed of carbon dioxide and water) into the freezing tube in order to keep out
dioxide and water, flowing at a rate of 10 mL ⁄ min to water vapor. Start the stirrer and allow the sample to cool down
20 mL ⁄min. Fill the jacket of the freezing tube with air freed of to within about 15°C of the freezing point, then begin evacu-
carbon dioxide and water. ation of the jacket of the freezing tube.
9.2 As required, the operator must be prepared to induce 9.4 Observe the time and the resistance of the thermometer
crystallization in the sample as soon as possible after the at even intervals of 0.02 Ω to 0.05 Ω (about 0.2 °C to 0.5 °C)
temperature has passed below the freezing point of the sample to determine the rate of cooling, which is continually changing
(to prevent excessive undercooling). In some cases, crystalli- as the pressure in the jacket of the freezing tube is reduced.
zation may be induced by introducing into the sample at the Care must be taken to close the stopcock to the freezing tube
appropriate time a small rod (ABC in Fig. 4) which has been when the desired cooling rate is obtained. In case the cooling
kept at an appropriate lower temperature (near 0 °C, − 80 °C, rate is allowed to become too slow, the pressure and likewise
or − 180 °C) (J in Fig. 4). In other cases, crystallization can be the cooling rate can be increased by bleeding in air (freed of
induced by introducing into the sample at the appropriate time carbon dioxide and water) through stopcocks P' and P (Fig. 1).
crystals of the sample on the coiled end of the small rod (ABC When a cooling rate is obtained that will give a change of 1 °C
in Fig. 4). When inducing crystallization, the cold rod (with or in about 1 min to 3 min in the range of about 5 °C to 10 °C
without crystals) should be immersed in the sample in the above the freezing point, close the stopcock controlling the
freezing tube for about 2 s (if necessary, this is repeated every jacket of the freezing tube. (The optimum rate of cooling will
2 min or 3 min). These crystals are made by placing several vary with the material being examined.)
millilitres of the sample in a small test tube, incased in a thin 9.5 When the temperature reaches a point about 5 °C above
metal tube, as shown at E in Fig. 4, immersed in a refrigerant the expected freezing point, record the time to 1 s (or 0.01 min)
whose temperature is below the freezing point of the sample. A at which the resistance of the thermometer equals 0.1 Ω or
slurry or mush of liquid and crystals is produced. The rod (ABC 0.05 Ω. At the appropriate time (see 9.2) induce crystallization.
in Fig. 4), with wet crystals adhering to the helical coil C, is The beginning of crystallization will be accompanied by a halt
raised above the liquid level in the tube E and held in position in the cooling of the liquid. After recovery from undercooling
with a cork stopper until required for seeding. is substantially complete, record the resistances at intervals of
9.3 Fill the Dewar flask surrounding the freezing tube with about 1 min. If a galvanometer is being used, also record the
the appropriate refrigerant. Temporarily remove the thermom- galvanometer scale at full sensitivity and with no current
eter and stopper and then introduce the sample (usually 50 mL through the galvanometer. These observations, together with
of liquid in amount) through a pipet if the material is normally the sensitivity of the galvanometer system in terms of ohms per
liquid, or by pouring the refrigerated liquid sample through the millimetre of scale reading, yield a sensitivity of nearly

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 D1015 − 05 (2015)
0.0001 °C. Approximately equal sensitivity is obtained when equilibrium portion of the melting curve as along the equilib-
using a microvolt ammeter. Continue observations until the rium portion of the freezing curve. When melting is substan-
stirrer begins to labor, then stop the stirrer. After several tially complete, as evidenced by a marked change in the rate of
minutes (when a steady rate is obtained) make alternate N and change of resistance, make observations of time at even
R readings through the commutator at fixed intervals of about intervals of 0.05 Ω (0.5 °C). The experiment is concluded
1 min. Determine the difference between the two at any given when the temperature has gone about 5 °C to 10 °C above the
time from a plot of the values against time. freezing point.

10. General Procedure for Determining a Melting Curve 11. Evaluation of the Freezing Point from a Freezing
Curve
10.1 For determining a melting curve, proceed exactly as
described in Section 9 for a freezing curve, up to the point 11.1 To locate zero time (the time at which crystallization
where the stirrer begins laboring. When the stirrer shows signs would have begun in the absence of undercooling), make a
of laboring, make a comparison of N and R readings through preliminary plot of the time-resistance observations covering
the commutator, as in 9.5 except that the stirrer is still the liquid cooling line and the equilibrium portion of the
operating. When the laboring of the stirrer becomes quite freezing curve. For this plot, as shown in Fig. 6, the time scale
pronounced, the freezing curve (with the stirrer still operating) is taken so that 10 mm is equivalent to 1 min and the resistance
is changed to a melting curve. The energy for melting is scale (for a 25 Ω thermometer) is taken so that 10 mm is
supplied in either of the two following ways: (1) the cooling equivalent to 0.02 Ω (0.2 °C). Zero time is determined by a
bath is replaced by a warming bath and simultaneously the visual extrapolation, on this plot, of the equilibrium portion of
jacket is evacuated for an appropriate length of time (3 min to the freezing curve back to its intersection with the liquid
10 min). The stopcock on the freezing tube is closed; or (2) the cooling line.
cooling bath is left in position or replaced by a warming bath 11.2 In order to locate accurately the resistance correspond-
and the jacket evacuated as much as possible, leaving the ing to the freezing point, plot the time-resistance observations
stopcock to the freezing tube open to the vacuum system as shown in with the time scale as before but with the scale of
during the entire melting curve. In this case, the thermal temperature magnified 10 to 200 times. The equilibrium
conductivity across the jacket is so small that the energy portion of the curve, GHI, is extended back to its intersection
introduced by the stirrer provides the energy for melting. at F with the liquid line by the simple geometrical construction
Continue the observations of time and resistance along the shown in Fig. 8, selecting for this purpose three points (near the

NOTE 1—The scale of ordinates gives the resistance in ohms of the platinum resistance thermometer, and the scale of abscissas gives the time in
minutes. GHI represents the equilibrium portion of the freezing curve. Zero time is given by the intersection of the liquid cooling line with GHI extended.
The same data are plotted in Fig. 7 with a magnified scale of temperature.
FIG. 6 Time-Temperature Cooling Curve for Determining “Zero” Time in an Experiment on a Sample of Benzene

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 D1015 − 05 (2015)
ends and the middle) of the equilibrium portion of the curve
(Note 3). The point F gives the resistance corresponding to the
freezing point.11
NOTE 3—The location of the resistance corresponding to the freezing
point can be made using algebraic expressions derived from the geometri-
cal construction. These are as follows:
Rf 5 R g 1 @ ~ R g 2 R i ! / ~ uvw 2 1 ! # (3)
where:
u 5 @ ~ R h 2 R i! / ~ R g 2 R h! # , (4)
v 5 @ ~ Z h 2 Z g! / ~ Z i 2 Z h! # , (5)
and
w 5 @ ~ Z i 2 Z f! / ~ Z g 2 Z f! # . (6)
Z f, Zg, Zh and Zi are the times corresponding to the points F, G, H, and
I, respectively, and Rf, Rg, Rh and R i are the resistances in ohms corre-
sponding to the points F, G, H, and I, respectively.
It is nearly always possible to select the point H equidistant in time
NOTE 1—The scale of ordinates gives the resistance in ohms of the between G and I, so the v = 1.
platinum resistance thermometer, and the scale of abscissas gives the time
11.3 The observed resistance at the point F, corrected by
in minutes. GHI represents the equilibrium portion of the freezing curve.
The freezing point F is determined as described in the text and Fig. 8. one half the difference between the N and R readings, and by
These data are the same as those plotted in Fig. 6. a bridge zero correction, appropriate calibration corrections to
FIG. 7 Time-Temperature Cooling Curve for Determining the the coils of the bridge, and by an ice point correction, if
Freezing Point of a Sample of Benzene necessary, is converted to temperature in degrees Celsius. (See
Fig. 7.)
12. Evaluation of the Freezing Point from a Melting
Curve
12.1 Determine zero time from a preliminary plot (as for the
freezing curve (Section 11)) of the time-resistance observations
covering the equilibrium portion of the melting curve and the
liquid warming line, as shown in Fig. 9. Zero time can usually
be determined by visual extrapolation, on this plot, of the
equilibrium portion of the melting curve to its intersection with
the liquid warming line extended down in temperature to its
intersection with the extension of the equilibrium portion of the
curve.
12.2 The location of the freezing point at F is done exactly
as in the case of the freezing curve, except that the geometrical
extrapolation is made to the right as shown in Fig. 10. (See Fig.
8 and the reference in Footnote 10 for details.)
12.3 Make the conversion of resistance to temperature as
described in Section 11.
13. Precision and Bias
NOTE 4—The precision of this test method was not obtained in
accordance with RR:D02-1007.
NOTE 1—Example: Given G, H, and I as any three points on the 13.1 Results should not differ from the mean by more than
equilibrium portion of the freezing curve, preferably spaced approxi- the following amounts:
mately as shown. Construction to determine Rf: Draw AC parallel to the
Repeatability One Reproducibility
temperature axis at “zero” time (the time at which crystallization would Operator and Different Operators
have begun in the absence of undercooling). Draw AB through I parallel Apparatus and Apparatus
to the time axis. Draw a line through G and H intersecting AB at E and AC Freezing point, °C ±0.005 ±0.015
at D. Draw a line through H and I intersecting AC at J. Draw a line through
J parallel to DE, intersecting B at K. Draw a line through K and G, NOTE 5—The precision data were obtained using a galvanometer.
intersecting AC at F. F is the described point, representing the freezing
point of the given sample (see Busse10). 11
For details regarding the identification of the equilibrium portion of the curve,
FIG. 8 Geometrical Construction for Determining the Freezing
and the geometrical construction for determining the freezing point, see Rossini, F.
Point D., and Taylor, W. J., “Theoretical Analysis of Time-Temperature Freezing and
Melting Curves as Applied to Hydrocarbons,” Journal of Research, JNBAA,
National Institute of Standards and Technology, Vol 32, No. 5, 1944, p. 197.

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NOTE 1—The scale of ordinates gives the resistance in ohms of the platinum resistance thermometer, and the scale of abscissas gives the time in
minutes. HG represents a part of the equilibrium portion of the warming curve. Zero time is given by the intersection of HG extended to its intersection
with the backward extension of the liquid warming line. The same data are plotted in Fig. 10 with a magnified scale of temperature.
FIG. 9 Time-Temperature Warming Curve for Determining “Zero” Time in an Experiment on a Sample of Ethylbenzene

Equivalent results would be expected when using a microvolt ammeter. be defined only in terms of this test method, which is a function
Deviations will be greater than those shown for very impure samples, for of the purity of the reference materials.
compounds in which the liquid-solid equilibrium is established sluggishly,
and for compounds having small values of the cryoscopic constant A.
14. Keywords
13.2 Bias:
13.2.1 The procedure in this test method for measuring 14.1 crystallization; freeze point; LPG; pure hydrocarbons;
freezing point has no bias because the freezing point value can purity

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NOTE 1—The scale of ordinates gives the resistance in ohms of the platinum resistance thermometer, and the scale of abscissas gives the time in
minutes. IHG represents the equilibrium portion of the warming curve. The freezing point F is determined as described in the text and Fig. 8. These data
are the same as those plotted in Fig. 9.
FIG. 10 Time-Temperature Warming Curve for Determining the Freezing Point of a Sample of Ethylbenzene

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